Thermal Degradation of Polymer Blends, Composites and Nanocomposites
Thermal Degradation of Polymer Blends, Composites and Nanocomposites
Thermal Degradation of Polymer Blends, Composites and Nanocomposites
P.M. Visakh
Yoshihiko Arao Editors
Thermal
Degradation of
Polymer Blends,
Composites and
Nanocomposites
Engineering Materials
More information about this series at http://www.springer.com/series/4288
P.M. Visakh Yoshihiko Arao
•
Editors
Thermal Degradation
of Polymer Blends,
Composites
and Nanocomposites
123
Editors
P.M. Visakh Yoshihiko Arao
Department of Ecology and Basic Safety Doshisha University
Tomsk Polytechnic University Kyoto
Tomsk Japan
Russia
v
vi Preface
overcome these undesired aspects. The introduction section also presents the most
common polymers used as crosslinked scaffolds either individual or for different
multicomponent polymeric materials. The subchapters that follow are focused on
recent studies on the thermal stability and degradation of thermosetting blends,
effect of reinforcement and nanofillers on the thermal stability of thermosetting
blends, and applications and future trends of thermosetting blends, dealing with the
latest issues and trying to reveal solutions.
The third chapter on thermal degradation of thermosetting nanocomposites
discusses the rapidly-developing nanotechnology and nanoscience in recent years
on thermosetting nanocomposites thermal degradation. The authors explain the
effect of different nanoparticles, their dispersion, and use of modifiers on the
polymer thermal stability. This chapter focuses on the thermal degradation study
of thermosetting nanocomposites materials, evaluating their effect in thermal sta-
bility and in thermal degradation steps. The thermal applications of these nano-
composites are also evaluated and the challenges to the nanocomposites field in the
following years are discussed. The next chapter manly concentrates on the effect of
thermo-oxidation on the mechanical performance of polymer-based composites for
high temperature applications. This chapter explains the effect of thermo-oxidation
on the mechanical properties of polymer-based composites for high temperature
applications. The polymer-based composites with high thermal stability and future
trend towards modification of this type of composites have been discussed in this
chapter.
The fifth chapter explains the analysis of thermal degradation of a polymer by
factor analysis. In this chapter is introduced an application of multivariate curve
resolution (MCR) technique based on factor analysis. The authors explain not only
series of IR spectra but also two-dimensional data series of nuclear magnetic res-
onance (NMR), mass spectrometry (MS), and X-ray diffraction (XRD) that can deal
in the same manner further two-dimensional data generated by hyphenated tech-
niques such as gas chromatography/mass spectrometry (GC/MS) and liquid chro-
matography/ultraviolet (LC/UV) analysis, which combine two functions based on
different principles, namely chromatography, which has a separating function, and
spectrometry, which provides information related to molecular structure. Another
chapter on radiation effects on polymer-based systems explains the improvements
in thermal properties of polymeric materials/composites with effect of crosslinking
and grafting on the thermal properties of polymer materials and composites. The
authors also explain with accelerated degradation by radiation exposure.
The seventh chapter explains thermal degradation of synthetic rubber nano-
composites. The authors explain synthetic rubbers nanocomposites that have cap-
tured and held the attention of scientists as the materials of the future; these
materials improve resistance to thermal degradation and stability of nanocompos-
ites. They explain in this chapter these new materials that exhibit enhanced prop-
erties at very low filler level, usually ≤5 wt %. The properties of rubber
nanocomposites strongly depend on the dispersion state of fillers and method of
preparation. The effect of different nanoparticles on rubber properties is studied
with thermal stability. This is mainly studied using TGA, TGA-MS TGA-FTIR
Preface vii
and other techniques. Finally, the authors explain that rubber synthetic nanocom-
posites play an important role in engineering, automotive, aerospace, construction,
packaging, and medical device applications due to the possibility to design new
materials with unprecedented and improvements in their physical properties, par-
ticularly from the perspective of applications.
The eighth chapter discusses the outdoor exposure degradation of Ethylene-Vinyl-
Acetate (EVA) encapsulant material for photovoltaic application. The authors explain
the outdoor exposure of the materials leading to changes in polymer morphology. The
main objective of this experimental investigation was to better understand the changes
due to thermal transitions and the molecular organizations of the crosslinked ethylene-
vinyl-acetate encapsulant material after aging in outdoor exposure. The authors dis-
cuss from the results, the significant decrease in most properties of EVA in natural
field exposure due principally to the specificity of the exposure site. For aged EVA
samples, the distinctive feature of these results is that there are two different endo-
thermic processes due to the recrystallization phenomenon. Furthermore, the differ-
ence in the magnitude of peak current by TSC technique suggests increased
crosslinking exposure occurring selectively in the high temperature phase as a result of
outdoor exposure. The final chapter on thermal degradation of bio-nanocomposites
explains the type of biomaterials and their nanocomposite thermal properties. This
chapter reviews the recent developments in bio-nanocomposites where the related
biodegradable polymers include Polylactic acid (PLA), polycaprolactone (PCL),
polyhydroxyvalerate (PHV), polyhydroxyalkanoates (PHAs), polyhydroxybutyrate
(PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), and poly(d,l-lac-
tide) (PDLLA). A concise history outlining the development of bio-nanocomposites
materials is explored, while the importance of environmental conditions and in par-
ticular the rate of biodegradability is highlighted. Furthermore, the authors discussed
in this chapter the steps of thermal degradation and the systematic approaches used to
overcome these concerns. It discusses the behavior of various nanoparticles on the
thermal stability of biopolymers and other topics related to research challenges, future
trends, and applications.
Finally, the editors would like to express their sincere gratitude to all the con-
tributors of this book, who gave excellent support for the successful completion of
this venture. We are grateful to them for the commitment and the sincerity they
have shown toward their contribution in the book. Without their enthusiasm and
support, the compilation of a book would not have not possible. We would like to
thank all the reviewers who have taken their valuable time to give critical comments
on each chapter. We also thank the publisher Springer for recognizing the demand
for such a book, and for realizing the increasing importance of the area of “Thermal
Degradation of Polymer Blends, Composites and Nanocomposites” and for starting
such a new project, in which not many other publishers put their hands on.
P.M. Visakh
Contents
ix
x Contents
xi
Thermal Degradation of Polymer Blends,
Composites and Nanocomposites
Outstanding properties of the epoxy resins, their great resistance to chemical agents
and corrosion are noteworthy. Other properties include excellent electrical and
mechanical behavior, flexibility and moderate toughness, great abrasion resistance,
excellent adhesion to various building materials, low shrinkage during and after
curing [1, 2]. Epoxy resins are also used in special application domains, such as
encapsulating materials for miniature components and laminates in the aircraft
industry. Carbon fiber reinforced epoxy resin composites are applied for structural
modifications in aeroplanes, whilst their aramid fiber based composites are building
materials for boats. Due to their properties, phenol-formaldehyde mouldings are
used for producing telephones, handles, knobs, electrical iron parts, welding tongs
and lamp housings, bottle caps and closures. Special applications include com-
pression presses for injection moldings of thermoplastics and fuse-box covers and
distributor heads in the automobile industry.
Urea-formaldehyde resins are applied in the field of electronics. They possess
superior electrical insulation properties compared to phenolic resins and are used
in the production of mainly sockets, plugs and switches. A special application of
urea-formaldehyde resins consists in the obtaining of foams for placing on airport
Stability can be said as the protection of polymeric materials from which lead to
deterioration of properties [9]. In literature, there are different and sometimes con-
tradictory reported papers concerning the effect of the nanoparticles on polymer
thermal stability. There are papers suggesting that nanoparticles have no obviously
effect on thermal stability, some of them suggested a small to substantial enhance-
ment and some others suggested acceleration of thermal decomposition. In a study
performed by Ollier et al. [10], the author incorporated 5 % weight of bentonite in
unsaturated polyester (UP) matrix. They noted that the addition of bentonite
Thermal Degradation of Polymer Blends, Composites and Nanocomposites 3
increases the thermal stability of the UP resin. Carrasco and Pagès [11] showed that,
at low clay contents (up to 5 wt%) the addition of clay had no effect on the thermal
stability of the epoxy matrix, whereas for higher concentration (10 wt%) a clear
increase on this parameter was observed. In addition, Lakshimi et al. [12] reported an
improvement in the thermal stability of epoxy resins with the incorporation of MMT
with the same chemical treatments used in this work. Saitoh et al. [13] found that the
phosphonium cations used to obtain the organoclays influenced the thermal resis-
tance of the resulting epoxy/clay nanocomposites. The explanation for this behavior
is that the dispersed MMT-Clay nanolayers can act as barrier protecting the epoxy
polymer matrix degradation gaseous products from volatilizing.
In some reported studies it has been shown that the introduction of clays into
polymeric matrices can accelerate the thermal decomposition of the polymer matrix,
consisted by condensation polymers, due to the catalysis effect of water in MMT
and hydroxyl groups on the clay platelets. The thermal stabilization effect on carbon
nanotubes could be attributed to the increased interfacial interaction between the
nanofibres and polymers which lead to an increase of the degradation’s activation
energy. Carrasco and Pagès [11] found that the thermal decomposition of cured
materials was independent of cure temperature but from the content of clay. With
the incorporation of crude clay, the initial temperature degradation and the maxi-
mum temperature degradation shifted towards higher temperature. The addition of
unmodified MWCNTs has a negative effect on thermal stability of the epoxy
nanocomposites. This is due to the poor affinity between as-received MWCNTs and
epoxy resin matrix, which increases vacancies or voids in the nanocomposite.
Organomodification of MMT have a negative effect in thermal degradation while
the exfoliated structure due to the finer dispersion of the clay nanoparticles can lead
to thermal stabilization than intercalated structure. Except montmorillonite, other
clays like layered double hydroxide (LDH) can enhance thermal degradation of
polymers. In such nanocomposites there are no reported for accelerating effect of
LDH on polymer thermal degradation. This is because LDH can be more easily
dispersed in intercalated or exfoliated structures, compared with MMT, into a
polymer matrix and thus the stabilization effect is higher [14]. Carbon nanotubes
(MWCNTs and SWCNTs) were also in all cases reported that can increase thermal
stability of polymers. This was because the CNTs have excellent thermal con-
ductivity. The improving thermal stability of the nanocomposites was also attrib-
uted to the formation and stabilization of MWCNTs-bonded macroradicals [15].
addition of which to polymers would not reduce their physical, chemical and
mechanical properties. Nanostructured materials are considered to be the promising
additives to enhance mechanical properties as well as flame retardancy of polymeric
materials [19–21]. The distinguishing characteristics of conventional fillers and
nanoparticles are explained by low loading rate (*0.1–2 vol%), particle-particle
correlation arising at low-volume fractions, large number density of particles per
particle volume (106–108 particles/m3), extensive interfacial area between the
polymer and the nanoparticles, short distances between particles.
The research [22] revealed high activity of nanoscale powders obtained by
electrical explosion of wires (EEW) to reduce polyolefin flammability. Aluminum
hydroxide Al(OH)3, bayerite β-Al2O3·3H2O, boehmiteγ-AlOOH, low-temperature
modification of aluminum oxide γ-Al2O3 produced by the method of electrical
explosion of wires (EEW) [23, 24] were used as fillers in polypropylene. All
additives are resistant to oxidation under heating up to 400 °C, all of them release
water in endothermic decomposition, except γ-Al2O3. The results of the study
indicated that the oxidation rate decreases when polypropylene was filled with
gibbsite and bayerite at concentration of 0.5–10 wt%.
The possibility of using aluminum nitride (AlN) nanopowders as flame retardant
additive was studied [25]. Concentration of the nanopowder AlN incorporated in a
polyethylene matrix was 0.1; 0.25; 0.75; 1.5 and 3 wt%. The incorporation of
1.5 wt% AlN in a polyethylene matrix caused the significant increase in the tem-
perature of the beginning of oxidation of 33 °C (to 183 °C) in comparison with pure
polyethylene (150 °C) and in the onset temperature of the intensive weight loss of
15 °C (to 375 °C) against 360 °C for pure polyethylene. The resulting effect is
explained by the influence of nanoparticles on the microstructural characteristics of
polyethylene. Nanoparticles are the crystallization centers and participate in the
formation of fine-grained structure.
The thermal energy storage phase change materials (PCM) based on paraffin/
high density polyethylene (HDPE) composites were prepared by using twin-screw
extruder technique. The morphology and properties of the PCM composites based
on the flame retardant system with expanded graphite (EG) and ammonium poly-
phosphate (APP) were characterized by Scanning electron microscope (SEM),
Differential scanning calorimeter (DSC), Thermogravimetric analyses (TGA) and
Cone calorimeter tests [33]. The thermal degradation mechanism of these nano-
composites is related to the kind of used nanoparticles and its amount, the structure
of the char formed during polymer degradation, the gas impermeability of inorganic
nanoparticles, which inhibit the formation and escape of volatile byproducts during
degradation and the interactions between polymer reactive groups and inorganic
nanoparticles [34]. The enhanced thermal stability was confirmed by thermal
analysis of the composite films, which showed an increase in the glass transition
temperature of the polymer [35]. Synthesis of reduced silanized graphene oxide/
epoxy-polyurethane (EPUAs/R-Si-GEO) composites with enhanced thermal and
mechanical properties was reported by Lin et al. [36].
Continuous fiber-reinforced polymers are now widely used in many industries
and provide properties that are superior to those of traditional ACSR (aluminum
conductor steel reinforced) cables [37]. Effects of thermal treatment on the
mechanical properties of poly(p-phenylenebenzobisoxazole) fiber reinforced phe-
nolic resin composite materials was studied by Bian et al. [38]. Researchers are
trying to improve the physical properties of the CNT/epoxy composites. Although
carbon nanotubes (CNTs) have superior properties the interfacial bonding between
the CNTs and the polymer matrix is weak. Kim et al. [39] treated CNTs by an
acidic solution to remove impurities and subsequently by amine treatment or
plasma oxidation for the improvement of interfacial bonding and dispersion of
nanotubes in the epoxy matrix. The mechanical properties of the modified CNT/
epoxy composites and rheological properties of nanotube containing epoxy resin
were improved. This may be ascribed to the modification of CNTs, which improved
dispersion and interaction between the CNT and the epoxy resin. The properties of
carbon nanotubes such as high strength, high stiffness, high aspect ratio and low
density have made them an excellent reinforcement for composite materials.
Functionally graded carbon nanotube reinforced composite (FG-CNTRC) materials
are being focused now to find out its prospect for future use [40]. Cellulose
nanocrystals (CNCs) are reinforcing fillers of considerable interest for polymers due
to their high modulus and potential for sustainable production. Xu et al. [41]
prepared CNC-based composites with a waterborne epoxy resin matrix and char-
acterized. The glass transition temperature (Tg) and modulus for the composites
increased with increasing CNC content. The tensile strength increased from 40 to
60 MPa, suggesting good adhesion between epoxy and CNC surfaces exposed to
the matrix.
6 P.M. Visakh and O.B. Nazarenko
In conventional analysis, one instance of analysis produces one data item, such as
single-value data (scalars) obtained by titration or weighing, or qualitative data
(category variables) obtained from a color reaction. The horizontal axis of a
spectrum generally represents a specific range of frequencies or wavelengths. It is a
collection of numeric absorbance data corresponding to that axis. The data can be
saved in a spreadsheet as one row or column of spectrum absorbance data. Two-
dimensional data can also be generated by hyphenated techniques such as gas
chromatography/mass spectrometry (GC/MS) and liquid chromatography/ultravi-
olet (LC/UV) analysis, which combine two functions based on different principles,
namely, chromatography, which has a separating function, and spectrometry, which
provides information related to molecular structure. Researchers in the field of
analysis generally refer to this as three-dimensional data, but more accurately, it is a
three-dimensional representation of two-dimensional data. Because three-dimen-
sional data result in a block data structure (suggestive of the Rubik’s cube), it is
difficult to represent these data in a single diagram, and thus, data compilation
techniques such as slicing the data parallel to each facet are necessary. The first
study on curve resolution, carried out by Kaiser [42] in 1958, proposed the varimax
method, wherein factor rotation was used in factor analysis. Studies by Lawton and
Sylvestre of Kodak clearly picked up on curve resolution technology as a means of
reaction analysis in chemistry (1971, 1974) [43]. Window factor analysis (WFA),
which was developed for data analysis of LC photo diode arrays by Malinowski
[44] in 1992, is thought to share a common concept in that it uses eigenvalues of
submatrices. SIMPLISMA, presented by Windig of Kodak in 1991, uses the con-
cept of peak purity as the key to extracting components, which was a novel
extension to the concepts used in the analysis methods proposed up to that point.
The orthogonal projection approach (OPA) proposed by Sanchez et al. [45] of
Bruges University (Belgium) in 1996, which uses the concept of spectral dissimi-
larity in peak extraction, is also an algorithm that has garnered attention.
High energy radiation induces the “clean” modifications and efficient modification
source of many applications. Along the time, several books and reviews presenting
the effects induced during high energy irradiation were issued [46–56]. In the
radiation field the polymer structures and reactivity are the features connected to
initial molecular configuration. New formed radicals are involved in further com-
plex processes, which define the final radiolysis products. The resistance of poly-
mers against the action of ionizing radiation places them in a stability sequence,
which depicts the material capacity to be modified. The successful irradiation
Thermal Degradation of Polymer Blends, Composites and Nanocomposites 7
New generation nano scale fillers are challenging the domination of traditional
fillers such a as carbon blacks and silica in the rubbery industry. Nanoscaled fillers
such as layered silicates, carbon nanotubes, carbon nanofibers (CNFs), exfoliated
graphite, spherical particles and Polyhedral oligomeric silsesquioxane (POSS), etc.,
dispersed as a reinforcing phase in a rubber matrix are emerging as a relatively new
form of useful material.
Polymer nanocomposite having inorganic particles within nanoscale dimensions
have received considerable attention because of their much improved unique
properties and numerous potential applications as in automotive, aerospace and
construction industry, manufacture of tires and inner tubes. Other industrial rubber
goods include various belts, oil seals, gasket and food packing. The morphology-
property correlations in nanocomposites the discussion now focuses on the different
types of nanofillers and reinforcing in synthetic rubbers nanocomposites. In styrene-
butadiene rubber (SBR) nanocomposites showed remarkable improvement in
thermal stability their compared to that of the pure SBR. From another study also
demonstrated that the increase in particle size is not beneficial in improving the
thermal stability [79]. Xiong reported that both the thermal stability and the thermal
conductivity of bromo-butyl rubber (BIIR) nanocomposites could be improved by
incorporating the ionic liquids (ILs) modified graphene oxide (GO-Ils) using a
solution compounding method [80]. Graphene has emerges as a subject of
enormous scientific interest due to its exceptional electron transport, mechanical
properties and high surface area.
Most of the reported literature on elastomer nanocomposites is based on solution
mixing technique, where a polymer is dissolved in a suitable solvent along with
nanofiller followed by evaporation of solvent to obtain the nanocomposite. Solution
mixing can seldom be used for bulk production of nanocomposites as dissolution of
elastomer in the solvent and subsequent removal of the solvent pose engineering
difficulties and environmental problems. Ganter et al. [81] found that the inter-
gallery distance of the organoclay increased more than two times when it was
incorporated in styrene/butadiene rubber (SBR) using toluene solvent. The solution
technique has been used in the past for SBR, ethylene/vinyl acetate [82], butadiene
rubber (BR), polyepichlorohydrin [83], acrylonitrile/butadiene rubber (NBR) [84]
and polyisoprene (IR) [85].
The addition of nanoparticles to synthetic rubber resulting in enhancement in
thermal, stiffness and resistance to fracture is one of the most important phenomena
in material science technology. Thermal and mechanical properties of clays mul-
tiwalled carbon nanotubes reinforced ethylene vinyl acetate (EVA) prepared
through melt blending showed synergistic effect in properties [86]. Malas et al.
reported (SBR/BR)/expanded graphite (EG) and black carbon (CB) nanocompos-
ites by melt blending, this study demonstrated that the presence of EG improvement
thermo-mechanical properties and the presence of CB are a factor important to
Thermal Degradation of Polymer Blends, Composites and Nanocomposites 9
improve such properties [87]. Recently carbon nanotubes are the organic
nanoparticle more attractive to be incorporate in different polymeric matrix, due to
their excellent electrical and conductive properties. The CNs can be surface mod-
ified using simple and economical methods [88], the modifications of the CNs are
important for good dispersion in synthetic rubber nanocomposites. An important
factor in study of thermal stability of synthetic rubber nanocomposites is the dis-
persion of the nanoparticle on the martix. The presence of nanoparticles exfolied
influences the thermal or fire behavior of nanocomposite [89]. Ponomarenko et al.
reported the melt‐compounded composites of synthetic styrene‐co‐butadiene rubber
(BUNA SL18) and silica particles (Silica VN3, Degussa). They showed that at low
elongations, silica particles provided a considerably weaker reinforcement effect of
the rubber matrix when compared to organoclay nanoparticles. Spherical and
anisotropic rod-like particles, dispersed in the nanocomposites, formed a network of
particles bridged by thin rubber layers throughout the SBR matrix [90].
In several papers, the thermal behavior of EVA material is discussed in detail. The
changes in thermal properties due to storage at room temperature and annealing at
elevated temperatures are investigated and explained by characterizing the changes
in polymer morphology. Many studies have been conducted, utilizing various
technical analyses to assess the conditions of the EVA. These methods require the
destructive extraction of samples of the polymer from the module [91, 92].
Extraction of EVA samples from field deployed PV module is very difficult and
contributes to the whole destruction of the PV module. For this reason, the dura-
bility in outdoor exposure of EVA encapsulant under the conditions simulating
those in PV module is often used to assess the weathering of polymeric materials
[93]. In several papers, the thermal behavior of EVA material is discussed in detail.
The changes in thermal properties due to storage at room temperature and annealing
at elevated temperatures are investigated and explained by characterizing the
changes in polymer morphology [94, 95]. TSC is based on the ability of polar
molecules to be moved by an electrostatic field and also has been frequently
employed to investigate the molecular motions in polymeric materials [96, 97].
Thermally Stimulated Current (TSC) TSC is a technique for detecting the transi-
tions that depend on changes in the mobility of molecular scale dipolar structural
units. TSC is based on the ability of polar molecules to be moved by an electrostatic
field. Two types of current are generated: thermally stimulated polarization current
(TSPC) and thermally stimulated depolarization current (TSDC). TSPC is generated
when dipolar structures orient in a static electric field with increasing in the
temperature.
10 P.M. Visakh and O.B. Nazarenko
References
1. Thomas, R., Vijayan, P., Thomas, S.: Recycling of thermosetting polymers. In: Fainleib, A.,
Grigoryeva, O. (eds.) Recent developments in polymer recycling, pp. 122–129. Transworld
Research Network, Kerala (2011)
2. Irfan, M.H.: Chemistry and Technology of Thermosetting Polymers in Construction
Applications, pp. 78–96, 230–239. Springer Science and Business Media, Dodrecht (1998)
3. Shojaei, A., Faghihi, M.: Physico-mechanical properties and thermal stability of thermoset
nanocomposites based on styrene-butadiene rubber/phenolic resin blend. Mat. Sci. Eng. A.
527, 917–926 (2010)
4. Honmute, S., Ganachari, S.V., Bhat, R., Naveen Kumar, H.M.P., Huh, D.S., Venkatarman,
A.: Studies on polyaniline-polyvinyl alcohol (PANI-PVA) interpenetrating polymer network
(IPN) thin films. Int. J. Sci. Res. 1(2), 102–106 (2012)
5. Merlin, L.M., Sivasankar, B.: Synthesis and characterization of semi-interpenetrating
polymer networks using biocompatible polyurethane and acrylamide monomer. Eur. Polym.
J. 45, 165–170 (2009)
6. Alamri, H., Low, I.M., Alothman, Z.: Mechanical, thermal and microstructural characteristics of
cellulose fibre reinforced epoxy/organoclay nanocomposites. Compos. B Eng. 43, 2762–2771
(2012)
7. Xu, S., Girouard, N., Schueneman, G., Shofner, M.L., Meredith, J.C.: Mechanical and
thermal properties of waterborne epoxy composites containing cellulose nanocrystals. Polym.
54, 6589–6598 (2013)
8. Hameed, N., Sreekumar, P.A., Francis, B., Yang, W., Thomas, S.: Morphology, dynamic
mechanical and thermal studies on poly(styrene-co-acrylonitrile) modified epoxy resin/glass
fibre composites. Compos. A Appl. Sci. Manuf. 38, 2422–2432 (2007)
9. Pandey, J.K., Reddy, K.R., Kumar, A.P., Singh, R.P.: An overview on the degradability of
polymer nanocomposites. Polym. Degrad. Stab. 88, 234 (2005)
10. Ollier, R., Rodriguez, E., Alvarez, V.: Unsaturated polyester/bentonite nanocomposites:
influence of clay modification on final performance. Compos. A Appl. Sci. Manuf. 48, 137–143
(2013)
11. Carrasco, F., Pagès, P.: Thermal degradation and stability of epoxy nanocomposites:
influence of montmorillonite content and cure temperature. Polym. Degrad. Stab. 93, 1000
(2008)
12. Lakshmi, M.S., Narmadha, B., Reddy, B.S.R.: Enhanced thermal stability and structural
characteristics of different MMT-Clay/epoxy-nanocomposite materials. Polym. Degrad. Stab.
93, 20125–45213 (2008)
13. Saitoh, K., Ohashi, K., Oyama, T., Takahashi, A., Kadota, J., Hirano, H.: Development of
high-performance epoxy/clay nanocomposites by incorporating novel phosphonium modified
montmorillonite. J. Appl. Polym. Sci. 122, 666 (2011)
14. Chrissafis, D.B.: Can nanoparticles really enhance thermal stability of polymers? Part I: an
overview on thermal decomposition of addition polymers. Thermochim. Acta 523, 1–24
(2011)
15. Sahoo, N.G., Rana, S., Cho, J.W., Li, L., Chan, S.H.: Polymer nanocomposites based on
functionalized carbon nanotubes. Prog. Polym. Sci. 35, 837 (2010)
16. Segev, O., Kushmaro, A., Brenner, A.: Environmental impact of flame retardants (persistence
and biodegradability). Int. J. Environ. Res. Public Health 6, 478–491 (2009)
17. Murphy, J.: Modifying specific properties: flammability-flame retardants. In: Additives for
Plastics, Handbooks, pp. 115–140. Elsevier Science Ltd., New York (2001)
18. Kumara, A.P., Depana, D., Tomerb, N.S., Singha, R.P.: Nanoscale particles for polymer
degradation and stabilization—Trends and future perspectives. Prog. Polym. Sci. 34, 479–515
(2009)
12 P.M. Visakh and O.B. Nazarenko
19. Laoutid, F., Bonnaud, L., Alexandre, M., Lopez-Cuesta, J.-M., Dubois, Ph: New prospects in
flameretardant polymer materials: from fundamentals to nanocomposites. Mater. Sci. Eng. R.
63(3), 100–125 (2009)
20. Zhang, J., Ji, Q., Zhang, P., Xia, Y., Kong, Q.: Thermal stability and flame-retardancy
mechanism of poly(ethyleneterephthalate)/boehmitena nocomposites. Polym. Degrad. Stab.
95, 1211–1218 (2010)
21. Ke, Y.C., Wu, T.B., Xia, Y.F.: The nucleation, crystallization and dispersion behavior of
PET with monodisperse SiO2 composites. Polymer 11, 3324–3336 (2007)
22. Ilyin, A.P., Nazarenko, O.B., Tikhonov, D.V., et al.: Hydroxide and oxide ultra fine powders
—effective retardant additives in polymers. In: Abstract 10th Branch Meeting Problems and
development prospects of the Tomsk Petrochemical Complex, Tomsk, Russia, p. 37 (1996)
(In Russian)
23. Gromov, A.A., Nazarenko, O.B., Tikhonov, D.V., Iljin, A.P., Pautova, Y.I.: Electroex
plosive Nanometals. In: Gromov, A., Teipel, U. (eds.) Metal Nanopowders Production,
Characterization, and Energetic Applications, pp. 67–78. Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim (2014)
24. Kwon, Y.-S., Kim, J.-C., Ilyin, A.P., Nazarenko, O.B., Tikhonov, D.V.: Electroexplosive
technology of nano powders production: current status and future prospect. J. Korean Powder
Metall. Inst. 19(1), 40–48 (2012)
25. Nazarenko, O.B., Amelkovich, Y.A., Ilyin, A.P., Sechin, A.I.: Prospects of using
nanopowders as flame retardant additives. Adv. Mater. Res. 872, 123–127 (2014)
26. Haque, M.H., Upadhyaya, P., Roy, S., Ware, T., Voit, W., Lu, H.: The changes in flexural
properties and microstructures of carbon fiber bismaleimide composite after exposure to a
high temperature. Compos. Struct. 108, 57–64 (2014)
27. La Mantia, F.P., Morreale, M.: Green composites: a brief review. Compos. A 42, 579–588
(2011)
28. Salavatian, M., Smith, L.: An improved analytical model for shear modulus of fiber
reinforced laminates with damage. Compos. Sci. Technol. 105, 9–14 (2014)
29. Yu, T., Jiang, N., Li, Y.: Functionalized multi-walled carbon nanotube for improving the
flame retardancy of ramie/poly(lactic acid) composite. Compos. Sci. Technol. 104, 26–33
(2014)
30. Srikanth, I., Padmavathi, N., Kumar, S., Ghosal, P., Kumar, A., Subrahmanyam, Ch.:
Mechanical, thermal and ablative properties of zirconia, CNT modified carbon/phenolic
composites. Compos. Sci. Technol. 80, 1–7 (2013)
31. Harle, S.M.: The performance of natural fiber reinforced polymer composites: review. Int.
J. Civil. Eng. Res. 5, 285–288 (2014)
32. Hanu, L.G., Simon, G.P., Cheng, Y.-B.: Thermal stability and flammability of silicone
polymer composites. Polym. Degrad. Stab. 91, 1373–1379 (2006)
33. Cai, Y., Wei, Q., Huang, F., Lin, S., Chen, F., Gao, W.: Thermal stability, latent heat and
flame retardant properties of the thermal energy storage phase change materials based on
paraffin/high density polyethylene composites. Renewable Energy 34, 2117–2123 (2009)
34. Chrissafis, D.B.: Can nanoparticles really enhance thermal stability of polymers? Part I: an
overview on thermal decomposition of addition polymers. Thermochim Acta 523, 1–24
(2011)
35. Vadukumpully, S., Paul, J., Mahanta, N., Valiyaveettil, S.: Flexible conductive graphene/
poly(vinyl chloride) composite thin films with high mechanical strength and thermal stability.
Carbon 49, 198–205 (2011)
36. Lin, J., Zhang, P., Zheng, C., Wu, X., Mao, T., Zhu, M., Wang, H., Feng, D., Qian, S., Cai,
X.: Reduced silanized graphene oxide/epoxy-polyurethane composites with enhanced
thermal and mechanical properties. Appl. Surf. Sci. 316, 114–123 (2014)
37. Santos, T.F.A., Vasconcelos, G.C., de Souza, W.A., Costa, M.L., Botelho, E.C.: Suitability
of carbon fiber-reinforced polymers as power cable cores: galvanic corrosion and thermal
stability evaluation. Mater. Des. 65, 780–788 (2015)
Thermal Degradation of Polymer Blends, Composites and Nanocomposites 13
38. Bian, L., Xiao, J., Zeng, J., Xing, S., Yin, C., Jia, A.: Effects of thermal treatment on the
mechanical properties of poly(p-phenylenebenzobisoxazole) fiber reinforced phenolic resin
composite materials. Mater. Des. 54, 230–235 (2014)
39. Kim, J.A., Seong, D.G., Kang, T.J., Youn, J.R.: Effects of surface modification on
rheological and mechanical properties of CNT/epoxy composites. Carbon 44, 1898–1905
(2006)
40. Liew, K.M., Lei, Z.X., Zhang, L.W.: Mechanical analysis of functionally graded carbon
nanotube reinforced composites: a review. Compos. Struct. 120, 90–97 (2015)
41. Xu, S., Girouard, N., Schueneman, G., Shofner, M.L., Carson Meredith, J.: Mechanical and
thermal properties of waterborne epoxy composites containing cellulose nanocrystals.
Polymer 54, 6589−6598 (2013)
42. Kaiser, H.F.: The varimax criterion for analytic rotation in factor analysis. Psychometrika 23,
187−200 (1958)
43. Sylvestre, E.A., Lawton, W.H., Maggio, M.S.: Curve resolution using a postulated chemical
reaction. Technometrics 16(3), 353−368 (1974)
44. Malinowski, E.R.: Factor Analysis in Chemistry, 3rd edn. Wiley, New York (2002)
45. Sanchez, F.C., Toft, J., van den Bogaert, B. and Massart, D.L.: Orthogonal projection
approach applied to peak purity assessment. Anal. Chem. Chem. 68, 79 (1996)
46. Chapiro, A.: Radiation Chemistry of Polymer Materials. Wiley Interscience Publishers, New
York (1962)
47. Clough, R.L.: Radiation-resistant polymers. In: Encyclopedia of Polymer Science and
Engineering, 2nd edn. pp. 667–708. Wiley, New York (1988)
48. Bhattacharya, A.: Radiation and industrial polymers. Prog. Polym. Sci. 25, 371–401 (2000)
49. Clegg, D.W., Collyer, A.A. (eds.): Irradiation Effects on Polymers. Elsevier Applied Science,
London (1999)
50. Woods, R.J.: Applied Radiation Chemistry: Radiation Processing. Wiley Interscience
Publishers, New York (1994)
51. Clough, R. L.: High-energy radiation and polymers. A review of commercial processes and
emerging applications. Nucl. Instrum. Methods Phys. Res. B. 185, pp. 8–33 (2001)
52. Spinks, J.W.T., Woods, R.J. (eds.): Introduction to Radiation Chemistry, 3rd edn. Wiley,
New York (1990)
53. Dawes, K., Glover, L.C., Vroom, D.A.: The effects of electron beam and γ-irradiation on
polymer materials. In: Mark, J.E. (ed.) Physical Properties of Polymer. Handbook, 2nd edn.
Springer, New York (2007)
54. Makuuchi, K., Chang, S. (eds.): Radiation Processing of Polymer Materials and its Industrial
Applications. Wiley, New York (2012)
55. Zaharescu, T., Jipa S.: Radiochemical modifications in polymers. In: Arndt, K.F., Lechner,
M.D. (eds.), Landolt-Börnstein Series, Polymer Solids and Polymer Melts, vol. VIII/6 C2,
pp. 95–184. Springer, Heidelberg (2013)
56. Drobny, J.G.: Ionizing radiation and polymers: principles, technology, and applications. PDL
Handbook Series, Elsevier (2012)
57. Cleland, M.R., Park, L.A., Chang, S.: Applications for radiation processes of material. Nucl.
Instrum. Meth. Phys. Res. B 208, 66–73 (2003)
58. Gehring, J.: With radiation crosslinking of polyolefin engineering plastics into the next
millennium. Radiat. Phys. Chem. 57, 361–365 (2000)
59. Nablo, S.V., Chrusciel, J., Cleghorn, D.A., Rangwalla, I.: Factors influencing equipment
selection in electron beam processing. Nucl. Instrum. Meth. Phys. Res. B 208, 90–101 (2003)
60. Miller, A.: Approval and control of radiation processing, EB and gamma. Radiat. Phys.
Chem. 31, 385–393 (1988)
61. Cleland M.R., Park L.A.: Medium and high-energy electron beam radiation processing for
commercial applications. Nucl. Instrum. Meth. Phys. Res. B 208, 74–89 (2003)
62. Saylor, M.C., Parks, L.A., Herring, C.H.: Technical and regulatory for radiation sterilization
facilities using electron beam accelerators. Nucl. Instrum. Meth. Phys. Res. B 79, 875–878
(1993)
14 P.M. Visakh and O.B. Nazarenko
86. Peeterbroeck, S., Lepoittevin, B., Pollet, E., Benali, S., Broekaert, C., Alexandre, M.,
Bonduel, D., Viville, P., Lazzaroni, R., Dubois, P.: Polymer layered silicate/carbon nanotube
nanocomposites: The catalyzed polymerization approach. Polym. Eng. Sci. 46, 1022–1030
(2006)
87. Malas, A., Pal, P., Das, Ch.K.: Effect of expanded graphite and modified graphite flakes on
the physical and thermo-mechanical properties of styrene butadiene rubber/polybutadiene
rubber (SBR/BR) blends. Mater. Des. 55, 664−673 (2014)
88. Cabello, Ch., Saénz, A., López, L.I., Pérez, C., Barajas, L., Ávila, C.: Modificación
superficial de (MWCNT) con H2SO4/HNO3 mediante ultrasonido. Afinidad 68, 370–374
(2012)
89. Cerin, O., Fontaine, G., Duquesne, S., Bourbigot, S.: Thermal stability of synthetic rubber
nanocomposites. In: Mittal, V. (ed.) Recent Advance in Elastomeric Nanocomposites.
Springer, Heidelberg (2011)
90. Scotti, R., Conzatti, L., D’Arienzo, M., Di Credico, B., Giannini, L., Hanel, T., Stagnaro, P.,
Susanna, A., Tadiello, L., Morazzoni, F.: Shape controlled spherical (0D) and rod-like (1D)
silica nanoparticles in silica/styrene butadiene rubber nanocomposites: role of the particle
morphology on the filler reinforcing effect. Polymer 55, 1497–1506 (2014)
91. Dhere, N.G., Gadre, K.S.: Comparison of mechanical properties of EVA encapsulant in new
and field-deployed PV modules. In: Proceedings of the 2nd World Photovoltaic Solar Energy
Conference and Exhibition, Vienna, Austria, 6–10 July 1998
92. Dechthummarong, C., Wiengmoon, B., Chenvidhya, D., Jivacate, C., Kirtikara, K.: Physical
deterioration of encapsulation and electrical insulation properties of PV modules after long-
term operation in Thailand. Sol. Energy Mater. Sol. Cells 94(9), 1437–1440 (2010)
93. ASTMD1435–05: Standard Practice for Outdoor Weathering of Plastics. ASTMD,
Philadelphia (1985)
94. Stark, W., Jaunich, M.: Investigation of Ethylene Vinyl Acetate copolymer (EVA) by thermal
analysis DSC and DMA. Polym. Test. 30(2), 236–242 (2011)
95. Oreski, G., Wallner, G.M.: Damp heat induced physical aging of PV encapsulation materials.
In: 12th IEEE Intersociety Conference on Thermal and Thermomechanical Phenomena in
Electronic Systems (Itherm 2010), pp. 1−6. Las Vegas, NV, 2–5 June 2010
96. Collins, G., Yoo, S.U., Recber, A., Jaffe, M.: Thermal analysis of complex relaxation
processes in Poly(Desaminotyrosyl-Tyrosine Arylates). Polymer 48(4), 975–988 (2007)
97. Saffell, J.R., Matthiesen, A., McIntyre, R., Ibar, J.P.: Comparing thermal stimulated current
(TSC) with other thermal analytical methods to characterize the amorphous phase of
polymers. Thermochim Acta 192, 243–264 (1991)
98. Kümmerer, K.: Sustainable from the very beginning: rational design of molecules by life
cycle engineering as an important approach for green pharmacy and green chemistry. Green
Chem. 9, 899–907 (2007)
99. Clarinval, A.M., Halleux, J.: Classification of biodegradable polymers, pp. 3–31. CRC Press,
Boca Raton (2005)
100. Rhim, J.W., Park, H.M., Ha, C.S.: Bio-nanocomposites for food packaging applications.
Prog. Polym. Sci. 38, 1629–1652 (2013)
101. Kumar, A.P., Depan, D., Singh Tomer, N., Singh, R.P.: Nanoscale particles for polymer
degradation and stabilization-trends and future perspectives. Prog. Polym. Sci. (Oxford). 34,
479–515 (2009)
102. Raquez, J.M., Habibi, Y., Murariu, M., Dubois, P.: Polylactide (PLA)-based nanocomposites.
Prog. Polym. Sci. 38, 1504–1542 (2013)
103. Sinha Ray, S., Bousmina, M.: Biodegradable polymers and their layered silicate nanocomposites:
in greening the 21st century materials world. Prog. Mater. Sci. 50, 962–1079 (2005)
104. Bikiaris, D.: Can nanoparticles really enhance thermal stability of polymers? Part II: an
overview on thermal decomposition of polycondensation polymers. Thermochim. Acta 523,
25–45 (2011)
105. Yang, K.K., Wang, X.L., Wang, Y.Z.: Progress in Nanocomposite of Biodegradable
Polymer. J Ind Eng Chem. 13, 485–500 (2007)
16 P.M. Visakh and O.B. Nazarenko
106. Mohanty, A.K., Wibowo, A., Misra, M., Drzal, L.T.: Development of renewable resource–
based cellulose acetate bioplastic: Effect of process engineering on the performance of
cellulosic plastics. Polym. Eng. Sci. 43, 1151–1161 (2003)
107. Ray, S.S., Bousmina, M.: Biodegradable polymers and their layered silicate nanocomposites:
in greening the 21st century materials world. Prog. Mater Sci. 50, 962–1079 (2005)
108. Bandyopadhyay, S, Chen, R, Giannelis, E.P.: Biodegradable organic-inorganic hybrids based
on poly(L-lactide). Polym. Mater. Sci. Eng. 81, 159−160 (1999)
109. Pluta, M., Galeski, A., Alexandre, M., Paul, M.A., Dubois, P.: Polylactide/montmorillonite
nanocomposites and microcomposites prepared by melt blending: Structure and some
physical properties. J. Appl. Polym. Sci. 86, 1497–1506 (2002)
110. Chen, C.X., Yoon, J.S.: Morphology and thermal properties of poly(L -lactide)/poly
(butylene succinate-co-butylene adipate) compounded with twice functionalized clay.
J. Polym. Sci. Part B Polym. Phys. 43, 478–487 (2005)
111. Marras, S.I., Zuburtikudis, I., Panayiotou, C.: Nanostructure vs. microstructure:
Morphological and thermomechanical characterization of poly(l-lactic acid)/layered silicate
hybrids. Eur. Polymer J. 43, 2191–2206 (2007)
112. Bafna, A., Beaucage, G., Mirabella, F., Mehta, S.: 3D Hierarchical orientation in polymer–
clay nanocomposite films. Polymer 44, 1103–1115 (2003)
113. Carrasco, F., Pagès, P., Gámez-Pérez, J., Santana, O.O., Maspoch, M.L.: Processing of poly
(lactic acid): Characterization of chemical structure, thermal stability and mechanical
properties. Polym. Degrad. Stab. 95, 116–125 (2010)
114. de Paula, E.L., Mano, V., Pereira, F.V.: Influence of cellulose nanowhiskers on the
hydrolytic degradation behavior of poly(d, l-lactide). Polym. Degrad. Stab. 96, 1631–1638
(2011)
115. Hossain, K.Z., Ahmed, I., Parsons, A., Scotchford, C., Walker, G., Thielemans, W., et al.:
Physico-chemical and mechanical properties of nanocomposites prepared using cellulose
nanowhiskers and poly(lactic acid). J. Mater. Sci. 47, 2675–2686 (2012)
Thermal Degradation of Thermosetting
Blends
Abstract The chapter coalesces literature studies on recent advances concerning the
thermal behavior of different thermosetting blends. The introduction debates the
general issue concerning polymer blends, that being the occurrence of phase separation
phenomena and lists a series of possibilities to overcome these undesired aspects.
The introduction section also presents the most common polymers used as crosslinked
scaffolds either individual or for different multicomponent polymeric materials. The
subchapters that follow are focused on recent studies on the thermal stability and
degradation of thermosetting blends, effect of reinforcement and nanofillers on the
thermal stability of thermosetting blends and applications and future trends of ther-
mosetting blends, dealing with the latest issues and trying to reveal solutions.
1 Introduction
The beginnings of the polymer industry date back to 1846 when the first polymer
blend was patented by Parkes which co-dissolved natural rubber (amorphous
cis-1,4-polyisoprene) and gutta-percha (semi-crystalline trans-1,4-polyisoprene) in
CS2. The blending process yielded a partially crosslinked material. The process was
known as co-vulcanization and the interesting aspect of the final blend was that its
rigidity could be controlled by composition. Due to this aspect, the blends were
used in multiple application domains. What followed was the obtaining of synthetic
R SH
C C S R
OH
O R NH2
C C C C NH R
OH
OH
R C O
OR
C C C O
OH
O
C
O R
C O
O C R
C O
O
O C C
OH
Thermal Degradation of Thermosetting Blends 19
OH OH
CH2
O
CH2
CH2
OH OH OH
CH2 CH2 CH2 C H2
CH2 OH
OH OH
CH2 CH2
O
CH2
OH OH
CH2 CH2 CH2
OH
CH2 CH2
Amongst the outstanding properties of the epoxy resins, their great resistance to
chemical agents and corrosion are noteworthy. Other properties include excellent
electrical and mechanical behavior, flexibility and moderate toughness, great
20 D. Rosu et al.
N N
NHCH2NH C C NHCH2NH C C NHCH2NH
N N N N
C C
NH NH
CH2 CH2
NH NH
C C
N N N N
N
NHCH2NH C C NHCH2NH C C NHCH2NH C C NHCH2NH
N N
N N
C
NH
CH2
NH
C
N N
NHCH2NH C C NHCH2NH
N
The general issue concerning polymer blends consists in the fact that most polymers
are highly immiscible and generate phase separation phenomena, this meaning that
the free energy change of the mixture is not negative, i.e. the heat of mixing is too
high, as previously discussed in this book. According to Hildebrand [4] the heat of
mixing can be expressed as:
22 D. Rosu et al.
DH ¼ V ð/1 /2 Þ2 t1 t2
where V is the total volume, υ1 and υ2 are the volume fractions of the respective
components, ϕ1 and ϕ2 are the solubility parameters.
1=2
DE
/¼
V
Fig. 5 TG and DTG thermograms recorded at 10 °C/min (reproduced with kind permission from
Elsevier—License no. 3280641074690)
reducing intensity until disappearance, and also three endothermic processes, cor-
responding to each individual thermal decomposition stage.
The global kinetic parameters values of the thermal decomposition process were
determined for the structure containing 20 % CER, since the other SIPNs presented
similar thermal behavior, by applying the differential and integral isoconversional
methods of Friedman and Ozawa, Flynn and Wall (OFW) [13, 14]. In both cases
activation energy (Ea) values increased with the conversion degree (α), suggesting a
complex thermal decomposition mechanism through successive and/or parallel
reactions [15]. A three consecutive stage thermal decomposition mechanism was
proposed. The OFW imposes a first order reaction model (i.e. 1 − α) in describing
the thermal decomposition process. If the process is indeed characterized by a first
order reaction model, then the straight lines of the OFW graph should respect the
same parallelism, however, in this case, this condition was not met. Authors tested
14 kinetic models, detailed in the literature [16], by multivariate non-linear
regression method, in order to find the real form of the conversion function which
best characterized the global thermal decomposition process and to determine the
values of the kinetic parameters (Ea, pre-exponential factor (A) and reaction order
(n)) characteristic to each individual stage of the thermal degradation, corre-
sponding to each DTG curve peak. A good correlation between simulated and
experimental data was found for an n-th order reaction model (i.e. (1 − α)n) for all
studied SIPNs. The first stage of thermal decomposition of SIPNs containing 5 and
10 % CER content were characterized by values of n > 2, indicating that mass loss
occurred through scission and intermolecular transfer phenomena [17]. For higher
Thermal Degradation of Thermosetting Blends 25
Fig. 6 Ea variation as
function of CER content for
the first stage of thermal
decomposition min
(reproduced with kind
permission from
Elsevier—License no.
3280641074690)
In the first instance, the SIPNs containing 5 and 10 % CER were characterized
by Ea values higher than the calculated ones, aspect attributed to the high mobility
of the polyurethane chains in the melt states, thus increasing the probability of
recombination reactions occurrence between macroradicals generated during ther-
mal decomposition [18].
In the second instance, the experimental Ea values of structures containing 15 and
20 % CER content were lower than the calculated ones, due to the enhanced stiffness
of the SIPNs induced by the increasing CER content which reduced the macroradicals
deactivation probability by diffusion processes and increased the thermal decom-
position rate [18]. For the structure containing 30 % CER content, the experimental
Ea value exceeds the calculated one due to a maximum crosslinking density and
afterwards phase separation phenomenon occurred and the Ea value of the SIPN
containing 40 % CER becomes lower than the calculated value [19].
A comparative study between experimental and calculated temperatures values
corresponding to 10, 25, 50 and 75 % weight loss is shown in Fig. 7, where ERN is
the epoxy resin content.
The occurrence of specific interactions between the two comprising polymers is
confirmed by the experimental values which are lower than the calculated ones for a
10 % mass loss and which decrease with CER concentration. The existing specific
interactions are lower for a CER concentration up to 10 % and become more intense
26 D. Rosu et al.
Fig. 7 Temperatures
corresponding to a specific
mass loss, as a function of
epoxy resin content
concentration (reproduced
with kind permission from
Elsevier—License no.
3280641074690)
(a)
CH2 C CH2 CH2 CH2 CH
O C O C O C O
CH2 CH CH2 CH H2C CH2
O R O R O R
C O C O
O R OH
O R
H2C CH2
(b) O
CH2 C CH2
C O
R= CH2 CH(C2H5) (CH2)3 CH3
O R OH
the second stage (180–240 °C) and decomposition of both comprising polymers
leading to polyene entities and volatile compounds in the temperature range
410–450 °C. The structures yielded char residue values of 26, 25 and 21 % at the
end of the thermal decomposition process.
IPN membranes based on poly(dimethyl siloxane) with vinyl terminations and
increasing concentrations of aromatic polyimide (5, 10, 15 %) for methanol and
toluene azeotrope separation were obtained and their thermal stability was studied
in both nitrogen and air atmospheres [31]. The blends were first cured at 300 °C,
which is the temperature for optimum imidization process. In both atmospheres the
structures exhibited thermal stability higher than 400 °C which increased with the
polyimide content due to electrostatic attraction between silicone moieties and
polyimide molecules. The blend components each decomposed following identical
pathways. The thermal stability of all structures slightly decreased in air compared
to nitrogen atmosphere and in both situations it was higher than that of neat poly
(dimethyl siloxane). The thermal decomposition processes of the IPNs and the pure
comprising polymers followed similar first order kinetics. Activation energy values
increased in both atmospheres with the polyimide content due to its shielding
mechanism which protected the poly(dimethyl siloxane) during thermal decom-
position. Char yields values at 800 °C varied in the range 46–56 % in nitrogen
atmosphere and in the range 0–49 % in air atmosphere.
Pielichowski and Janowski obtained a series of SIPNs based on polyurethane
and poly(vinyl chloride) by prepolymer method using partially polymerized
diphenylmethane-4,4ʹ-diisocyanate, polyoxypropylenediol and 1,4-butanediol as
chain extender. The networks were thermally characterized in order to gain new
insights in further understanding of the flame retardant effect of poly(vinyl chloride)
in different polymer based blends [32]. All structures thermally decomposed in
three stages in argon atmosphere. The first stage ranged between 313 and 503 °C
with a mass loss value of 12 % and was explained by decomposition initiation. The
second stage was found in the interval 503–693 °C with a mass loss value of 50 %
and was attributed to main thermal degradation during which the decomposition
rate was the fastest. The third thermal decomposition stage occurred in the range
693–863 °C with a mass loss value of 14 % and was attributed to the end of the
decomposition process leading to the formation of solid residue due to crosslinking
processes [33]. Authors reported the occurrence of a decrease of maximum thermal
decomposition rate (i.e. DTG peak maximum) for poly(vinyl chloride) in com-
parison to the crude polyurethane because of hydrogen chloride evolvement which
retards the burning process by playing a scavenger role for free radicals [34].
Furthermore, the amount of solid char remained after thermal decomposition pro-
cess exhibited an increase with molecular mass of polyoxypropylenediol increase,
due to the multiphase morphology of the polyurethane. The polyoxypropylenediol
comprises the soft segments creating a flexible matrix scattered between hard
segments domains which physically crosslink to form a complex temperature
dependent morphology with phase separations.
Merlin and Sivasankar obtained SIPNs based on low (1000 Da) and high
molecular weight (2000 Da) biocompatible polyurethane incorporated in poly
Thermal Degradation of Thermosetting Blends 29
attributed to absorbed water removal. The second mass loss occurred in the
temperature range 200–340 °C and was due to the thermal decomposition of
polymeric side chains. The last thermal decomposition stage occurred in the tem-
perature range 340–480 °C and was attributed to main chains degradation. Authors
observed a slight increase in the thermal decomposition rate with lower crosslinking
degree values. By comparison to the membranes with the same crosslinking degree,
the membrane with higher content of poly(4-styrenesulfonic acid) exhibited a larger
weight loss in the first thermal decomposition stage. This aspect was explained by
the strong hygroscopic character of poly(4-styrenesulfonic acid).
Huang et al. synthesized a class of thermosetting poly(2,6-dimethyl-1,4-pheny-
lene oxide)s containing pendant epoxide groups [38]. The procedure was conducted
by bromination reaction of poly(2,6-dimethyl-1,4-phenylene oxide) in halogenated
aromatic hydrocarbons to yield polymers with different bromination values (50, 35
and 26 %). The obtained compounds were afterwards submitted to a Witting
reaction to obtain vinyl-substituted polymer derivatives. The obtained vinyl-
substituted polymers, with vinyl ratios of 38, 31 and 23 %, were treated with m-
chlorobenzoic acid to yield epoxidized poly(2,6-dimethyl-1,4-phenylene oxide)
with different pendant epoxide molar ratios (35, 28 and 20 %). The thermal stability
of the brominated polymers in nitrogen atmosphere decreased slightly with the
increase of bromo substituent quantity and the char yield increased up to 45 % at
the end of the measurements (800 °C). The structures thermally decomposed in two
stages. The first stage, in the range 250–340 °C with a mass losses of 2–20 %, was
attributed to side chain decomposition due to weaker C–Br bond dissociation
energy compared to that of C–H benzylic bond. The second stage of thermal
decomposition occurred in the range 420–500 °C and was attributed to backbone
scission [39]. A similar thermal decomposition trend was followed by the vinyl-
substituted polymers. The increase of the degree of functionalization led to a slight
decrease in thermal stability, due to the greater disorder in the structural confor-
mation introduced by the vinyl group. The char yield increased in the range
33–50 %. The epoxidized compounds exhibited an intense exothermic peak in the
range 257–267 °C attributed to the curing reaction of the epoxy groups during
heating. The curing process led to a significant increase in the thermal stability of
the cured compounds in comparison to the epoxy analogues. The thermal decom-
position temperature corresponding to 5 % mass loss shifted from within the range
250–256 to 340–355 °C, with tolerable increase in char yield.
yield of these materials is correlated to their flame retardancy; the increased char
yield can limit the production of combustible gases and inhibit the thermal con-
ductivity of the material [40].
In the last years, natural fibres were investigated as reinforcement materials in
polymer composites instead of synthetic fibres, due to their properties such as low
cost, high specific strength, low weight, good thermal and acoustic insulation
properties or lack of toxicity for human health. Alamri et al. investigated the effect
of reinforcement with recycled cellulose fibres and nanoclay platelets (Cloisite 30B)
on the thermal behavior of epoxy systems [41]. The presence of cellulose fibres and
nanoclay slightly increased the rate of nanocomposites thermal degradation at low
temperatures. However, at higher temperatures the char yield of the nanocomposites
was significantly higher than that of the pure epoxy and epoxy reinforced only with
cellulose fibres. This means that nanoclay acted as a barrier and hindered the
diffusion of volatile decomposition products from the nanocomposites.
Shih studied the thermal behavior of an epoxy resin reinforced with water
bamboo husks fibres and powders [42]. The char yield increased from 8.9 % for the
epoxy resin to 10.1–13.6 % for the composites containing 10 % bamboo fibres or
powder. The results showed that the addition of bamboo powder or fibres to epoxy
systems would raise the char yield of the sample, therefore could improve the flame
retardancy of these materials. Similar results were obtained in the case of Phormium
tenax fibres reinforced epoxy composites, containing 20 % fibres. The presence of
plant fibres determined an increase of the composites thermal stability, due to the
improved fibre-matrix interactions [43].
Kenaf fibres were used as reinforcing materials for an epoxy resin [44]. The
maximum degradation temperature was shifted to higher values in the case of
composites. The remaining residue at 500 °C, after thermal degradation, was the
lowest in the case of neat epoxy and increased for the composites containing
modified fibres with NaOH and for the composites with unmodified fibres. The
composites containing modified fibres had a lower char yield than those containing
unmodified fibres due to the removal of lignin by alkalization treatment, lignin
being responsible for the char production in natural fibres. It was concluded that the
thermal stability of kenaf fibres/epoxy composites depends on the composition of
the fibres.
The thermal stability of composites containing natural fibres may also depend on
the nature of the matrix. In the case of composites containing unsaturated polyester
or unsaturated polyester modified with acrylic acid reinforced with jute fibres it was
shown that the composites with modified polyester matrix were more resistant to
temperature than the ones with unmodified polyester matrix. The reason for this
enhanced thermal stability was the presence of acrylic acid as modifier [45].
Cellulose nanocrystals were used as reinforcing filler for waterborne epoxy resin
matrix [46]. In the case of nanocomposites, the onset temperature of thermal
degradation decreased compared to neat epoxy. The same trend was obtained for
the temperature of maximum weight loss for the first degradation step, while the
temperature corresponding to the second step of degradation was slightly increased
with increasing the cellulose nanocrystals content in the nanocomposites. The
32 D. Rosu et al.
results of this study revealed that the addition of cellulose nanocrystals to the epoxy
matrix improved the mechanical properties without compromising the neat matrix
properties.
The thermal behavior of the composites based on raw and surface modified
Grewia optiva particle fibres reinforced unsaturated polyester matrix was studied
[47]. The fibres were modified by mercerization, silanation, benzoylation and graft
copolymerization. The thermal stability of the composites containing modified
fibres was improved compared to the unsaturated polyester matrix and to the
composites containing untreated fibres. This was a consequence of the additional
intermolecular bonding between fibres and matrix induced by the surface modifi-
cation. The highest thermal stability was obtained by the composites based on
silanated fibres due to the formation of strong covalent bonds between silanes and
cellulose.
Due to properties such as high tensile strength, high modulus and high chemical
resistance, glass fibres are also used as reinforcement materials for thermosetting
matrices. Epoxy resin modified with poly(styrene-co-acrylonitrile) was reinforced
with glass fibres [48]. The thermal stability of these composites was improved, their
decomposition starting at higher temperature than that of the neat epoxy. Also the
temperature at maximum weight loss was increased in the case of composites.
Moreover the char residue was around 60 % for composites, while for the neat
epoxy was only 6.6 %. This behavior was a consequence of the presence of ther-
mally stable glass fibres. Glass and aramid (aromatic polyamides) fibres were used
as reinforcement for epoxy foams [49]. All composites exhibited improved thermal
stability compared to the neat epoxy. However, samples reinforced with glass fibres
exhibited higher thermal stability than those reinforced with aramid fibres. The ash
content was of 95 % for the samples reinforced with glass fibres, while the ash
content of the samples containing aramid fibres was 45 %. This proved that the
addition of glass fibre produced epoxy foams with improved thermal stability.
In the last years the thermal behavior of carbon fibre reinforced epoxy resins has
been investigated by different research groups [50]. Régnier et al. performed a
kinetic study on the thermal degradation of carbon fibre/epoxy composites, both in
air and in inert atmosphere. The thermal degradation of the composites occurred in
three stages [51]. The presence of vapour-grown carbon nanofibres into the epoxy
resin matrix did not influence the thermal stability of the resin. The decomposition
temperatures in the case of composites were almost the same with the decompo-
sition temperature of epoxy resin [52].
Huntite (Mg3Ca(CO3)4) was used as reinforcement for an unsaturated polyester
resin [53]. A content of 3 % huntite had a reinforcing effect for the resin, which
caused an improvement of the mechanical and thermal properties. Regarding the
thermal behavior, the onset temperature of composites thermal degradation was
increased with approximately 50 °C, while the maximum degradation temperature
was improved with 16 °C, compared to the polyester matrix.
The properties of a composite material can be changed with the particle size or
distribution, dispersion state and geometric shape. The incorporation of nanometer
sized fillers has become an important strategy for the enhancement of polymers
Thermal Degradation of Thermosetting Blends 33
degradation were increased for the nanocomposites, compared to pure PFA. The
highest increase was obtained for nanocomposites containing cellulose whiskers,
due to a stronger matrix-nanoparticle interaction as compared to the nanocom-
posites containing MMT. Above 400 °C the nanocomposites containing organo
modified MMT exhibited superior weight retention, compared to the nanocom-
posites containing cellulose nanowhiskers or to pure PFA. This increase was
attributed to the complete exfoliation of the clay in the nanocomposites.
In the case of Novolac phenolic resin, the incorporation of highly dispersed
organoclays containing cationic pillaring agents, did not improved the thermal
stability of the resin [64]. Upon reaching the resins decomposition temperatures, the
clay surfaces may provide some catalytic activity which promotes decomposition.
The thermal stabilities of the nanocomposites, expressed by their 5 and 10 % weight
loss temperatures, were established for the initially cured samples (80 °C/2 h) and
for the samples which were additionally cured at 100 °C for 0.5 h. These tem-
peratures were higher for the samples cured than for the nanocomposites partially
cured. Moreover, the char yield at 900 °C was higher for the totally cured
nanocomposites.
The effects of Cloisite loading on the thermal decomposition behavior of an
epoxy resin were reported by Ingram et al. [65]. It was shown that the addition of
Cloisite in the systems improved the thermal stability of the epoxy resins which
underwent an initial cure at 180 °C. However, when the nanocomposites were post
cured at 220 °C, the nanoclay incorporation induced a decrease in the thermal
stability of the systems. This behavior may be attributed to the dissociated alkyl
chains, which destabilize the thermal properties after being subjected to high
temperatures [66]. Therefore, a careful selection of cure and post cure temperatures
must be made in order to obtain nancomposites with improved physical properties
and with enhanced thermal stability.
The thermal stability of some thermosetting nanocomposites obtained by thermal
cationic cure of diglycidilether of bisphenol A and γ-valerolactone using rare earth
metal triflates (trifluoromethanesulfonate) as initiators and containing different types
of Cloisite was studied. The addition of clay into the polymeric matrix was found
to increase the thermal stability, acting as a superior insulator and mass transport
barrier to the volatile products evolved during thermal decomposition [67].
In the case of phenolic resin/organic expanded vermiculite nanocomposites
(a mica-type silicate) the thermal behavior was investigated in both air and nitrogen
atmosphere [68]. The onset temperature of thermal degradation, as well as the
temperature of 15 % weight loss showed a significant increase in the presence of
vermiculite. Also, the mass loss rate of the resin was higher than that of the
nanocomposites. These results were obtained for the experiments carried out in both
atmospheres. The addition of 1.5 % vermiculite in the nanocomposites determined
an increase in the temperature of 15 % weight loss from 476 to 511 °C, in nitrogen
atmosphere and from 422 to 467 °C in oxidative conditions. The improvement
of thermal stability in the case of nanocomposites was attributed to a uniform
dispersion of the exfoliated platelets of vermiculite into the polymer matrix.
Thermal Degradation of Thermosetting Blends 35
These platelets acted as superior insulator and as barrier for oxygen transport and
volatilization of the products resulted after the thermal degradation.
The incorporation of 5 % organically modified sepiolite, which is a micro-
crystalline-hydrated magnesium silicate, in a bisphenol A-based epoxy resin has no
significant effect over the thermal stability of the epoxy resin, due to the poor
dispersion of the clay and poor diffusion of the resin between fibres [69]. The effect
of attapulgite (magnesium aluminium phyllosilicate) over the thermal properties of
hyperbranched polyimides was studied. The presence of this silicate in the nano-
composites significantly improved the thermal stability of the neat polyimide [70].
Ollier et al. reported the effects of modified and unmodified bentonite loading on
the decomposition behavior of unsaturated polyester thermosets [71]. It was shown
that the addition of bentonite increased the thermal stability of the resin. Further-
more, the clay modification did not significantly influence the degradation tem-
peratures of the nanocomposites.
The incorporation of other type of nanoparticles, such as CuO, TiO2,
silsequioxanes was found to affect the thermal degradation of the thermosetting
materials. The thermal stability of the epoxy resin/cupric oxide (CuO) nanocom-
posites in air atmosphere was improved by the presence of CuO nanoparticles.
Furthermore, the presence of these nanoparticles affected the degradation mecha-
nism of the epoxy resin [72].
Cupric oxide unmodified and functionalized with methacryloxypropyl
trimethoxysilane was used to obtain vinyl-ester resin polymeric nanocomposites
[73]. The resistance to thermal degradation was improved for the nanocomposites
with and without postcuring, compared to the pure cured resin. The thermal stability
of the nanocomposites containing functionalized CuO was higher than that of the
nanocomposites containing the unmodified CuO nanoparticles. The presence of the
coupling agent prevented the intimate contact between CuO and vinyl-ester resin,
passivating the particle surface, and thus increasing the thermal stability of the
nanocomposites with functionalized CuO nanoparticles. Similar results were
obtained in the case of vinyl-ester resin nanocomposites with iron oxide nanopar-
ticles (un-modified and functionalized with the same coupling agent) [74, 75].
In the case of Ni–La–Fe–O/epoxy nanocomposites, the thermal degradation
showed a more complicated behavior than the neat epoxy resin, with two peaks in
the 300–475 °C temperature range. Moreover, the thermal stability of the resin
decreased in the presence of Ni–La–Fe–O nanoparticles, due to the fact that these
nanoparticles may act as catalysts to degrade the epoxy matrix [76].
The thermal stability of epoxy resin/TiO2 nanocomposites was found to be
dependent on the nanoparticles loading, as well as on their dispersion state [77]. At
a very low TiO2 loading into the matrix, the nanoparticles were dispersed uniformly
and formed a barrier to heat and oxygen, due to their ceramic nature. When the
content of the nanoparticles was increased, they tended to agglomerate into lumps,
which were non-uniformly distributed into the matrix. In this case the nanoparticles
were less effective in blocking the heat and oxygen, but still more effective than the
neat epoxy resin.
36 D. Rosu et al.
between CNTs and the polymer matrix. The addition of multi-walled carbon
nanotubes (MWCNTs) leads to a decrease of the thermal stability of epoxy matrices
[87, 88]. This effect is caused by the increase of the polymer thermal conductivity
as a consequence of MWCNTs addition. It was also reported that the nanotubes
length and modification with amino groups has no significant influence on the
thermal stability of MWCNTs/epoxy nanocomposites. The activation energies of
the thermal degradation reactions were calculated using the method proposed by
Flynn-Wall-Ozawa. For all studied nanocomposites, the activation energy had
lower values, for all conversion degrees, compared to the neat epoxy. This proved
that the addition of MWCNTs to the epoxy matrix increased the materials degra-
dation efficiency. MWCNTs have high thermal conductivity properties, facilitating
heat transportation in nanocomposites and implicitly decreasing the activation
energy [89]. Similar results were reported in the case of single-walled CNTs [90].
Nanocomposites containing functionalized CNTs exhibited increased thermal
stability, compared to the neat epoxy resin. In this case the functionalized CNTs had
a better affinity for the polymeric matrix than the un-functionalized CNTs [91].
Kuan et al. reported that the incorporation of the MWCNTs functionalized with
vinyltriethoxysylane into an epoxy resin increased its thermal stability [92]. The
same effects were obtained in the case of MWCNTs grafted with triethylenetetra-
mine [91] and MWCNTs functionalized with silane [88].
The thermal stability of nanocomposites containing cyanate ester/MWCNTs was
found to be dependent on the surface modification of CNTs [93]. The results
showed that the presence of unmodified MWCNTs in the nanocomposites produced
a decrease of the initial decomposition temperature and a char yield similar to the
neat resin. On the contrary, the initial decomposition temperature increased with
20 °C in the presence of modified MWCNTs. Moreover, the char yield of the
nanocomposites containing modified MWCNTs was much higher than that of the
cyanate ester resin. These results proved that the nature of carbon nanofiller is
important for developing new nanocomposites with enhanced thermal properties.
The nanocomposites obtained from phenolic resin and carboxylated MWNTs
showed an improvement of the thermal stability than the neat phenolic resin. The
highest thermal stability was obtained in the case of the nanocomposites obtained
by in situ polymerization, due to the quality of dispersion of the functionalized
MWCNTs [94]. An enhancement of the thermal stability was also obtained in the
case of nanocomposites containing boron phenolic resin and MWCNTs modified
with nitric acid, 4,4ʹ-diaminodiphenyl methane and boric acid. This effect was
ascribed to better interfacial interactions between modified MWCNTs and the resin
matrix [95].
The effect of carbon nanofibres on the thermal behavior of phenolic resins was
studied by Bafekrpour et al. [96]. The presence of carbon nanofibres produced an
increase in the thermal stability of the nanocomposites, compared to the neat
phenolic resin. Thus, the decomposition temperature was shifted to higher values
with an increase of the nanofibres content. The same trend was obtained for the
nanocomposites char yield.
Thermal Degradation of Thermosetting Blends 39
Faraz et al. obtained new composites from carbon nanofibres (CNFs) and
bismaleimide, using a thermokinetic mixing method [97]. The addition of CNFs
slightly improved the thermal stability of the nanocomposites. The presence of
CNFs caused the formation of more char residue, but this char was thermally
unstable and it degraded faster compared to the char formed in the case of pure
resin.
Graphene is a new type of nanofiller, with two-dimensional structure and with
excellent mechanical, thermal and electrical properties [98]. The addition of two
kinds of nanofillers: graphene and magnetic graphene (graphene nanosheets coated
with iron core iron oxide shell nanocomposites, Fe@Fe2O3) to an epoxy resin
matrix caused a decrease of the thermal decomposition temperatures. This effect
was attributed to the spatial obstruction of the nanoparticles on the formation of
highly cross-linked epoxy structure. The nanocomposites containing magnetic
graphene showed a much lower weight loss compared to the pure epoxy and epoxy
matrix containing graphene, due to protruding Fe@Fe2O3 nanoparticles on the
surface of graphene, which favored the char formation during the thermal degra-
dation process [99]. Wang et al. reported an improvement in the thermal stability of
epoxy nanocomposites containing 0.1 % graphene oxide nanoparticles [100].
The presence of graphene oxide slightly changed the thermal stability of the
polyurethane/graphene oxide/epoxy nanocomposites. In the case of these nano-
composites, a content of 0.033 % graphene oxide casued a slight increase of the
degradation temperatures [101]. Isocyanate-treated graphene oxide and cyanate
ester resin were used to prepare nanocomposites by a solution intercalated method.
The composites presented a higher char residue than the cyanate ester resin, as a
result of the interactions between graphene oxide and the resin matrix. Also the
degradation temperatures slightly increased with increasing the grapheme oxide
content and the decomposition rates significantly decreased [102].
New materials can be developed by using interpenetrating polymer networks
(IPN) as matrices for various nano-reinforcing agents. Polyhedral oligomeric
silsequioxanes (POSS) was used for the reinforcement of dimethacrylic/epoxy IPN.
The addition of POSS to the neat resin caused a slightly decrease of the onset
temperature of degradation and no change in the maximum weight loss rate. More-
over, the presence of POSS did not influence the thermal stability of the IPN [103].
The thermal decomposition of polyurethane/epoxy resin interpenetrating poly-
mer network (IPN) nanocomposites containing organophilic montmorillonite was
found to be a complex, two-stage process. The thermal stability of these nano-
composites was improved by the presence of nanoclay [104]. Potassium titanate
whiskers were used as reinforcement of polyurethane/epoxy resin IPN [105]. The
incorporation of the whiskers enhanced the thermal stability of the polyurethane/
epoxy resin IPN. The temperatures for 20 and 80 % mass loss were increased
compared to the IPN in the absence of potassium titanate whiskers. Moreover the
residual weight at 600 °C increased from 11.13 % for the IPN to 19.27 % for the
IPN containing 5 % potassium titanate whiskers. When carbon nanotubes were used
as reinforcement for these polyurethane/epoxy resin IPNs, the thermal stability
decreased slightly. This was caused by the CNTs high thermal conductivity [106].
40 D. Rosu et al.
There are several emerging domains incorporating a great deal of research from
multidisciplinary fields and from which great expectations arise for the future. Such
continuous evolving domains include the obtaining of new construction materials,
drug delivery systems, biomaterials, fuel cells [107], cells for solar energy capta-
tion, renewable resources for biofuels, biodegradable polymer systems and smart
materials which are covered in a series of recent reviews [108–110].
Paduraru et al. obtained cryogels based on crosslinked poly(vinyl alcohol) and
increasing quantities of microcristalline cellulose (10, 30, 50 %) and conducted
in vitro tests for the release of vanillin (4-hydroxy-3-methoxybenzaldehyde), an
antimicrobial and antioxidant agent, from poly(vinyl alcohol)/cellulose matrices
[111]. The tests yielded good results due to the increased release percent of bio-
active agent with cellulose content increase in the cryogels and also shortening of
the half and maximum release time. Prior to the in vitro tests authors conducted
thermal stability studies of the cryogel supports. Varganici et al. conducted thermal
decomposition kinetics and evolved gas analysis of the cryogels in nitrogen
atmosphere as background to industrial processing of the future bioactive formu-
lations for wound dressings [112]. According to the two latter literature reports,
pure microcrystalline cellulose exhibited one thermal decomposition stage in the
range 30–124 °C with a 2.1 % mass loss, corresponding to physical dehydration.
This was followed by a main and major decomposition stage with a maximum
temperature at 345 °C, characterized by the highest mass loss (86.09 %), due to the
unzipping of cellulose chains and levoglucosan formation with char and volatile
products yield. Pure poly(vinyl alcohol) thermally decomposed in four stages,
generating water loss, partial dehydration of poly(vinyl alcohol) together with
polyene formation, decomposition of the polyenes formed in the second stage
together with destruction of macroradicals followed by advanced degradation of the
polymeric backbone and scission reactions in the last stage. The highest mass loss
occurred in the range 306–419 °C for poly(vinyl alcohol). These temperature values
shifted to lower domains for the cryogels and remained situated between those of
the pure components. The second thermal decomposition stage (217–306 °C)
characteristic to poly(vinyl alcohol) disappeared due to the cellulose influence over
the cryogels. An increase of the residual mass with cellulose content increase was
also observed, from 3.4 % for the poly(vinyl alcohol) to 11.18 %. The evolved gas
analysis indicated that the major volatile thermal decomposition products were
water, carbon dioxide and carbonyl and olefin structures.
Other excellent wound healing accelerators consists in various materials based
on modified chitosan. The modification of chitosan is necessary, due to its poor
solubility in common organic solvents and water, thus inhibiting its utilization.
Various modification methods, such as chemical grafting, physical blending or
crosslinking have been reported in the literature [113–116]. Rodkate et al. obtained
SIPN hydrogels based on polydimethylsiloxane (PDMS)/polyethylene glycol
(PEG) modified chitosan by interpenetrating 20 wt% of PDMS and PEG into the
Thermal Degradation of Thermosetting Blends 41
with curable thermosets. Such structures give great heat resistance and toughness to
circuit boards, good adhesion to copper wiring and little thermal deformation. They
also make fine patterns formation possible [122].
5 Conclusions
Most developments in the field of polymer blends have aimed at improving materials
final properties. Amongst other plastics, thermosetting polymer blends continue
playing a significant role in the development and application of polymer based
materials because of their advantageous overall cost-performance relation and their
capacity to improve the performance of single resins. Although in the majority of
cases thermosetting polymer blends provided great combination of properties to
single resins, blending techniques require a rich interdisciplinary knowledge,
including surface and phase phenomena characteristics, thermodynamic principles of
miscibility, morphology, processing, and performance. It is a known fact that the vast
majority of commercial blends are not in a thermodynamic equilibrium state, thus
occurring the possibility of generating phase separation phenomena. The selection
of adequate processing method determines the product performance. With the con-
tinuous improvement of fundamental knowledge and research grows the demand
for materials with enhanced performances, making the role of blending more and
more important. Processability is also improved by blending. Blending may lead to
a reduction in viscosity which is of crucial importance to processing. Since the final
properties of the blends are dictated by the properties, composition and morphology
of the individual components, processing must be very carefully examined.
Different special applications of thermosetting blends require different process-
ing techniques of such materials, thus their thermal stability, along with other
properties, is very important in proving the miscibility of the phases and settling the
threshold temperatures for the processing of the future materials. It is for such
purposes that fundamental knowledge must be gained on the different thermal
decomposition mechanisms and their influence on the miscibility and morphology
of the comprising polymers.
Acknowledgments Authors of this chapter acknowledge a grant of the Romanian National Authority
for Scientific Research, CNCS—UEFISCDI, project number PN-II-ID-PCE-2011-3-0187.
References
1. Utracki, L.A.: In: Utracki, L.A. (ed.) Polymer Blends Handbook, vol. 1. Kluwer Academic
Publishers, Dordrecht (2002)
2. Thomas, R., Vijayan, P., Thomas, S.: Recycling of thermosetting polymers. In: Fainleib, A.,
Grigoryeva, O. (eds.) Recent Developments in Polymer Recycling, pp. 122–129. Transworld
Research Network, Kerala (2011)
44 D. Rosu et al.
26. Bandyopadhyay, D., Chakrabarty, D., Mandal, P.K., Goswami, S.: Novolac resin-poly(ethyl
methacrylate) interpenetrating polymer networks: morphology and mechanical and thermal
properties. J. Appl. Polym. Sci. 90, 412–420 (2003)
27. Goswami, S., Nad, S., Chakrabarty, D.: Modification of novolac resin by interpenetrating
network formation with poly(butyl acrylate). J. Appl. Polym. Sci. 97, 2407–2417 (2005)
28. Goswami, S., Kiran, K.: Application of Kissinger analysis to glass transition and study of
thermal degradation kinetics of phenolic-acrylic IPNs. Bull. Mater. Sci. 35(4), 657–664
(2012)
29. Goswami, S., Chakrabarty, D.: Synthesis and characterization of sequential interpenetrating
polymer networks of novolac resin and poly(ethyl acrylate). J. Appl. Polym. Sci. 99,
2857–2867 (2006)
30. Honmute, S., Ganachari, S.V., Bhat, R., Naveen, H.M.P., Kumar, D.S., Venkatarman, H.A.:
Studies on polyaniline-polyvinyl alcohol (PANI-PVA) interpenetrating polymer network
(IPN) thin films. Int. J. Sci. Res. 1(2), 102–106 (2012)
31. Garg, P., Singh, R.P., Choudhary, V.: Selective polydimethylsiloxane/polyimide blended IPN
pervaporation membrane for methanol/toluene azeotrope separation. Sep. Purif. Technol. 76,
407–418 (2011)
32. Pielichowski, K., Janowski, B.: Semi-interpenetrating polymer networks of polyurethane and
poly(vinyl alcohol). Thermal stability assessment. J. Therm. Anal. Calorim. 80, 147–151
(2005)
33. Vieira, E.F.S., Cestari, A.R., Zawadzki, S.F., Rocha, S.M.: Evaluation of tg data of htpb-
based polyurethanes. J. Therm. Anal. Calorim. 75(2), 501–506 (2004)
34. Starnes Jr., W.H.: Structural and mechanistic aspects of the thermal degradation of poly(vinyl
chloride). Progr. Polym. Sci. 27, 2133–2170 (2002)
35. Merlin, L.M., Sivasankar, B.: Synthesis and characterization of semi-interpenetrating
polymer networks using biocompatible polyurethane and acrylamide monomer. Eur. Polym.
J. 45, 165–170 (2009)
36. Mathew, A.P., Packirisamy, S., Thomas, S.: Studies on the thermal stability of natural
rubber/polystyrene interpenetrating polymer networks: thermogravimetric analysis. Polym.
Degrad. Stab. 72, 423–439 (2001)
37. Boonpoo-nga, R., Sriring, M., Nijpanich, S., Wongbuth, L., Martwiset, S.: Semi-interpenetrating
polymer networks of poly(4-styrenesulfonic acid) and poly(acrylic acid) for fuel cell
applications. KKU Res. J. 16(7), 757–763 (2011)
38. Huang, C.-C., Yang, M.-S., Liang, M.: Synthesis of new thermosetting poly(2,6-dimethyl-
1,4-phenylene oxide)s containing epoxide pendant groups. J. Polym. Sci. A Polym. Chem.
44, 5875–5886 (2006)
39. Takayama, S., Mathubara, T., Arai, T., Takedo, K.: Rearrangement of the main-chain and
subsequent thermal degradation of polyphenylene-ether. Polym. Degrad. Stab. 50(3), 277–284
(1995)
40. Pearce, E.M., Liepins, R.: Flame retardants. Environ. Health Perspect. 11, 59–70 (1975)
41. Alamri, H., Low, I.M., Alothman, Z.: Mechanical, thermal and microstructural characteristics
of cellulose fibre reinforced epoxy/organoclay nanocomposites. Compos. B Eng. 43,
2762–2771 (2012)
42. Shih, Y.F.: Mechanical and thermal properties of waste water bamboo husk fiber reinforced
epoxy composites. Mater. Sci. Eng. A 445–446, 289–295 (2007)
43. De Rosa, I.M., Santulli, C., Sarasini, F.: Mechanical and thermal characterization of epoxy
composites reinforced with random and quasi-unidirectional untreated Phormium tenax leaf
fibers. Mater. Des. 31, 2397–2405 (2010)
44. Azwa, Z.N., Yousif, B.F.: Characteristics of kenaf/epoxy composites subjected to thermal
degradation. Polym. Degrad. Stab. 98, 2752–2759 (2013)
45. Manfredi, L.B., Rodríguez, E.S., Przybylak, M.W., Vázquez, A.: Thermal degradation and
fire resistance of unsaturated polyester, modified acrylic resins and their composites with
natural fibres. Polym. Degrad. Stab. 91, 255–261 (2006)
46 D. Rosu et al.
46. Xu, S., Girouard, N., Schueneman, G., Shofner, M.L., Meredith, J.C.: Mechanical and thermal
properties of waterborne epoxy composites containing cellulose nanocrystals. Polymer 54,
6589–6598 (2013)
47. Singha, A.S., Rana, A.K., Jarial, R.K.: Mechanical, dielectric and thermal properties of
Grewia optiva fibers reinforced unsaturated polyester matrix based composites. Mater. Des.
51, 924–934 (2013)
48. Hameed, N., Sreekumar, P.A., Francis, B., Yang, W., Thomas, S.: Morphology, dynamic
mechanical and thermal studies on poly(styrene-co-acrylonitrile) modified epoxy resin/glass
fibre composites. Compos. A Appl. Sci. Manuf. 38, 2422–2432 (2007)
49. Alonso, M.V., Auad, M.L., Nutt, S.: Short-fiber-reinforced epoxy foams. Compos. A Appl.
Sci. Manuf. 37, 1952–1960 (2006)
50. Daoa, D.Q., Luche, J., Richard, F., Rogaume, T., Bourhy-Weber, C., Ruban, S.: Determination
of characteristic parameters for the thermal decomposition of epoxy resin/carbon fibre
composites in cone calorimeter. Int. J. Hydrogen Energy 38, 8167–8178 (2013)
51. Régnier, N., Fontaine, S.: Determination of the thermal degradation kinetic parameters of
carbon fibre reinforced epoxy using TG. J. Therm. Anal. Calorim. 64, 789–799 (2001)
52. Pervin, F., Zhou, Y., Rangari, V.K., Jeelani, S.: Testing and evaluation on the thermal and
mechanical properties of carbon nano fiber reinforced SC-15 epoxy. Mater. Sci. Eng. A 405,
246–253 (2005)
53. Seki, Y., Sever, K., Sarikanat, M., Sakarya, A., Elik, E.: Effect of huntite mineral on
mechanical, thermal and morphological properties of polyester matrix. Compos. B Eng. 45,
1534–1540 (2013)
54. Sun, Y., Zhang, Z., Moon, K.S., Wong, C.P.: Glass transition and relaxation behavior of
epoxy nanocomposites. J. Polym. Sci. B Polym. Phys. 42, 3849–3858 (2004)
55. Bikiaris, D.: Can nanoparticles really enhance thermal stability of polymers? Part II: an
overview on thermal decomposition of polycondensation polymers. Thermochim. Acta 523,
25–45 (2011)
56. Preghenella, M., Pegoretti, A., Migliaresi, C.: Thermo-mechanical characterization of fumed
silica-epoxy nanocomposites. Polymer 46, 12065–12072 (2005)
57. Lakshmi, M.S., Narmadha, B., Reddy, B.S.R.: Enhanced thermal stability and structural
characteristics of different MMT-Clay/epoxy-nanocomposite materials. Polym. Degrad. Stab.
93, 20125–45213 (2008)
58. Saad, G.R., Elhamid, E.E.A., Elmenyawy, S.A.: Dynamic cure kinetics and thermal
degradation of brominated epoxy resin-organoclay based nanocomposites. Thermochim.
Acta 524, 186–193 (2011)
59. Narteh, A.T., Hosur, M., Triggs, E., Jeelani, S.: Thermal stability and degradation of
diglycidyl ether of bisphenol A epoxy modified with different nanoclays exposed to UV
radiation. Polym. Degrad. Stab. 98, 759–770 (2013)
60. Brnardic, I., Macan, J., Ivankovic, H., Ivankovic, M.: Thermal degradation kinetics of epoxy/
organically modified montmorillonite nanocomposites. J. Appl. Polym. Sci. 107, 1932–1938
(2008)
61. Carrasco, F., Pages, P.: Thermal degradation and stability of epoxy nanocomposites:
influence of montmorillonite content and cure temperature. Polym. Degrad. Stab. 93, 1000–
1007 (2008)
62. Jiang, W., Chen, S.H., Chen, Y.: Nanocomposites from phenolic resin and various organo-
modified montmorillonites: preparation and thermal stability. J. Appl. Polym. Sci. 102,
5336–5343 (2006)
63. Pranger, L.A., Nunnery, G.A., Tannenbaum, R.: Mechanism of the nanoparticle-catalyzed
polymerization of furfuryl alcohol and the thermal and mechanical properties of the resulting
nanocomposites. Compos. B Eng. 43, 1139–1146 (2012)
64. Zhang, Z., Ye, G., Toghiani, H., Pittman Jr, C.U.: Morphology and thermal stability of
novolac phenolic resin/clay nanocomposites prepared via solution high-shear mixing.
Macromol. Mater. Eng. 295, 923–933 (2010)
Thermal Degradation of Thermosetting Blends 47
65. Ingram, S.E., Liggat, J.J., Pethrick, R.A.: Properties of epoxy nanoclay system based on
diaminodiphenyl sulfone and diglycidyl ether of bisphenol F: influence of post cure and
structure of amine and epoxy. Polym. Int. 56, 1029–1034 (2007)
66. Park, J., Jana, S.C.: Adverse effects of thermal dissociation of alkyl ammonium ions on
nanoclay exfoliation in epoxy-clay systems. Polymer 45, 7673–7679 (2004)
67. Arasa, M., Pethrick, R.A., Mantecón, A., Serra, A.: New thermosetting nanocomposites
prepared from diglycidyl ether of bisphenol and γ-valerolactone initiated by rare earth triflate
initiators. Eur. Polym. J. 46, 5–13 (2010)
68. Chongqing, Y., Shunping, L., Jianying, Y., Yong, N., Congcong, F., Hua, W., Yufeng, C.:
Preparation and thermal properties of phenolic resin/organic expanded vermiculite
nanocomposites. Adv. Chem. Lett. 1, 51–55 (2013)
69. Nohales, A., Solar, L., Porcar, I., Vallo, C.I., Gómez, C.M.: Morphology, flexural, and
thermal properties of sepiolite modified epoxy resins with different curing agents. Eur.
Polym. J. 42, 3093–3101 (2006)
70. Zhang, Y., Shen, J., Li, Q., Pang, L., Zhang, Q., Xu, Z., Yeung, K.W.K., Yi, C.: Synthesis and
characterization of novel hyperbranched polyimides/attapulgite nanocomposites. Compos.
A Appl. Sci. Manuf. 55, 161–168 (2013)
71. Ollier, R., Rodriguez, E., Alvarez, V.: Unsaturated polyester/bentonite nanocomposites:
influence of clay modification on final performance. Compos. A Appl. Sci. Manuf. 48,
137–143 (2013)
72. Zabihi, O., Ghasemlou, S.: Nano-CuO/epoxy composites: thermal characterization and
thermo-oxidative degradation. Int. J. Polym. Anal. Charact. 17, 108–121 (2012)
73. Guo, Z., Liang, X., Pereira, T., Scaffaro, R., Hahn, H.T.: CuO nanoparticle filled vinyl-ester
resin nanocomposites: fabrication, characterization and property analysis. Compos. Sci.
Technol. 67, 2036–2044 (2007)
74. Guo, Z., Lei, K., Li, Y., Ng, H.W., Prikhodko, S., Hahn, H.T.: Fabrication and
characterization of iron oxide nanoparticles reinforced vinyl-ester resin nanocomposites.
Compos. Sci. Technol. 68, 1513–1520 (2008)
75. Zabihi, O., Hooshafza, A., Moztarzadeh, F., Payravand, H., Afshar, A., Alizadeh, R.:
Isothermal curing behavior and thermo-physical properties of epoxy-based thermoset
nanocomposites reinforced with Fe2O3 nanoparticles. Thermochim. Acta 527, 190–198
(2012)
76. Asiri, A.M., Hussein, M.A., Abu-Zied, B.M., Hermas, A.E.A.: Effect of NiLaxFe2-xO4
nanoparticles on the thermal and coating properties of epoxy resin composites. Compos.
B Eng. 51, 11–18 (2013)
77. Chatterjee, A., Islam, M.S.: Fabrication and characterization of TiO2–epoxy nanocomposite.
Mater. Sci. Eng. A 487, 574–585 (2008)
78. Omrani, A., Afsar, S., Safarpour, M.A.: Thermoset nanocomposites using hybrid nano
TiO2–SiO2. Mater. Chem. Phys. 122, 343–349 (2010)
79. Guigo, N., Mija, A., Zavaglia, R., Vincent, L., Sbirrazzuoli, N.: New insights on the thermal
degradation pathways of neat poly(furfuryl alcohol) and poly(furfuryl alcohol)/SiO2 hybrid
materials. Polym. Degrad. Stab. 94, 908–913 (2009)
80. Schutz, M.R., Sattler, K., Deeken, S., Klein, O., Adasch, V., Liebscher, C.H., Glatzel, U.,
Senker, J., Breu, J.: Improvement of thermal and mechanical properties of a phenolic resin
nanocomposite by in situ formation of silsesquioxanes from a molecular precursor. J. Appl.
Polym. Sci. 117, 2272–2277 (2010)
81. Nagendiran, S., Alagar, M., Hamerton, I.: Octasilsesquioxane-reinforced DGEBA and
TGDDM epoxy nanocomposites: Characterization of thermal, dielectric and morphological
properties. Acta Mater. 58, 3345–3356 (2010)
82. Wang, Y., Liu, F., Xue, X.: Synthesis and characterization of UV-cured epoxy acrylate/POSS
nanocomposites. Prog. Org. Coat. 76, 863–869 (2013)
83. Zhang, Y., Lee, S., Yoonessi, M., Liang, K., Pittman, C.U.: Phenolic resin-trisilanolphenyl
polyhedral oligomeric silsesquioxane (POSS) hybrid nanocomposites: structure and
properties. Polymer 47, 2984–2996 (2006)
48 D. Rosu et al.
84. Aflori, M., Simionescu, B., Bordianu, I.-E., Sacarescu, L., Varganici, C.-D., Doroftei, F.,
Nicolescu, A., Olaru, M.: Silsesquioxane-based hybrid nanocomposites with methacrylate
units containing titania and/or silver nanoparticles as antibacterial/antifungal coatings for
monumental stones. Mater. Sci. Eng. B Solid–State Mater. Adv. Technol. 178(19), 1339–1346
(2013)
85. Bazzar, M., Ghaemy, M.: 1,2,4-Triazole and quinoxaline based polyimide reinforced with
neat and epoxide-end capped modified SiC nanoparticles: Study thermal, mechanical and
photophysical properties. Compos. Sci. Technol. 86, 101–108 (2013)
86. Ma, P.C., Siddiqui, N.A., Marom, G., Kim, J.K.: Dispersion and functionalization of carbon
nanotubes for polymer-based nanocomposites: a review. Compos. A Appl. Sci. Manuf. 41,
1345–1367 (2010)
87. Zhou, Y., Pervin, F., Lewis, L., Jeelani, S.: Experimental study on the thermal and
mechanical properties of multi-walled carbon nanotube-reinforced epoxy. Mater. Sci. Eng. A
452–453, 657–664 (2007)
88. Ma, P.C., Kim, J.K., Tang, B.Z.: Effects of silane functionalization on the properties of
carbon nanotube/epoxy nanocomposites. Compos. Sci. Technol. 67, 2965–2972 (2007)
89. Ciecierska, E., Boczkowska, A., Kurzydlowski, K.J., Rosca, I.D., Hoa, S.V.: The effect of
carbon nanotubes on epoxy matrix nanocomposites. J. Therm. Anal. Calorim. 111, 1019–1024
(2013)
90. Loosa, M.R., Coelhoa, L.A.F., Pezzina, S.H., Amicob, S.C.: Effect of carbon nanotubes
addition on the mechanical and thermal properties of epoxy matrices. Mater. Res. 11, 347–352
(2008)
91. Yang, K., Gu, M.: The Effects of triethylenetetramine grafting of multi-walled carbon
nanotubes on its dispersion, filler-matrix interfacial interaction and the thermal properties of
epoxy nanocomposites. Polym. Eng. Sci. 49, 2158–2167 (2009)
92. Kuan, C.F., Chen, W.J., Li, Y.L., Chen, C.H., Kuan, H.C., Chiang, C.L.: Flame retardance
and thermal stability of carbon nanotube epoxy composite prepared from sol–gel method.
J. Phys. Chem. Sol. 71, 539–543 (2010)
93. Han, C., Gu, A., Liang, G., Yuan, L.: Carbon nanotubes/cyanate ester composites with low
percolation threshold, high dielectric constant and outstanding thermal property. Compos.
A Appl. Sci. Manuf. 41, 1321–1328 (2010)
94. Cui, J., Yan, Y., Liu, J., Wu, Q.: Phenolic resin-MWNT nanocomposites prepared through an
in situ polymerization method. Polym. J. 40, 1067–1073 (2008)
95. Liu, L., Ye, Z.: Effects of modified multi-walled carbon nanotubes on the curing behavior
and thermal stability of boron phenolic resin. Polym. Degrad. Stab. 94, 1972–1978 (2009)
96. Bafekrpour, E., Simon, G.P., Naebe, M., Habsuda, J., Yang, C., Fox, B.: Preparation and
properties of composition-controlled carbon nanofiber/phenolic nanocomposites. Compos.
B Eng. 52, 120–126 (2013)
97. Faraz, M.I., Bhowmik, S., De Ruijter, C., Laoutid, F., Benedictus, R., Dubois, Ph, Page, J.V.S.,
Jeson, S.: Thermal, morphological, and mechanical characterization of novel carbon nanofiber-
filled bismaleimide composites. J. Appl. Polym. Sci. 117, 2159–2167 (2010)
98. Potts, J.R., Dreyer, D.R., Bielawski, C.W., Ruoff, R.S.: Graphene-based polymer
nanocomposites. Polymer 52, 5–25 (2011)
99. Zhang, X., Alloul, O., He, Q., Zhu, J., Verde, M.J., Li, Y., Wei, S., Guo, Z.: Strengthened
magnetic epoxy nanocomposites with protruding nanoparticles on the graphene nanosheets.
Polymer 54, 3594–3604 (2013)
100. Wang, X., Jin, J., Song, M.: An investigation of the mechanism of graphene toughening
epoxy. Carbon 65, 324–333 (2013)
101. Li, Y., Pan, D., Chen, S., Wang, Q., Pan, G., Wang, T.: In situ polymerization and
mechanical, thermal properties of polyurethane/graphene oxide/epoxy nanocomposites.
Mater. Des. 47, 850–856 (2013)
102. Lin, Q., Qu, L., Lü, Q., Fang, C.: Preparation and properties of graphene oxide nanosheets/
cyanate ester resin composites. Polym. Test. 32, 330–337 (2013)
Thermal Degradation of Thermosetting Blends 49
103. Lungu, A., Florea, N.M., Iovu, H.: Dimethacrylic/epoxy interpenetrating polymer networks
including octafunctional POSS. Polymer 53, 300–307 (2012)
104. Jia, Q.M., Zheng, M.S., Chen, H.X., Shen, R.J.: Morphologies and properties of polyurethane/
epoxy resin interpenetrating network nanocomposites modified with organoclay. Mater. Lett.
60, 1306–1309 (2006)
105. Chen, S., Wang, Q., Wang, T., Pei, X.: Preparation, damping and thermal properties of
potassium titanate whiskers filled castor oil-based polyurethane/epoxy interpenetrating
polymer network composites. Mater. Des. 32, 803–807 (2011)
106. Chen, S., Wang, Q., Wang, T.: Damping, thermal, and mechanical properties of carbon
nanotubes modified castor oil-based polyurethane/epoxy interpenetrating polymer network
composites. Mater. Des. 38, 47–52 (2012)
107. Wu, X., He, G., Gu, S., Hu, Z., Yao, P.: Novel interpenetrating polymer network sulfonated
poly(phthalazinone ether sulfone ketone)/polyacrylic acid proton exchange membranes for
fuel cell. J. Membr. Sci. 295, 80–87 (2007)
108. Banerjee, S., Ray, S., Maiti, S., Sen, K.K., Bhattacharyya, U.K., Kaity, S., Ghosh, A.:
Interpenetrating polymer network (IPN): a novel biomaterial. Int. J. Appl. Pharm. 2(1), 28–
34 (2010)
109. Patel, J.M., Savani, H.D., Turakhiya, J.M., Akbari, B.V., Goyani, M., Raj, H.A.: Interpenetrating
polymer network: a novel approach for controlled drug delivery. UJP 1(1), 1–11 (2012)
110. Shivashankar, M., Mandal, B.K.: A review on interpenetrating polymer network. Int.
J. Phram. Phram. Sci. 4(5), 1–7 (2012)
111. Paduraru, O.M., Ciolacu, D., Darie, R.N., Vasile, C.: Synthesis and characterization of
polyvinyl alcohol/cellulose cryogels and their testing as carriers for a bioactive component.
Mater. Sci. Eng. C 32, 2508–2515 (2012)
112. Varganici, C.-D., Paduraru, O.M., Rosu, L., Rosu, D., Simionescu, B.C.: Thermal stability of
some cryogels based on poly(vinyl alcohol) and cellulose. J. Anal. Appl. Pyrol. 104, 77–83
(2013)
113. Gibson, S.L., Walls, H.J., Kennedy, S.B., Welsh, E.R.: Reaction kinetics and gel properties
of blocked diisocyanate crosslinked chitosan hydrogels. Carbohydr. Polym. 54, 193–199
(2003)
114. Zeng, M., Fang, Z., Xu, C.: Effect of compatibility on the structure of the microporous
membrane prepared by selective dissolution of chitosan/synthetic polymer blend membrane.
J. Membr. Sci. 230, 175–181 (2004)
115. Zeng, M., Fang, Z.: Preparation of sub-micrometer porous membrane from chitosan/
polyethylene glycol semi-IPN. J. Membr. Sci. 245, 95–102 (2004)
116. Welsh, E.R., Schauer, C.L., Qadri, S.B., Price, R.R.: Chitosan crosslinking with a water-
soluble, blocked diisocyanate. 1. Solid state. Biomacromolecules 3, 1370–1374 (2002)
117. Rodkate, N., Wichai, U., Boontha, B., Rutnakornpituk, M.: Semi-interpenetrating polymer
network hydrogels between polydimethylsiloxane/polyethylene glycol and chitosan.
Carbohydr. Polym. 81, 617–625 (2010)
118. Dinu, M.V., Cazacu, M., Dragan, E.S.: Mechanical, thermal and surface properties of
polyacrylamide/dextran semi-interpenetrating network hydrogels tuned by the synthesis
temperature. Cent. Eur. J. Chem. 11(2), 248–258 (2013)
119. Grishchuk, S., Karger-Kocsis, J.: Hybrid thermosets from vinyl ester resin and acrylated
epoxidized soybean oil (AESO). Express Polym. Lett. 5(1), 2–11 (2011)
120. Wang, R., Schuman, T.P.: Vegetable oil-derived epoxy monomers and polymer blends: a
comparative study with review. Express Polym. Lett. 7(3), 272–292 (2013)
121. Mustata, F., Tudorachi, N., Rosu, D.: Curing and thermal behavior of resin matrix for
composites based on epoxidized soybean oil/diglycidyl ether of bisphenol A. Compos.
B Eng. 42, 1803–1812 (2011)
122. Harrats, C., Mekhilef, N.: Cocontinuous phase morphologies: predictions, generation and
practical applications. In: Harrats, C., Thomas, S., Groeninckx, G. (eds.) Micro- and
Nanostructured Multiphase Polymer Blend Systems: Phase Morphology and Interfaces,
p. 124. Taylor & Francis Group, USA (2006)
Thermal Degradation of Thermosetting
Nanocomposites
1 Introduction
The use of organic and inorganic reinforcements as vegetal fibers, clays and inor-
ganic powder (as barium sulfate) has become very common in polymeric systems
[1–13]. This can be mainly attributed to reduce the cost of the end-products. Polymer
composites are manufactured commercially for many diverse applications such as sport
engineering [14] aerospace components [15] and automobile industry [7, 16, 17].
These applications are due among other characteristics, intrinsic lightweight and
M. Poletto (&)
Center of Exact Sciences, Nature and Technology (CENT),
Caxias do Sul University (UCS), Rua Francisco Getúlio Vargas,
1130 Caxias do Sul/RS, Brazil
e-mail: [email protected]; [email protected]
H.L. Ornaghi Júnior
Engineering and Materials Science Graduate Program (PGMAT),
Caxias do Sul University (UCS), 95070-490 Caxias do Sul/RS, Brazil
A.J. Zattera
Laboratory of Polymers (LPOL), Caxias do Sul University (UCS),
Rua Francisco Getúlio Vargas, 1130 Caxias do Sul/RS, Brazil
tailor-ability of composites that clearly promoted their rapid utilization [18, 19].
However, there are concerns related to their overall durability particularly when under
load and exposed to harsh and changing environmental conditions [20, 21]. Besides,
some properties cannot be reached in using reinforcement in the micro/macro scale.
With the rapid development of nanotechnologies and nanomaterials since 1990s,
the studies on polymer-based nanocomposites have been extensively focused on the
enhancement of their properties. Among these, it is focused on highlighting the
effect of different nanoparticles, their dispersion and the used modifiers on polymer
thermal stability. The whole range of polycondensation polymer matrices has
reactive end groups which can interact with inorganic nanoparticles surface.
Hydrogen or covalent bonds can be formed, which can increase the adhesion of
nanoparticles with the polymer matrix, resulting in higher dispersion degrees. This,
in most cases, leads to substantial enhancement in thermal decomposition proper-
ties. Only in nanocomposites containing montmorillonite there are conflicting
results and accelerated degradation process were also reported. Organoclays also
have similar effect on polymers thermal stability and in this case the achieved clay
dispersion (intercalated-exfoliated), as well the used modifier, can alter the thermal
decomposition of polymers. The used amount of nanoparticles plays an important
role on the thermal stability of nanocomposites. In most cases thermal stability
enhancement takes place at low loading (4–5 wt%) of nanoparticles, while at higher
contents the stabilization becomes progressively smaller [22].
Nanocomposites materials can be defined as composite materials, that combine
one or more separate components in order to improve performance properties, for
which at least one dimension of the dispersed particles is in the nanometer range
[23]. In polymer clay nanocomposites, nanoscale particles have typically
10–100 nm in size [24]. Depending on the reinforcement, remarkable improvement
in material properties when compared with neat polymer or conventional micro and
macro-composites can be obtained. These improvements can include high moduli,
increased strength and heat resistance, decreased gas permeability and flammability,
and increased biodegradability of biodegradable polymers [25].
Among all the nanocomposite precursors, those based on clay and layered silicates
have been most widely investigated, probably because the starting clay materials are
easily available and because their intercalation chemistry has been studied for a long
time [26]. Besides clay [2, 9], it can be cited other examples of nanocomposite as
reinforcements (some of them previously cited) such as polyhedral oligomeric sils-
esquioxanes (POSS) [10], nanodiamonds [27] and carbon nanotubes [28]. Simulta-
neously, the rapid growth of the computer technology has made it easier to
characterize and predict the properties at the nanoscale via modeling and simulation
[29]. In general, the unique combination of the nanomaterial’s characteristics, such as
size, mechanical properties, and low concentration are necessary to promote changes
in a polymer matrix, coupled with the advanced characterization and simulation
techniques now available have generated much interest in the field of nanocom-
posites. In addition, many polymer nanocomposites can be fabricated and processed
in ways similar to that of conventional polymer composites, making them particularly
attractive from a manufacturing point of view [30].
Thermal Degradation of Thermosetting Nanocomposites 53
Two terms are used to describe the two general classes of nano-morphology that
can be prepared: intercalated and delaminated (exfoliated). Intercalated structures are
well ordered multi-layered structures where the extended polymer chains are inserted
into the gallery space between the individual silicate layers. The delaminated
(exfoliated) structures result when the individual silicate layers are no longer close
enough to interact with the adjacent layers’ gallery cations. In the latter, the interlayer
spacing can be on the order of the radius of gyration of the polymer; therefore, the
silicate layers may be considered well dispersed in the organic polymer. Furthermore,
the silicate layers in a delaminated structure may not be as well ordered as in an
intercalated structure. X-ray diffraction measurements are used to characterize the
nanostructures. Reflections in the low angle region indicate the d-spacing (basal
spacing) of ordered intercalated and ordered delaminated nanocomposites; disor-
dered delaminated nanocomposites show no peaks in this region due to the loss of
structural registry of the layers and the large d-spacings (>10 nm) [30].
This chapter has as objective to evaluate the thermal degradation of thermo-
setting nanocomposite and the effect of the reinforcement on the thermal stability of
the nanocomposites.
Degradation is a process where the deterioration in the properties of the polymer takes
place due to different factors like ultraviolet (UV) radiation, thermal energy or
mechanical loading. As a consequence of degradation, the resulting smaller fragments
do not contribute effectively to the mechanical properties, the component becomes brittle
and the life of the material becomes limited. Thus, any polymer or its composite, which is
to be used in outdoor applications, for example, must be highly resistant to all envi-
ronmental conditions [31]. There is a well-established mechanism of polymer degra-
dation as well as their stabilization. The study of degradation and stabilization of
polymers is an extremely important area from a scientific and industrial point of view and
a better understanding of polymer degradation will ensure the long life of the product.
More specifically, Fig. 1 shows some properties commonly used for evaluating the
polymer degradation. Several techniques were used for characterization of the
polymer degradation. Among the mechanical properties characterization that can be
obtained, it can be cited dynamic mechanical analysis, where the influence of the
mechanical properties, such as the flexural and impact strengths can be directly
related with the storage modulus and the tan delta dissipation energy [4, 8]. The
percentage degradation can be estimated by the weight loss (from TGA) [5], for
example. Scanning electron microscopy (SEM) or transmission electron microscopy
(TEM) [9] and X-ray diffraction [2] can be used when a physical property is required.
Finally, in chemical properties, functional changes can be measured by FTIR or UV
spectroscopy [1, 13] and molecular weight changes by GPC and viscosity [25].
There is a well-established mechanism of polymer degradation as well as their
stabilization, as can be seen in Fig. 2. The study of degradation and stabilization of
54 M. Poletto et al.
Fig. 1 Different properties commonly used for evaluate the polymer degradation. Adapted from [31]
Fig. 2 Different pathways of degradation and stabilization in polymeric materials. Adapted from [31]
Thermal Degradation of Thermosetting Nanocomposites 55
polymers is an extremely important area from the scientific and industrial point of
view and a better understanding of polymer degradation will ensure the long life of
the product and leads to the development of more efficient stabilizers.
The scheme above is based on an original scheme for autocatalytic oxidation of
hydrocarbons. The oxidation of polymers begins during processing (mechano-
oxidation), and the hydroperoxides formation during fabrication affects further the
rate of thermal/photo-oxidation during subsequent use (aging and weathering). So,
degradation of polymers is like a double-edged sword: it has harmful aspects as
well as beneficial aspects. If unchecked it can play havoc with a polymers per-
formance, if uncontrolled it can lead to safety hazards of fire and toxicity, but if
properly harnessed it can be used for producing new and better materials.
For various applications, the service life of polymeric materials can be tuned by
incorporating additives externally. In order to induce and promote oxidation of
polymers, the sensitizers, which transfer the energy to polymer or decompose itself
to give single oxygen molecule which can initiate the oxidation are added. Certain
organic and inorganic compounds are excited in presence of light, heat, high-energy
radiations, and transfer energy to polymers or free radicals [31].
Stability can be said as the protection of polymeric materials from which lead to
deterioration of properties [31]. In literature, there are different and sometimes
contradictory reported papers [31–38] concerning the effect of the nanoparticles on
polymer thermal stability. There are papers suggesting that nanoparticles have no
obviously effect on thermal stability, some of them suggested a small to substantial
enhancement and some others suggested acceleration of thermal decomposition.
Nanocomposites based on clay or with other nanoparticles with a larger amount of
hydroxyl groups can exhibited a much more pronounced degradation because the
hydroxyl groups acted as Bronzed acidic sites and accelerated the polymer’s deg-
radation. It was suggested that during thermal decomposition in nitrogen the clay
can slow down degradation of polymer as a mass transport protective barrier, but
the catalytic effect of the metal derivatives in the clays could accelerate the
decomposition behavior of a polymer. The combination of these two effects
determined the final thermal stability of the nanocomposite. Furthermore, some
nanoparticles have reactive groups such as −COOH and −OH, which can also
accelerate the decomposition of polymers or to form covalent bonds leading to their
thermal degradation enhancement [32]. Thus, the main question is what is the really
effect of nanoparticles on polymer thermal stability?
In a study performed by Ollier et al. [33], the author incorporated 5 % weight of
bentonite in unsaturated polyester (UP) matrix. They noted that the addition of
bentonite increases the thermal stability of the UP resin. Bharadwaj et al. [34]
showed that the incorporation of commercially modified MMT to UP was detri-
mental for the thermal stability of the nanocomposites. The most important finding
56 M. Poletto et al.
is that there was the formation of a nanocomposite with decreasing of the tensile
modulus, storage and loss moduli as clay content was incorporated. In addition, the
rate of thermal degradation was slightly but progressively hastened upon formation
of a nanocomposite. These trends have been explained on the basis of a progressive
decrease in the degree of crosslinking with increasing clay concentration. Becker
et al. [35] also observed a slight decreased in the onset temperature (in the order of
5–10 °C) of the degradation process of epoxy resin by increasing organoclay
content (at a clay concentration of 10 %). The changes in thermal stability are of
very low significance and it is unlikely that they would be considered as a drawback
to any possible industrial application. Carrasco and Pagès [36] showed that, at low
clay contents (up to 5 wt%) the addition of clay had no effect on the thermal
stability of the epoxy matrix, whereas for higher concentration (10 wt%) a clear
increase on this parameter was observed. Other authors demonstrated that the
thermal stability of epoxy based nanocomposite is dependent upon the dispersion of
the organoclay in the epoxy matrix but that all the epoxy nanocomposites had
enhanced thermal stability compared with the neat epoxy resin. In addition,
Lakshimi et al. [37] reported an improvement in the thermal stability of epoxy
resins with the incorporation of MMT with the same chemical treatments used in
this work. The author incorporated two different modified clays with four different
epoxies using 5 wt% modified clay. The SAXS and SEM characterization reveals
that the modified clay is highly exfoliated and uniformly dispersed in the matrix.
There was an increase in the thermal stability observed in all modified systems. This
was attributed to the nanolayer acted as a barrier for volatile degradation of polymer
matrix. Saitoh et al. [38] found that the phosphonium cations used to obtain the
organoclays influenced the thermal resistance of the resulting epoxy/clay nano-
composites. The explanation for this behavior is that the dispersed MMT-Clay
nanolayers can act as barrier protecting the epoxy polymer matrix degradation
gaseous products from volatilizing.
For the majority of polymers, due to their hydrophobic character, the clay must
be modified with a surfactant in order to make the gallery space sufficiently
organophilic to permit it to interact with the polymer. In fact, several factors were
found to govern the thermal stability of nanocomposite materials, such as intrinsic
thermal resistance of polymer matrix, nanofiller content, chemical constitution of
organic modifier and chemical character of polar compatibilizers as well as an
access of oxygen to composite material during heating. For surface modification of
clay, the surfactant is usually described as an ‘onium’ salt. The quaternary
ammonium ion is nominally chosen to compatibilize the layered silicate with a
given polymer resin. However, the molecular structure (length and number of alkyl
chains and unsaturations) is also the determining factor of the thermal stability of
the polymer/MMT nanocomposites [39]. The amount of surfactants with multiple
alkyl tails has greater thermal stability than those with a single alkyl tail. It has been
proposed that the organic modifiers starting at a temperature around 200 °C, and the
small molecular weight organics are released first while the high-molecular weight
organic species are still trapped by organically modified layered silicates (OLS)
matrix. With the increase of temperature, the high-molecular organic polymer
Thermal Degradation of Thermosetting Nanocomposites 57
chains may still exist between the interlayers until the temperature is high enough to
lead to their further decomposition. The incorporation of silicate layers with high-
aspect ratio decomposed/charred material on the clay surface act as carbonaceous
insulators. The silicate has an excellent barrier property that prevents against per-
meation of various degraded gaseous products. The addition of clay enhanced the
performed by acting as a superior insulator and mass transport barrier to the volatile
products generated during decomposition. The clay acts as a heat barrier, which
could enhance the overall thermal stability of the system, as well as assisting in the
formation of char during thermal decomposition. In the case of the nanocomposite,
the temperature at which volatilization occurs, increases as compared of the micro-
composite. Moreover, the thermal oxidation process of the polymer is strongly
slowed down in the nanocomposite with high-char yield both by a physical barrier
effect, enhanced by ablative reassembling of the silicate, and by a chemical catalytic
action due to the silicate and to the strongly acid sites created by thermal decom-
position of the protonated amine silicate modifier. The polymers that show good fire
retardancy upon nanocomposite formation exhibit significant intermolecular reac-
tions, such as inter-chain aminolysis/acidolysis, radical recombination and hydro-
gen abstraction. In the case of the polymers that degrade through a radical pathway,
the relative stability of the radical is the most important for the prediction of the
effect that nanocomposite formation has on the reduction in the peak heat release
rate. The more stable is the radical produced by the polymer; the better is the fire
retardancy, as measured by the reduction in the peak release rate, of the polymer/
clay nanocomposite [40, 41].
The particles can behave in a different way on the polymers’ thermal stability. In
some reported studies it has been shown that the introduction of clays into poly-
meric matrices can accelerate the thermal decomposition of the polymer matrix,
consisted by condensation polymers, due to the catalysis effect of water in MMT
and hydroxyl groups on the clay platelets. Meanwhile, some metallic derivatives
that can be found in clays interspaces have significant catalytic activity on thermal
degradation, and reduce the thermal stability of nanocomposites. Furthermore, most
of the used organic modifiers for clays have low thermal stability that condensation
polymers, like alipharomatic polyesters or polyamides, and this can form byprod-
ucts that can accelerate thermal decomposition [42, 43]. Ammonium surfactants
experience Hofmann elimination reaction, producing acidic sites which can
accelerate thermal degradation of polycondensation polymers. Also, the architec-
ture (trimethyl or dimethyl), chain length, surfactant mixture, exchanged ratio, or
preconditioning (washing) does not alter the initial onset temperatures. However,
these factors do affect the initial mass loss [44].
58 M. Poletto et al.
Except for these studies there are also some others, but limited which report that
the addition of clays can enhance thermal stability. In these papers the improved
thermal stability is probably due to the high thermal stability of clay and due to the
interactions between the clay particles and the polymer matrices. Furthermore, the
hindrance effect of clays was due to the formation of char layers obtained via
collapsing of the nanocomposite structure and reformulation of silicate layers. This
carbon silicate structure on the surface may act as a mass transport barrier that
hinders volatilization of decomposed gaseous products via the degradation. How-
ever, the most probably reason to achieve a thermal stability is due to homogeneous
dispersion of nanoclay platelets within the matrix that may act as thermal insulation
layers, thus reducing the degraded volatile products’ diffusion out of the matrix. In
order to achieve this, thermally stable modifiers without the above-mentioned
problems should be used. Using such modifiers intercalated or exfoliated disper-
sions can be prepared which cause higher stabilization than unmodified clays. In the
latter case usually microcomposites can be prepared instead of nanocomposites,
since it is very difficult for the clay plates to separate and be dispersed as individual
plates in the polymer matrix. Furthermore, the exfoliated clay may also promote
char formation under degradation, which can act as physical barriers (labyrinth
effect) to the volatile products generated during decomposition [42, 43]. Except of
the particle dispersion its size plays also important role, as was reveled in some
studies. Particles with smaller sizes can be dispersed more homogeneously into
polymer matrix and thus the barrier effect is higher.
The stabilization effect of carbon nanotubes (CNTs) is explained by a barrier
effect of the nanotubes that usually agglomerate due to van der Waals force and
them form aggregates, which hinder the diffusion of the degradation products from
the bulk of the polymer onto gas phase [35, 45]. Furthermore, the thermal stabil-
ization effect on carbon nanotubes could be attributed to the increased interfacial
interaction between the nanofibres and polymers which lead to an increase of the
degradation’s activation energy. Besides, there are several preparation methods and
types of functionalizations [45]. As an example, one can cite the carboxylated and
fluorinated MWCNT systems. In the former, there are higher activation energy
value in comparison with neat epoxy resin and the latter. This difference may be
attributed to differences in nanotubes dispersion; the fluorinated MWCNT system is
more uniformly dispersed in the matrix whereas the more heterogeneously dis-
persed carboxylated MWCNTs can hinder mobility of the reactive species and
disrupt the reaction stoichiometric on the local scale [46]. The improvement thermal
stability of such nanocomposites is generally attributed to: (i) the creation of a
tortuous path, resulting by the nanoparticles dispersion into the polymer matrix,
slowing the diffusion of the produced substances in the material, (ii) the formation
of a carbonaceous char insulating the material and slowing the release of the
decomposition products [35].
Except of the kind of nanoparticles, its amount is also very crucial for thermal
stabilization enhancement. It was reported that at two amounts, usually 2–5 wt%,
Thermal Degradation of Thermosetting Nanocomposites 59
and depending the type of nanoparticles, the highest thermal stabilization can be
achieved. This is due to the fine dispersion of nanoparticles into the polymer
matrices and, thus, high surface area of a non-degradable material, as most of the
nanoparticles used are, is available to protect the macromolecular chains from
thermal decomposition. However, at higher nanoparticles content, due to the for-
mation of aggregates, a deterioration of thermal stability was mentioned in most of
the reported nanocomposites in the present review. In this case, it seems that a
microcomposite is formed instead of a nanocomposite. Thus, the shielding effect of
the nanoparticles is lessened.
In nitrogen, pure epoxy resin thermally degrades through a double step process
with maximum rates at 301 and 414 °C. The first step of degradation involves water
elimination which results in formation of C–C unsaturations. Carbon-oxygen bonds
in beta positions to these unsaturations (allylic bonds) become the thermally
weakest bonds in the epoxy network. They break down giving fragmentation of the
crosslinked structure that eventually produces fragments small enough to evaporate
at these temperatures. Volatilization is, however, limited up to 350 °C because it is
contrasted by rearrangements such as cyclization that produces a relatively stable
structure which breaks down in the second step of degradation. In this step
extensive break down of chemical bonds of the epoxy network takes place
including C-phenyl bonds of bisphenol-A, leading to almost complete volatiliza-
tion. A minor amount of charred residue is formed (ca. 4 %) due to limited
recombination to a thermally stable charred material of reactive degrading species
during decomposition.
The incorporation of clay in the epoxy system results in increased thermal
stability when nanocomposite is cured at 180 °C. As found from TGA analysis the
onset of degradation is delayed and the temperature range of degradation has been
influenced by the addition of clay. In contrast, however, when the nanocomposite
material is post-cured at 220 °C, the addition of nanoclay resulted in a decrease in
the thermal stability of the epoxy resin. This can be associated with the dissociated
alkyl chains, after being subjected to the high temperature and destabilizing the
thermal properties. This finding is critical for maximing the enhancements from
nanoclay. All cure cycle temperatures must be carefully selected otherwise detri-
mental effects may be realized, even when similar levels of exfoliation and
mechanical properties are achieved [47]. However, Carrasco and Pages [36] found
that the thermal decomposition of cured materials was independent of cure tem-
perature but from the content of clay. With the incorporation of crude clay, the
initial temperature degradation and the maximum temperature degradation shifted
towards higher temperature. The enhancement on the resin’s thermal stability was
more significant in the initial stage of decomposition. This behavior may be
attributed to the protection of epoxy polymer chains present between hard MMT-
clay nanolayers that act as a barrier protecting from volatizing the epoxy polymer
matrix. The polymer networks present between the clay layers undergo the
restricted segmental motion which reflected in higher thermal stability properties
than the urethane modified epoxy (UME) systems.
60 M. Poletto et al.
Organoclays have also similar effects on polymers thermal stability and in this
case the achieved clay dispersion (intercalated-exfoliated) as well as the used
modifier can also alter thermal decomposition of polymers. Cationic compounds
used for organomodification of MMT have a negative effect in thermal degradation
while the exfoliated structure due to the finer dispersion of the clay nanoparticles
can lead to thermal stabilization than intercalated structure.
Except montmorillonite, other clays like layered double hydroxide (LDH) can
enhance thermal degradation of polymers. In such nanocomposites there are no
reported for accelerating effect of LDH on polymer thermal degradation. This is
because LDH can be more easily dispersed in intercalated or exfoliated structures,
compared with MMT, into a polymer matrix and thus the stabilization effect is
higher [22].
Carbon nanotubes (MWCNTs and SWCNTs) were also in all cases reported that
can increase thermal stability of polymers. This was because the CNTs have
excellent thermal conductivity. The improving thermal stability of the nanocom-
posites was also attributed to the formation and stabilization of MWCNTs-bonded
macroradicals [45].
Except of the commonly used nanoparticles, other less important, like graphite,
carbon nanoparticles, Ag, TiO2, magnesium hydroxide, CaCO3, ZnO, POSS,
boehmite (AlOOH), Al2O3, etc., were also found to have substantial stabilization
effect on polymer degradation [22].
In a study performed by Bharadwaj et al. [34] the onset of degradation of
polymer nanocomposites was slightly but progressively hastened upon addition of
clay to the nanocomposites as compared to the neat polymer. The neat polymer is
completely decomposed at 400 °C. The nanocomposites degrade at a faster rate in
the temperature range 25–400 °C compared to the neat polymer and thereafter the
situation reverses. The monotonic increase in the rate of degradation in the nano-
composites may be due to the presence of increasing amount of hydroxyl group in
the organic modifier that provides a supply of oxygen.
The main conclusion from all the above is that except of MMT, where contra-
dictory results were reported, in all other nanocomposites the addition of nano-
particles can lead to thermal stabilization effect of polymers during their
decomposition. However, in this direction the effect of nanoparticles content is very
crucial. In most of the cases the thermal stability enhancement takes place at low
loading (4–5 wt%) of nanoparticles while at higher contents thermal stabilization
becomes progressively lower. This is because at higher concentrations nanoparti-
cles can form aggregates and thus effective area of nanoparticles in contact with
polymer macromolecular is lower. In this case microcomposites may are formed
instead of nanocomposites and thus the protective effect of nanoparticles becomes
lower [22].
Thermal Degradation of Thermosetting Nanocomposites 63
Nanoparticles are used as reinforcement and usually increase the thermal stability in
comparison to the unfilled thermoset. The clay slows the cure process because
influences the nature of the network structure formed because the activated
monomer mechanism favors chain transfer processes [57].
According to recent investigation, the thermal degradation of nanocomposites
depends on the clay loading, structure and the nature of the ambient gas. A
nanocomposite with 2 wt% loading showed one step degradation; whereas 10 wt%
clay loading showed two steps and the maxima degradation were at 395 and
397 °C, indicating that degradation started at lower temperature with increasing
loading of clay. There are two factors which have opposite influences on the
thermal stability of epoxy-clay nanocomposites. The first factor is that the addition
of clay to epoxy decreases the curing reactivity of epoxy resin. Lower reactivity of
the resin generally results in lower crosslinking density of the cured resin and the
longer polymer chains among the cross-linking points. It is known that for a longer
polymer chain, the nanocomposites resulted are easier to degrade than the neat
epoxy resin. Secondly, silicate layers have good barrier to gases such as oxygen and
nitrogen, they can insulate the underlying materials and slow the mass loss rate of
decomposition products [49, 58]. Moreover, exfoliated nanocomposites have better
barrier properties and thermal stability than intercalated ones. In the case of
intercalated nanocomposites (10 wt% clay), the first factor is dominant, whereas for
an exfoliated nanocomposites (2 wt% clay), the second factor is dominant.
In another study, Bafekrpour and et al. [60] designed and fabricated functionally
graded carbon nanofiber-phenolic nanocomposites (FGN) using four different
gradient patterns and the same overall carbon nanofiber (CNF) content and
geometry. The composition across the thickness of the samples was controlled in
eight 600-mm-thick layers with clear interlayer boundaries. They observed that the
incorporation of CNF into the phenolic matrix increased the thermal conductivity of
the resin. For example, the thermal conductivity of the matrix increased 28.1, 49.5
and 90.4 % with the incorporation of 2, 4 and 16 wt% CNF, at room temperature,
respectively. The authors attributed this thermal conductivity enhancement in the
phenolic matrix is due to the formation of inter-connected mesh of CNFs.
Badrinarayanan and Kessler [61] explored the potential for development of bulk
polymer nanocomposites with tailored thermal expansivity. The authors incorpo-
rated zirconium tungstate (ZrW2O8) nanoparticles (characterized by a negative
coefficient of thermal expansion (CTE) in a low viscosity bisphenol E cyanate ester
(BECy) thermosetting resin. In general, the dimensional stability of composites can
be enhanced by reducing the differences in the CTE between polymer matrix and
fiber. The high CTE of the polymer matrix and the low CTE of the fiber leads to
development of residual stresses and matrix microcracking. A potential strategy to
diminish these residual stresses involves development of polymer nanocomposites
with well dispersed nanoparticles that reduce the extent of disparity in CTE. The
authors verified that the incorporation of up to 10 vol% whisker-like nanoparticles
results in a 20 % reduction in the CTE of the polymer matrix.
Xing et al. [62] development an UV-curing flame retardant film, which consisted
of epoxy acrylate resin (EA) used as an oligomer, tri(acryloyloxyethyl) phosphate
(TAEP) and triglycidyl isocyanurate acrylate (TGICA) used as flame retardants
(FR). The authors also used alpha-zirconium phosphate α-Zr (HPO4)2H2O (α-ZrP)
for reinforced the flame retardancy and improve the thermal properties of the films.
They observed that the peak heat release rate (PHRR) and heat release capacity
(HRC) of the nanocomposites were significantly reduced. The incorporation of 1, 3
and 5 wt% of α-ZrP reduced the PHRR in 57, 50 and 47 % respectively, mean-
while, the HRC were reduced in 58, 52 and 47 %, respectively. According to the
authors, the α-ZrP nanoparticles could further retard the degradation of polymer
matrix due to the dispersion of α-ZrP exfoliated or intercalated nanometer sheets.
This was due the films formed were more effective protective char layer and reduce
the release rate of inflammable gas.
Bora et al. [63] prepared nanocomposites based on graphene oxide (GO) and
unsaturated polyester resin (UPR). They verified that the incorporation of 3 wt% of
GO improved the major degradation temperature of polyester from 230 to 285 °C.
This improvement in thermal stability was attributed to the strong interaction
between GO and UPR which restricts the mobility of the polymer matrix segments
at the interface. The interaction may be attributed to the formation of hydrogen
bonding between oxygen functionality on reinforcement and polymer or probably
dipolar interactions between the two components.
Arasa et al. [64] developed thermosetting nanocomposites prepared from
diglycidyl ether of bisphenol and c-valerolactone with different organically
Thermal Degradation of Thermosetting Nanocomposites 65
Ablation is the process of removing material from a surface or other erosive process
and usually associated with materials for space reentry vehicles and rocket nozzles
[65–67]. Ablative materials represent the traditional approach to thermal protection,
used for over 40 years in a broad range of applications [68]. The ablative materials
are used as thermal protection materials for rocket nozzles, space vehicles and
combustion chambers of rocket motors. These materials should withstand very high
temperatures in the order of thousands of degrees Celsius, generally between 1000
and 4000 °C, highly thrust and high impact resistance. The final material should be
able to form complex shapes and be as light as possible. Currently, the main
consumers of ablative materials are military, NASA and commercial space
launching company [65].
Most ablative thermal protection system (TPS) materials are reinforced com-
posites where organic resins are used as matrices. When heated, the resin pyrolyzes
generating gaseous products, mostly composed by hydrocarbons that permeate the
solid diffusing toward the external heated surface and proceed into the boundary
layer, where the heat transfer processes take place. The resin pyrolysis also pro-
duces a carbonaceous residue, indicated as char. The process is typically endo-
thermic and pyrolysis gases are heated as they percolate toward the surface, thus
transferring energy from the solid to the gas [68]. The transformations and energy
accommodation mechanisms of an ablative TPS material are schematically illus-
trated in Fig. 3. The entering of the pyrolysis gases into the boundary layer modifies
its properties, generally producing a reduction of convective heating. However, the
gases may undergo chemical reactions with the boundary layer gases, thus influ-
encing the net heat transfer to the surface. Furthermore, chemical reactions can
result in consumption of the surface material leading to surface recession [67–69].
Two categories of ablative materials are available: melting and non-melting
types. In melting type (represented by thermoplastics), the liquid is removed
immediately after formation and new surface is exposed, thus the thermal protection
66 M. Poletto et al.
erosion of the higher loaded CNF-NRAM without the rayon fabric was 42 % lower
than MX-4926. However, the residual mass of MX-4926 was higher in comparison
of CNF-NRAMs. Additionally, the surface temperatures of the CNF-NRAM
samples were higher than that of MX-4926.
Liu et al. [72] used POSS nanomodification in phenolic resin with carbon fiber
reinforcement. SEM analysis showed the production of best charred surface on
burnt samples that enhanced the ablation performance. Novel flake graphite was
introduced into barium-phenolic resin by Yu and Wan [73]. Nanocomposites were
made by roller-coating technology and its ablation property was tested under long
pulse laser radiation. Nanocomposites showed better ablation performance com-
pared to the control system. It was also observed that the size of the graphite flake
affected the ablation rate [73]. Srikanth et al. [74] prepared ablative nanocomposites
by introducing nanosilica into the phenolic resin with carbon fiber reinforcement.
Ablation resistance of nanocomposites increased with the nanosilica content up to
2 wt%. However, beyond this point ablation resistance decreased.
The ablation performance, thermal decomposition and temperature distribution
through the thickness of asbestos/phenolic composites modified with layered sili-
cate were compared with traditional asbestos/phenolic composites by Bahramian
et al. [75]. Nanofillers were introduced at 3, 4 and 6 wt% content ratio. Samples
were tested at the heat flux of 900 W/cm2. The 6 wt% nanocomposite samples
showed the best ablation performance. Natali et al. [70, 76, 77] produced two
different mixtures, both consisting of 50 wt% phenolic matrix (PR) and 50 wt%
nanofiller. One of them with carbon black (CB) referred to as PR-CB, constituted
by 50 %-PR and 50 %-CB. The other with MWCNTs, constituted by 50 %-PR and
50 %-MWCNTs referred to as PR-MWCNT. Their analyses included thermo-
gravimetric analysis, evaluation of the heat capacity, oxy-acetylene test, and the
post burning morphology. They observed better performance in nanomodified
samples. Koo et al. [78] prepared ablative nanocomposites by using MMT or-
ganoclay, POSS and CNF with and without carbon fibers in a phenolic resin. The
combination of high loading of MMT organoclay, low loading of POSS, and high
loading of CNF in phenolic resin showed better ablation performance than control
carbon/phenolic composite.
Recently, Srikanth et al. [79] development thermal protection system (TPS)
materials using 3.5, 6.5 and 9.5 wt% of zirconia dispersed in a resol based phenolic
resin. The results showed that the presence of zirconia has increased the ablation
rate. This is probably due to enhanced conversion of solid char into zirconium
carbide (ZrC) and carbon monoxide leading to under protection of the carbon fibers
facing the plasma jet used. In another work, Chen et al. [80] improved ablation
resistance of carbon-phenolic composites by introducing zirconium diboride (ZrB2)
particles. Results indicated that the employed method of introducing ZrB2 into
carbon-phenolic composites could profoundly improve the ablation performance.
The linear ablation rate of ZrB2 carbon-phenolic composites reduced by 79 % in
comparison with carbon-phenolic composites.
68 M. Poletto et al.
The massive use of polymer materials in our everyday life is driven by their
remarkable combination of properties, low weight and ease of processing. How-
ever, polymers are also known for their relatively high flammability; most often
accompanied by the production of corrosive or toxic gases and smoke during
combustion [81, 82]. Consequently, improving the fire retardant behavior of
polymers is a major challenge for extending their use to most applications. Safety
requirements are currently becoming more and more drastic in terms of polymers’
reaction to fire and their fire resistance performances. And various flame retardant
additives, such as halogenated additives, are being phased out for their proven or
suspected adverse effects on the environment [81]. The combined challenge thus
consists in developing effective and environmentally friendly flame retardant sys-
tems for polymer materials [81–83].
Many polymer composites ignite when exposed to high heat flux, releasing heat
that can, in some circumstances, contribute to the growth of the fire. Significant
quantities of smoke and toxic fumes may also be released, respectively limiting
visibility and posing a health hazard [81, 83]. For these reasons, stringent fire
regulations govern the use of composites in aircraft, ships, buildings, land transport,
oil and gas facilities, among other applications. These regulations require that the
fire reaction properties reach specified levels [81, 83]. The reaction properties that
are often used to define the fire hazard include the heat release rate (HRR), time-to-
ignition and flame spread rate [81, 82]. These properties are important because they
influence the temperature and spread of a fire. Other important properties include
smoke density and yield of carbon monoxide gas because these determine sur-
vivability [82, 83].
Of the many fire reaction properties, it is generally recognized that HRR is the
single most important in controlling fire hazard. HRR is defined as the mass loss
rate of the material times its heat of combustion. The amount of heat released from a
polymer composite is controlled by the combustion of flammable gas products
resulted from the decomposition of the organic components [82]. The resin matrix
is generally the main source of flammable volatiles. The reactions of the polymers
generally used in composites are endothermic, so these reactions absorb heat.
Therefore, the net HRR is a complex property determined by the heat generated by
the decomposition reactions of the volatiles released by the decomposing composite
less the heat absorbed by the endothermic decomposition reactions of the polymer
matrix [82, 83].
Cone calorimetry (CC) is one of the most effective medium-sized polymer fire
behavior tests. The principle of cone calorimeter experiments is based on the
measurement of the decreasing oxygen concentration in the combustion gases of a
sample subjected to a given heat flux, in general from 10 to 100 kW/m2 [83].
Figure 4 illustrates the experimental set-up of a cone calorimeter. Standardized in
the United States (ASTM E 1354), the cone calorimeter test is also the subject of an
international standard (ISO 5660).
Thermal Degradation of Thermosetting Nanocomposites 69
The sample is placed on a load cell in order to evaluate the evolution of mass loss
during the experiment [81]. A conical radiant electrical heater uniformly irradiates
the sample from above [81, 82]. The combustion is triggered by an electric spark.
The combustion gases produced pass through the heating cone and are captured by
means of an exhaust duct system with a centrifugal fan and a hood [81]. The gas
flow, oxygen, CO and CO2 concentrations and smoke density are measured in the
exhaust duct. The measurements of the gas flow and oxygen concentration are used
to calculate the quantity of heat released per unit of time and surface area: HRR is
expressed in kW/m2. The evolution of the HRR over time, in particular the value of
its peak/maximum (PHRR or HRRmax), is usually taken into account in order to
evaluate the fire properties [81–83]. The calculation is based on Huggett’s obser-
vation that most organic materials release a quantity of heat practically proportional
to the quantity of oxygen consumed while burning [81]. Integration of the HRR
versus time curve gives the total heat released (THR)—expressed in kJ/m2 [81, 82].
In addition, the cone calorimeter test also enables characterization of the time to
ignition (TTI), time of combustion or extinction (TOF), mass loss during combus-
tion, quantities of CO and CO2 and total smoke released (TSR) [81, 84].
Nowadays a variety of nanoparticles have been used to fabricate fire retardant
nanocomposites with improved mechanical and functional properties. The common
70 M. Poletto et al.
8.2.1 Nanoclays
Jash and Wilkie [86] reported that even when the fraction of clay was as low as
0.1 wt% the PHRR in a cone calorimeter was lowered by 40 %. Lee et al. [87]
demonstrated that incorporation of 6, 8 and 10 wt% of MMT into epoxy resin
increased linearly the char yield from 9.1 to 15.4 % reducing the thermal degra-
dation of the epoxy matrix. Nazaré et al. [88] studied the flammability properties of
unsaturated polyester resin with nanoclays using cone calorimetry. The authors
verified that the incorporation of 5 wt% of nanoclays reduces the PHRR by
23–27 % and THR values by 4–11 %. While incorporation of condensed-phase
flame retardants (such as ammonium polyphosphate, melamine phosphate and
alumina trihydrate) reduce the PHRR and THR values of polyester resin, the
inclusion of small amounts of nanoclay (5 % w/w) in combination with these char
promoting flame retardants causes total reductions of the PHRR of polyester resin
in the range 60–70 %. Ammonium polyphosphate, in particular and in combination
with polyester-nanoclay hybrids show the best results compared to other flame
retardants.
Frache et al. [89] development epoxy resin composites based on a hydrotalcites,
[Mg0.67Al0.33(OH)2][CO3]0.165·0.5H2O, containing 5 wt% of hydrotalcites. The
sample containing the hydrotalcite showed a decrease of 30 % in the PHRR during
cone calorimetry tests. Pereira et al. [90] evaluated the flame retardant behavior of
unsaturated polyester (UP) nanocomposites based on layered double hydroxides
(LDH). Two different organo-LDH were used (adipate-LDH (A-LDH) and
2-methyl-2-propene-1-sulfonate–LDH (S-LDH)) using 1 and 5 wt% of reinforce-
ment. The fire reaction study, using CC, reveals a reduction in the flammability of
UP resin in 46 and 32 % by incorporating 1A-LDH and 5S-LDH, respectively. The
incorporation of a relatively low amount of organomodified nanoclay in the
Thermal Degradation of Thermosetting Nanocomposites 71
Rahatekar et al. [92] observed that an addition of only 0.0025 wt% of highly
aligned MWCNTs showed a 45 % reduction in the peak mass loss rate during
gasification of epoxy/MWCNTs composites when compared with neat epoxy.
Reduction in peak of mass/heat release rate is an important factor in controlling
flame spread. The authors attribute this effect to highly aligned MWCNTs which
can be easily exfoliated using high shear mixing. Zhao and Gou [93] developed
multifunctional thermoset composites with polyester resin, glass fiber and CNF
sheets. The authors also observed that lower quantity (0.38 wt%) of CNF sheets
lowered the HRR.
Lee et al. [87] observed that the addition of 1 wt% of MWCNT into epoxy resin
clay nanocomposites increased the char yield from 15.4 to 19.5 % demonstrating
the synergistic effects of MMT/MWCNT additives. It is well known that char yield
generated on a surface can act as a heat barrier and thermal insulator. Thus, the
increased char yield is expected to reduce the degradation of the epoxy polymer.
The limit oxygen index (LOI) defined as the minimum fraction of O2 in a gas
mixture of O2 and N2 that will support flaming combustion of the samples was also
investigated. LOI showed a similar trend with char yield, with additives increasing
the oxygen content required for ignition, making it more difficult to ignite the
additives/epoxy resin complexes. The layered structured network formed by MMT
and MWCNTs likely played an important role as a shield by re-emitting the oxygen
radicals from the surface of epoxy to outside, decreasing the rate of polymer
degradation.
Wu et al. [94] incorporated SWCNT and MWCNT membranes (buckypaper)
and CNF paper onto the surface of epoxy carbon fiber composites. The authors
observed that SWCNT buckypaper and CNF paper did not show notable
improvement on fire retardancy. However, MWCNT buckypaper acted as an
72 M. Poletto et al.
effective flame retardant shield and reduce the PHRR by more than 60 % and also
reduce smoke generation by 50 % during combustion.
According to Im et al. [95] at temperatures above 250 °C the thermal oxidation
rate of a polymer depends on oxygen radical initiation through hydrogen abstraction
by oxygen in MWCNT and MMT fire retardant nanocomposites. However, the play
of oxygen radicals can be hindered by the formation of a thin protective film of
MWCNT/carbon char generated by oxidative dehydrogenation on the surface of the
epoxy complex, as can be seen in Fig. 5. It is assumed that the free radical scav-
enger effect of MWCNTs is the main reason for the improvement in the thermal
stability of the epoxy resin. Thus, the main role of MWCNTs on the surface of an
epoxy complex is the formation of compact charred layers promoted by MWCNTs
acting as a heat barrier and as thermal insulation. Even though the charred layer acts
as a heat barrier and as thermal insulation, MWCNTs primarily promote the gen-
eration of a charred layer through the excellent thermal conductivity of MWCNTs.
The thermal energy from the outside can be dispersed well by the presence of
MWCNTs, generating the charred layer effectively.
MWCNTs inside the epoxy resin also play an important role in the flame
retardant properties. Flame retardation by MWCNTs may hinder the spread of fire
to other places due to the formation of gel-type epoxy resin even during combustion
[95]. A clay such as MMT has a high specific heat; thus, MMT can act as a heat
storage medium [87, 95]. During combustion of the complex, the applied thermal
energy can be stored in MMT and hinder the spread of thermal energy to the epoxy
resin [87, 95].
8.2.3 Silsesquioxane
POSS with phenyl groups, the PHRR is decreased by 40 % in this case as compared
to 25 % for isobutyl-based POSS network. It was demonstrated that POSS na-
noclusters induced an effective fire retardant effect, which was controlled by several
factors. The authors showed that POSS bearing phenyl bonds were far more
effective than POSS with isobutyl bonds. Also, the presence of a chemical linkage
between the phenyl-based POSS clusters and the matrix favored the dispersion of
the nanoclusters, resulting in enhanced fire retardancy. The fire retardant effect was
only slightly enhanced by increasing the amount of POSS nanoclusters. The authors
also verified some interesting information by visual observation of the end of test
residues. On cross sections of the residues, it can be seen that the phenyl POSS
nanoclusters form during combustion a solid sponge-like structure. This structure is
not formed on neat epoxy network or in presence of isobutyl containing POSS
clusters. Remarkable reduction of HRR values observed for phenyl POSS hybrid
networks is likely to be due to the presence of this char layer formed during
combustion. The char layer generated is thought to act as a barrier for both heat
flow and mass transport.
Wu et al. [97] synthesized a named functional POSS (NPOSS) with two epoxy
ring groups via the reaction between trisilanolisobutyl-POSS and triglycidyl isoc-
yanurate. Then a halogen-free epoxy composite containing silicon/nitrogen was
prepared. The results of microscale combustion calorimeter indicate that the pres-
ence of 10 wt% of NPOSS in epoxy resin can decrease its PHRR by about 30 %.
The authors believed that NPOSS can retards the movement and scission of
polymeric chains of epoxy resin and forms a stable charred layer in the condensed
phase to prevent the underlying materials from further combustion.
Zhang et al. [98] used cage-type octaphenyl silsesquioxane (OPS) and ladder-
type polyphenyl silsesquioxane (PPSQ) as flame-retardants into epoxy resin. For
the epoxy/OPS sample, a weak blowing-out effect, by which the sample self-
extinguished after around 45 s, was observed. For the epoxy/PPSQ however, no
such blowing-out effect was observed. The PHRR of epoxy/OPS is seen to be
reduced remarkably from 855 to 626 kW/m2. However, most unexpectedly, the
PHRR of epoxy/PPSQ was measured as 925 kW/m2, which is higher than that of
pure epoxy. The authors observed that OPS seemingly had a better flame retardancy
than PPSQ for pure epoxy. Therefore, it seems that the respective structures of OPS
and PPSQ play an important role in their flame retardancy and blowing-out effects
in epoxy. According to the authors, one possible explanation is in that once PPSQ
ladder chain may break down as like a zip is zipped even though the ladder
structure is very stable before zipping. The active broken segments of PPSQ
accelerate the decomposition of the epoxy matrix and cause high heat release.
Relatively, the OPS can produce limited broken segments when one OPS cage
breaks [98, 99]. The fire retardancy performances of the corresponding networks
appear to be more influenced by the nature of the non-reactive bonds borne by the
POSS cages, rather than the presence of a chemical linkage between POSS and
matrix. In the case of POSS containing phenyl-groups, the decrease in PHRR
observed has been ascribed to the initial tendency of the phenyl-containing POSS to
char when decomposing [96, 99].
74 M. Poletto et al.
Rallini et al. [100] modified epoxy matrix with boron carbide nanoparticles at 1 and
5 wt% concentrations and the nanostructured polymer was used as a matrix to
impregnate carbon fiber fabrics. The CC tests showed that even after the exposure
to a heat-flux of 50 kW/m2 for 600 s, the composite based on 5 wt% of boron
carbide exhibited residual structural integrity as well as significant reduction of the
HRR than the control sample. These benefits were related to the chemical reactions
of boron carbide when exposed to an oxidizing hyper-thermal environment. B4C
can react with oxygen to produce liquid boron oxide and carbon dioxide. Boron
carbide can also react with other combustion products of the polymeric matrix such
as carbon monoxide and water vapor to yield boron oxide and amorphous carbon.
In this way, the release of gaseous by-products can be reduced and a solid residue
can be produced, minimizing the volumetric shrinkage of the charring material. A
more resistant residue enabled the reduction of the degradation rate and reduced the
heat transmitted to the inner layers of the laminates thus improving both thermal
stability and fire resistance. Additionally, the glassy network produced by the liquid
boron oxide acted as a protective layer for the carbon fibers, inhibiting their oxi-
dation processes, and also serving as a high temperature adhesive that bound the
plies of the composite materials together. In another work, Wang et al. [101] also
observed that the incorporation of 10 wt% of boron particles into phenolic resin/
clay nanocomposites increases the decomposition temperature at about 42 °C when
compared with nanocomposites without boron particles. These results suggested
that the incorporation of boron is effective in promoting thermal stability and flame
retardancy of thermosetting nanocomposites.
Tibiletti et al. [102] incorporated nano-alumina and submicron alumina trihy-
drate particles into UP resin. Synergistic effects on thermal stability and HRR were
observed for combinations between both submicron filler and nanofiller. The best
result for fire behavior was obtained for a global loading of 10 wt% with an equal
mass ratio for both types of particles. Combining both particles leads to a 32 %
reduction in PHRR. These synergistic effects can be ascribed to physical effects
resulting from the arrangement of both kinds of mineral particles of very different
median size at the surface of the composite during polymer combustion and
ablation. The formation of this mineral barrier promotes catalytic effects ascribed to
the huge specific surface area of oxide nanoparticles.
9 Future Trends
10 Conclusions
References
1. Ornaghi Jr, H.L., Poletto, M., Zattera, A.J., Amico, S.C.: Cellulose. doi:10.1007/s10570-013-
0094-1
2. Pistor, V., Ornaghi Jr, H.L., Ferreira, C.A., Zattera, A.J.: J. Appl. Polym. Sci. 125, E462
(2012)
Thermal Degradation of Thermosetting Nanocomposites 77
3. Rossa, L.V., Scienza, L.C., Zattera, A.J.: Polym. Compos. 34, 450 (2013)
4. Pistor, V., Ornaghi, F.G., Ornaghi Jr, H.L., Zattera, A.J.: Mater. Sci. Eng. A 532, 339 (2011)
5. Pigatto, C., Almeida Jr, J.H.S., Ornaghi Jr, H.L., Rodríguez, A.L., Mahlmann, C.M., Amico,
S.C.: Polym. Compos. 33, 2262 (2012)
6. Romanzini, D., Lavoratti, A., Ornaghi Jr, H.L., Amico, S.C., Zattera, A.J.: Mater. Des. 47, 9
(2013)
7. Ornaghi Jr, H.L., Bolner, A.S., Fiorio, R., Zattera, A.J., Amico, S.C.: J. Appl. Polym. Sci.
118, 887 (2010)
8. Ornaghi Jr, H.L., da Silva, H.S.P., Zattera, A.J., Amico, S.C.: J. Appl. Polym. Sci. 125, E110
(2012)
9. Piazza, D., Lorandi, N.P., Pasqual, C.I., Scienza, L.C., Zattera, A.J.: Mater. Sci. Eng. A 528,
6769 (2011)
10. Ornaghi Jr, H.L., Pistor, V., Zattera, A.J., Non-Cryst, J.: Solids 358, 427 (2012)
11. Poletto, M., Zattera, A.J., Forte, M.M.C., Santana, R.M.C.: Bioresour. Technol. 109, 148
(2012)
12. Poletto, M., Zattera, A.J., Santana, R.M.C.: Bioresour. Technol. 126, 7 (2012)
13. Borsoi, C., Scienza, L.C., Zattera, A.J.: J. Appl. Polym. Sci. 128, 653 (2013)
14. Savage, G.: Eng. Fail. Anal. 17, 92 (2010)
15. Loutas, T.H., Panopoulou, A., Roulias, D., Kostopoulos, V.: Expert Syst. Appl. 39, 8412
(2012)
16. Júnior, J.H.S.A., Ornaghi Jr, H.L., Amico, S.C., Amado, F.D.R.: Mater. Des. 42, 111 (2012)
17. Ornaghi Jr, H.L., da Silva, H.S.P., Zattera, A.J., Amico, S.C.: Mater. Sci. Eng. A 528, 7285
(2011)
18. Romanzini, D., Ornaghi Jr, H.L., Amico, S.C., Zattera, A.J.: J J. Reinf. Plast. Compos. 31,
1652 (2012)
19. Romanzini, D., Ornaghi Jr, H.L., Amico, S.C., Zattera, A.J.: Mater. Res. 15, 415 (2012)
20. Poletto, M., Dettenborn, J., Zeni, M., Zattera, A.J.: Waste Manage. 31, 779 (2011)
21. Borsoi, C., Berwig, K.H., Scienza, L.C., Zattera, A.J.: Polym. Compos. 34, 967 (2013)
22. Chrissafis, K., Bikiaris, D.: Thermochim. Acta 523, 1 (2011)
23. Gangopadhyay, R., De, A.: Chem. Mater. 12, 608 (2000)
24. Yamamoto, T., Kanda, N., Non-Newton, J.: Fluid 1, 181 (2012)
25. Ray, S.S., Okamoto, M.: Prog. Polym. Sci. 28, 1539 (2003)
26. Carrado, K.A.: Appl. Clay Sci. 17, 1 (2000)
27. Melendez, I.M., Neubauer, E., Angerer, P., Danninger, H., Torralba, J.M.: Compos. Sci.
Technol. doi:10.1016/j.compscitech.2011.04.005
28. Lustig, S.R., Boyes, E.D., French, R.H., Gierke, T.D., Harmer, M.A., Hietpas, P.B., Jagota,
A., McLean, R.S., Mitcheli, G.P., Onoa, G.B., Sams, K.D.: Nano Lett. 3, 1007 (2003)
29. Scocchi, G., Posocco, P., Danani, A., Pricl, S., Fermeglia, M.: Fluid Phase Equilib. 261, 366
(2007)
30. Gilman, J.W.: Appl. Clay Sci. 15, 31 (1999)
31. Pandey, J.K., Reddy, K.R., Kumar, A.P., Singh, R.P.: Polym. Degrad. Stab. 88, 234 (2005)
32. Bikiaris, D.: Thermochim. Acta 523, 25 (2011)
33. Ollier, R., Rodriguez, E., Alvarez, V.: Compos. A 48, 137 (2013)
34. Bharadwaj, R.K., Mehrabi, A.R., Hamilton, C., Trujillo, C., Murga, M., Fan, R., Chavira, A.,
Thompson, A.K.: Polymer 43, 3699 (2002)
35. Becker, O., Varley, R.J., Simon, G.P.: Eur. Polym. J. 40, 187 (2004)
36. Carrasco, F., Pagès, P.: Polym. Degrad. Stab. 93, 1000 (2008)
37. Lakshmi, M.S., Narmadha, B., Reddy, B.S.R.: Polym. Degrad. Stab. 93, 201 (2008)
38. Saitoh, K., Ohashi, K., Oyama, T., Takahashi, A., Kadota, J., Hirano, H.: J. Appl. Polym.
Sci. 122, 666 (2011)
39. Xie, W., Gao, Z., Liu, K., Pan, W.-P., Vaia, R., Hunter, D., Singh, A.: Thermochim. Acta
339, 367 (2001)
40. Zheng, X., Wilkie, C.A.: Polym. Degrad. Stab. 82, 441 (2003)
41. Hwu, J.M., Jiang, G.J., Gao, Z.M., Xie, W., Pan, W.-P.: J. Appl. Polym. Sci. 83, 1702 (2002)
78 M. Poletto et al.
42. Leszczyńska, A., Njuguna, J., Pielichowski, K., Banerjee, J.R.: Thermochim. Acta 453, 75
(2007)
43. Leszczyńska, A., Njuguna, J., Pielichowski, K., Banerjee, J.R.: Thermochim. Acta 454, 1
(2007)
44. Xie, W., Gao, Z., Pan, W.-P., Hunter, D., Singh, A., Vaia, R.: Chem. Mater. 13, 2979 (2001)
45. Sahoo, N.G., Rana, S., Cho, J.W., Li, L., Chan, S.H.: Prog. Polym. Sci. 35, 837 (2010)
46. Abdalla, M., Dean, D., Robinson, P., Nyairo, E.: Polymer 49, 3310 (2008)
47. Ingram, S.E., Liggat, J.J., Pethrick, R.A.: Polym. Int. 56, 1029 (2007)
48. Guo, B., Jia, D., Cai, C.: Eur. Polym. J 40, 1743 (2004)
49. Gu, A., Liang, G.: Polym. Degrad. Stab. 80, 383 (2003)
50. Brnardić, I., Macan, J., Ivanković, H., Ivanlović, M.: J. Appl. Polym. Sci. 107, 1932 (2008)
51. Yang, K., Gu, M.: Polym. Eng. Sci. 49, 2158 (2009)
52. Liu, Y.-L., Wei, W.-L., Hsu, K.-Y., Ho, W.-H.: Thermochim. Acta 412, 139 (2004)
53. Montero, B., Ramírez, C., Rico, M., Barral, L., Díez, J., López, J.: Polym. Int. 59, 112 (2010)
54. Nagendiran, S., Alagar, N., Hamerton, I.: Acta Mater. 58, 3345 (2010)
55. Chatterjee, A., Islam, M.S.: Mater. Sci. Eng. A 487, 574 (2008)
56. Hackman, I., Hollaway, L.: Compos. A 37, 1161 (2006)
57. Arasa, M., Pethrick, R.A., Mantecón, A., Serra, A.: Eur. Polym. J 45, 1282 (2009)
58. Pinnavaia, J., Beall, G.W.: Polymer Clay Nanocomposites. Wiley, Chichester (2000)
59. Bafekrpor, E., Simon, G.P., Yang, C., Chipara, M., Habsuda, J., Fox, B.: Compos. A 46, 80
(2013)
60. Bafekrpor, E., Simon, G.P., Yang, C., Chipara, M., Habsuda, J., Fox, B.: Polymer 54, 3940
(2013)
61. Badrinarayanan, P., Kessler, M.R.: Compos. Sci. Technol. 71, 1385 (2011)
62. Xing, W., Jie, G., Song, L., Wang, X., Lv, X., Hu, Y.: Mater. Chem. Phys. 125, 196 (2011)
63. Bora, C., Gogoi, P., Baglari, S., Dolui, S.K.: J. Appl. Polym. Sci. 129, 3432 (2013)
64. Arasa, N., Pethrick, R.A., Mantecón, A., Serra, A.: Eur. Polym. J 46, 5 (2013)
65. Tate, J.S., Gaikwad, S., Theodoropoulou, N., Trevino, E., Koo, J.H.: J. Compos. 2013, ID
403656 (2013)
66. Ogasawara, T., Aoki, T., Hassan, M.S.A., Mizokami, Y., Watanabe, N.: Compos. A 42, 221
(2011)
67. Bahramian, A.R., Kokabi, M., Famili, M.H.N., Bheshty, M.H.: Polymer 47, 3661 (2006)
68. Pulci, G., Tirillò, J., Marra, F., Fossati, F., Bartuli, C., Valente, T.: Compos. A 41, 1483
(2010)
69. Laub, B., Venkatapathy, E.: International Workshop on Planetary Probe Atmospheric Entry
and Descent Trajectory Analysis and Science (2003)
70. Natali, M., Monti, M., Puglia, D., Kenny, J.M., Torre, L.: Compos. A 43, 174 (2012)
71. Koo, J.H., Stretz, H., Weispfenning, J.T., Luo, Z.P., Wootan, W.: AIAA Paper No AIAA-
2004-1996 (2004)
72. Liu, Y., Lu, Z., Chen, X., Wang, D., Liu, J., Hu, L.: Proceedings of the 4th IEEE
International Conference on Nano/Micro Engineered and Molecular Systems, p. 605 (2009)
73. Yu, Q.-C., Wan, H.: J. Inorg. Mater. 27, 157 (2012)
74. Srikanth, I., Daniel, A., Kumar, S., Padmavathi, N., Singh, V., Ghosal, P., Kumar, A., Devi,
G.R.: Scripta Mater. 63, 200 (2010)
75. Bahramian, A.R., Kokabi, M., Famili, M.H.N., Bheshty, M.H.: J. Hazard. Mater. 150, 136
(2008)
76. Natali, M., Monti, M., Kenny, J., Torre, L.: J. Appl. Polym. Sci. 120, 2632 (2011)
77. Natali, M., Monti, M., Kenny, J., Torre, L.: Compos. A 42, 1197 (2011)
78. Koo, J.H., Natali, M., Tate, J.S., Allcorn, E.: Int. J. Energ. Mater. Chem. Prop. 12, 119
(2013)
79. Srikanth, I., Padmavathi, N., Kumar, S., Ghosal, P., Kumar, A., Subrahmanyam, Ch.: Compos.
Sci. Technol. 80, 1 (2013)
80. Chen, Y., Chen, P., Hong, C., Zhang, B., Hui, D.: Compos. B 47, 320 (2013)
Thermal Degradation of Thermosetting Nanocomposites 79
81. Laoutid, F., Bonnaud, L., Alexandre, M., Lopez-Cuesta, J.-M., Dubois, Ph: Mater. Sci. Eng.
R 63, 100 (2009)
82. Mouritz, A.P., Mathys, Z., Gibson, A.G.: Compos. A 37, 1040 (2006)
83. Pavlidou, S., Papaspyrides, C.D.: Prog. Polym. Sci. 33, 1119 (2008)
84. Koo, J.H., Venumbaka, S., Cassidy, P.E., Fitch, J.W., Grand, A.F., Bundick, J.: Fire Mater.
24, 209 (2000)
85. Zhao, Z., Gou, J., Biett, S., Ibeh, C., Hui, D.: Compos. Sci. Technol. 69, 2081 (2009)
86. Jash, P., Wilkie, C.A.: Polym. Degrad. Stab. 88, 401 (2005)
87. Lee, S.K., Bai, B.C., Im, J.S., In, S.J., Lee, Y.-S.: J. Ind. Eng. Chem. 16, 891 (2010)
88. Nazaré, S., Kandola, B.K., Horrocks, A.R.: Polym. Adv. Technol. 17, 294 (2006)
89. Frache, A., Monticelli, O., Nocchetti, M., Tartaglione, G., Constantino, U.: Polym. Degrad.
Stab. 96, 164 (2011)
90. Pereira, C.M.C., Herrero, M., Labajos, F.M., Marques, A.T., Rives, V.: Polym. Degrad. Stab.
94, 939 (2009)
91. Gerád, C., Fontaine, G., Bellayer, S., Bourbigot, S.: Polym. Degrad. Stab. 97, 1366 (2012)
92. Rahatekar, S.S., Zammarano, M., Matko, S., Koziol, K.K., Windle, A.H., Nyden, M.,
Kashiwagi, T., Gilman, J.G.: Polym. Degrad. Stab. 95, 870 (2010)
93. Zhao, Z., Gou, J.: Sci. Technol. Adv. Mater. 10, 1 (2009)
94. Wu, Q., Zhu, W., Zhang, C., Liang, Z., Wang, B.: Carbon 48, 1799 (2010)
95. Im, J.S., Lee, S.K., In, S.J., Lee, Y.-S.: J. Anal. Appl. Pyrol. 89, 225 (2010)
96. Franchini, E., Galy, J., Gérad, J.-F., Tabuani, D., Medici, A.: Polym. Degrad. Stab. 94, 1728
(2009)
97. Wu, K., Song, L., Hu, Y., Lu, H., Kandola, B.K., Kandare, E.: Prog. Org. Coat. 65, 490
(2009)
98. Zhang, W., Li, X., Jiang, Y., Yang, R.: Polym. Degrad. Stab. 98, 246 (2013)
99. Zhang, W., Li, X., Jiang, Y., Yang, R.: Polym. Degrad. Stab. 96, 2167 (2011)
100. Rallini, M., Natali, M., Kenny, J.M., Torre, L.: Polymer 54, 5154 (2013)
101. Wang, D.-C., Chang, G.-W., Chen, Y.: Polym. Degrad. Stab. 93, 125 (2008)
102. Tibiletti, L., Longuet, C., Ferry, L., Coutelen, P., Mas, A., Robin, J.-J., Lopez-Cuesta, J.-M.:
Polym. Degrad. Stab. 96, 67 (2011)
103. Kumar, A.P., Depan, D., Tomer, N.S., Singh, R.P.: Prog. Polym. Sci. 34, 479 (2009)
104. Hojjati, F.H.M., Okamoto, M., Gorga, R.E.: J. Compos. Mater. 40, 1511 (2006)
105. Jancar, J., Douglas, J.F., Starr, F.W., Kumar, S.K., Cassagnau, P., Lesser, A.J., Sternstein, S.S.,
Buehler, M.J.: Polymer 51, 3321 (2010)
106. Paul, D.R., Robeson, L.M.: Polymer 49, 3187 (2008)
107. Pfaendner, R.: Polym. Degrad. Stab. 95, 369 (2010)
108. Fairbrother, A., Fairbrother, J.R.: Ecotox. Environ Safe 72, 1327 (2009)
109. Savolainne, K., Pylkkänen, L., Norppa, H., Falck, G., Lindberg, H., Tuomi, T., Vippola, M.,
Alenius, H., Hämeri, K., Koivisto, J., Brouwer, D., Mark, D., Bard, D., Berges, M.,
Jankowska, E., Posniak, M., Farmer, P., Singh, R., Krombach, F., Bihari, P., Kasper, G.,
Seipenbusch, M.: Saf. Sci. 48, 957 (2010)
110. Boczkowski, J., Lanone, S.: Adv. Drug Deliver. Rev. 64, 1694 (2012)
111. Savolainne, K., Alenius, H., Norppa, H., Pylkkänen, L., Tuomi, T., Kasper, G.: Toxicology
269, 92 (2010)
Effect of Thermo-oxidation
on the Mechanical Performance
of Polymer Based Composites for High
Temperature Applications
Sumana Ghosh
1 Introduction
S. Ghosh (&)
Bio-ceramics and Coating Division, CSIR–Central Glass and Ceramic Research Institute,
Kolkata 700 032, India
e-mail: [email protected]
effect on the thermal stability. The melting temperature of virgin LDPE and HDPE
decreased with the addition of 10 % LW. The melting temperature of virgin PP also
decreased with the addition of LW. Enthalpy of virgin polymers also decreased
with the addition of LW. This study proved the necessity of thermal stability for the
consolidation process of composite materials [9].
Hanu et al. [10] developed silicone polymer composites filled with mica, glass frit,
ferric oxide and/or a combination of these for electrical power cables and other high
temperature applications. The thermal stability of the polymer composites was
determined by thermogravimetric techniques, thermal conductivity and heat release
rate was measured by cone calorimetry. They investigated that fillers e.g. mica and
ferric oxide had stabilizing effect on the thermal stability of silicone polymer and they
lower the heat release rates during combustion. However, mica was only found to
increase time to ignition [10]. Conducting composite systems have been prepared by
Elyashevich et al. [11]. Microporous polyethylene films were obtained by melt
extrusion with subsequent annealing, uniaxial extension, and thermal fixation.
Polyaniline layers were formed by in situ polymerization of aniline onto polyethylene
porous support placed into the aqueous reaction mixture. Structural and chemical
transformations upon heating of these systems in air without any load application and
in vacuum under load have been investigated by thermo-mechanical tests, IR spec-
trometry and electron microscopy. Composite systems demonstrated a considerably
lower shrinkage upon heating than microporous polyethylene substrates. It has been
noted that the composites retained mechanical integrity on heating up to temperatures
much higher than the polyethylene melting point. It is concluded that thermo-
mechanical behavior of the composites is determined by the presence of polyaniline
phase on the surface and the bulk of polyethylene support [11].
Single-walled carbon nanotube (SWNT)–poly(vinylidene fluoride) (PVDF)
composites were fabricated by dispersion of SWNT in an aqueous surfactant solution,
followed by mixing with PVDF powder, filtration and hot pressing. The thermal
properties of the composites at various SWNT volume fraction up to 49 % were
investigated. The coefficient of thermal expansion (CTE) was decreased with increase
of the SWNT content. The thermal conductivity increased with temperature from 25
to 150 °C. The thermal conductivity did not enhance to the level required by heat sink
applications. The melting point was not affected significantly by the addition of
SWNT. The degree of crystallinity was increased and the decomposition temperature
of the matrix was decreased with increasing the amount of SWNT [12]. The thermal
stability of wood polymer composites made with extractive-free wood from four
different wood species was studied. Hot water (HW) extractives, ethanol/cyclohexane
(E/C) extractives and both types of extractives were eliminated. Composites of
LLDPE and 10 wt% of wood were prepared using poly vinyl alcohol-co-ethylene
(EVOH) as a compatibilizer. The thermal degradation behavior of the composites was
characterized with thermogravimetric analysis (TGA). In all the cases, the degrada-
tion temperatures increased after removal of the extractives. The removal of E/C
extractives was less effective in the thermal stability improvement than the removal of
HW extractives. The highest improvement on the thermal stability of WPCs was
achieved when both types of extractives (E/C and HW) were removed [13].
84 S. Ghosh
The thermal energy storage phase change materials (PCM) based on paraffin/
high density polyethylene (HDPE) composites were prepared by using twin-screw
extruder technique. The morphology and properties of the PCM composites based
on the flame retardant system with expanded graphite (EG) and ammonium poly-
phosphate (APP) were characterized by Scanning electron microscope (SEM),
Differential scanning calorimeter (DSC), Thermogravimetric analyses (TGA) and
Cone calorimeter tests. The SEM images showed that paraffin dispersed well in the
three-dimensional net structure formed by the HDPE. The EG and APP were well
dispersed in the PCM composites. The DSC measurements indicated that the
additives of flame retardant had little effect on the peak temperatures of phase
change and thermal energy storage property. The TGA results showed that the
loadings of the EG and APP increased the temperature of the maximum weight loss
and the charred residue of the PCM composites at 650 °C, which contributed to the
improved thermal stability properties. Cone calorimeter tests showed that the peak
of heat release rate (PHRR) decreased significantly. The homogeneous and compact
charred residue structure after combustion contributed to the enhanced thermal
stability, improved flammability and increased self-extinguishing properties of the
PCM composites [14].
Liu et al. [15] reported the effects of CNTs on the crystallization and melting
behavior, thermal stability and fire retardancy properties of polymer composites.
Finally, they assessed the challenges for the future and the research that needs to be
done to achieve high performance polymer/CNT composites [15]. Su et al. [16]
described the thermal degradation/stability of polymer–CNT composites and their
development trends. The thermal degradation of polymer–carbon nanotube (CNT)
composites plays a crucial role in determining their processing and applications.
The mechanisms of thermal degradation/stability improvement by carbon nano-
tubes are affected by the barrier effect, thermal conductivity of CNT, physical or
chemical adsorption, radical scavenging action, and polymer–nanotube interaction.
There is a huge scope to further investigate the thermal degradation of polymer–
CNTs [16]. Polymer nanocomposites are an important class of polymers that have
wide application in a number of different industrial sectors. Nanoscale fillers
include layered silicates (such as montmorillonite), nanotubes (mainly carbon
nanotubes, CNTs), fullerenes, SiO2, metal oxides (e.g., TiO2, Fe2O3, Al2O3),
nanoparticles of metals (e.g., Au, Ag), polyhedral oligomeric silsesquioxane
(POSS), semiconductors (e.g., PbS, CdS), carbon black, nanodiamonds, etc. The
thermal degradation mechanism of these nanocomposites is related to the kind of
used nanoparticles and its amount, the structure of the char formed during polymer
degradation, the gas impermeability of inorganic nanoparticles, which inhibit the
formation and escape of volatile byproducts during degradation and the interactions
between polymer reactive groups and inorganic nanoparticles [17].
Vadukumpully et al. [18] described the fabrication and characterization of ultra-
thin composite films of surfactant-wrapped graphene nanoflakes and poly(vinyl
chloride). Free-standing composite thin films were prepared by a simple solution
blending, drop casting and annealing route. A significant enhancement in the
mechanical properties of pure poly(vinyl chloride) films was obtained with 2 wt%
Effect of Thermo-oxidation on the Mechanical Performance … 85
enhanced the thermal stability of PDMS [23]. Composite bipolar plates based on
the proper mixing of multi-walled carbon nanotubes (MWNTs), synthetic graphite
particles and acrylonitrile–butadiene–styrene (ABS) powder have been produced by
hot compression molding [24]. Thermal stability of the composites was examined
by thermogravimetric analysis (TGA). The thermal behavior was little affected by
the addition of MWNTs [24]. New rigid polypropylene composite foams filled with
high amounts of flame-retardant systems based on synthetic hydromagnesite, a
basic magnesium carbonate obtained from an industrial by-product were developed.
The combination of hydromagnesite with an intumescent additive (ammonium
polyphosphate) and layered nanoparticles improved the thermal stability. In par-
ticular, the intumescent additive delayed the beginning of the thermal decomposi-
tion temperature and the layered nanoparticles split the second step of thermal
decomposition in a third peak observed at higher temperatures. Improved flame
retardancy was noted in the samples having the intumescent additive [25].
Fire safety properties of polymers were improved by using bismuth subcarbonate
((BiO)2CO3·xH2O) nanoplate, a bismuth-containing layered nanomaterial. The
introduction of (BiO)2CO3·xH2O (≤6.2 wt%) into poly(methyl methacrylate)
(PMMA) matrix by in situ polymerization method increased the thermal stability,
flame retardancy and smoke suppression properties remarkably. Moreover, the
onset degradation temperature and mid-point degradation temperature was
increased. On the other hand, peak heat release rate, total heat release, toxic volatile
organic products and smoke density was decreased. Morphological studies of
PMMA/(BiO)2CO3·xH2O nanoplate composites showed that (BiO)2CO3·xH2O
nanoplates were well dispersed in the PMMA matrix. Thermal decomposition
behaviors and char analysis demonstrated the catalytic charring effect of (BiO)2-
CO3·xH2O to PMMA matrix. The (BiO)2CO3·xH2O nanoplates combines several
flame-retardant strategies including the char formation, dilution effect of CO2 and
water, and physical barrier effect, and thus enhanced the thermal stability, flame
retardancy and smoke suppression of PMMA/(BiO)2CO3·xH2O composites
simultaneously [26]. Synthesis of reduced silanized graphene oxide/epoxy-poly-
urethane (EPUAs/R-Si-GEO) composites with enhanced thermal and mechanical
properties was reported by Lin et al. [27]. Graphene oxide (GEO) prepared from
natural graphite flakes was modified with methacryloxypropyltrimethoxysilane to
prepare silanized GEO (Si-GEO), and was then reduced by NaHSO3 to prepare R-
Si-GEO (partially reduced Si-GEO). EPAc/R-Si-GEO (R-Si-GEO/epoxy acrylate
copolymers) was synthesized via an in situ polymerization of R-Si-GEO and epoxy
acrylic monomers. EPUAs/R-Si-GEO was obtained by curing reaction between
EPAc/R-Si-GEO and an isocyanate curing agent. Thermal gravimetric analysis
(TGA), tensile strength, elongation at break, and cross-linking density measure-
ments showed that the thermal stability and mechanical properties of EPUAs/R-Si-
GEO were greatly enhanced by the addition of R-Si-GEO [27].
Simultaneous influence of polypropylene-graft-maleic anhydride (MAPP) and
silane-treated hemp fibers (HF) on morphology, thermal and mechanical prope-
rties of high-flow polypropylene (PP) modified with poly[styrene-b-(ethylene-
co-butylene)-b-styrene] (SEBS) was studied. Thermal stability of HF was improved
Effect of Thermo-oxidation on the Mechanical Performance … 87
after silane treatment and less than 2 % weight loss was observed at 240 °C in
composites with 30 wt% HF. Better dispersion of fibers and better efficiency in
enhancing static and dynamic mechanical properties of PP, doubling its strength
and stiffness were observed in composites with treated fibers compared to untreated
ones. High strength and stiffness were showed by PP modified with SEBS and
MAPP containing 30 wt% HFs. These composites were studied as an alternative to
conventional PP/glass fibers composites for injection molding of small to medium
auto parts [28]. Continuous fiber-reinforced polymers are now widely used in many
industries and provide properties that are superior to those of traditional ACSR
(aluminum conductor steel reinforced) cables [29]. Although composite core cables
show good performance in terms of corrosion, the contact of carbon fibers with
aluminum promotes galvanic corrosion, which affects the mechanical performance.
Three different types of fiber coatings were tested (phenol formaldehyde resin,
epoxy-based resin, and epoxy resin with polyester braiding). The use of epoxy resin
combined with polyester braiding provided the best resistance to the galvanic
corrosion. Investigation of thermal stability revealed that use of phenol formalde-
hyde resin resulted in a higher glass transition temperature. A post-cure process
applied to epoxy-based resin helped to achieve glass transition temperatures up to
200 °C [29]. The nanocomposite materials with polymeric matrices, especially
using layered silicates are an alternative to composites with conventional fillers.
The investigation regarding the presence of montmorillonite clay in the degradation
of polypropylene-montmorillonite nanocomposites (PP/OMMT) showed that the
clay contributed to the beginning of exothermic oxidation reactions and to the
kinetics decrease of volatile release and its formation [30].
resin composite material laminates and exposed in a muffle furnace of 300, 550,
700, and 800 °C for 5 min, respectively in order to study the effects of thermal
treatment on mechanical properties of the composites. After thermal treatments at
300, 550 and 700 °C for 5 min, the flexural strength was reduced by 17, 37 and
80 %, respectively, the flexural modulus was decreased by 5, 14 and 48 %,
respectively, and the interlaminar shear strength was lowered by 12, 48 and 80 %,
respectively. The phenolic resin began to pyrolyze and shrink resulting in the
irreversible damage of the composites after thermal treatment at 300 °C. After
thermal treatment at 550 °C, the phenolic resin pyrolyzed mostly. But the PBO fiber
had no obvious pyrolyze while the interface had severely broken. As the phenolic
resin formed amorphous carbonaceous and PBO fiber pyrolyzed mostly so the
mechanical properties dropped dramatically after thermal treatment at 700 °C. After
heating at 800 °C for 5 min, the fiber was nearly totally pyrolyzed and kept fibrous
carbonaceous and the specimen became very brittle [32].
The effect of thermo-oxidation on the local mechanical behavior of two polymer
materials was investigated through the employment of instrumented Ultra-Micro
Indentation (UMI) and Confocal Interferometric Microscopy (CIM). The UMI
curves gave good indication of the local short-time behavior whereas the CIM
observation provided some information about the long-time behavior. Significant
modification of the local mechanical behavior for both studied epoxy resins with
oxidation level was noted [33]. The effects of Cloisite 20A (C20A) nano-clay
compounding on the thermo-oxidative degradation and thermal oxidation induced
residual stresses were studied for a thermoset polymer. A variant of bismaleimide
(BMI) was used having high temperature airframe applications. Isothermal aging
experiments were conducted at 250 °C on nano-clay modified BMI with 3 wt%
C20A and baseline BMI in different oxygen environments (0, 20 and 60 % O2) for
more than 1000 h for the examination of the influence of nano-clay compounding
on the thermo-oxidative behavior of BMI. It was observed that nano-clay enhanced
the thermal stability of thermoset polymer BMI by reducing oxygen diffusion and
oxidative degradation during isothermal aging. A significant (*25 %) reduction in
the residual radial and hoop stresses for the 3 wt% C20A modified BMI was
observed because the dispersed nano-clay improved the resin shrinkage [34]. The
thermo-oxidation of carbon-fiber-reinforced polymers (CFRPs) exposed to high
temperatures up to 150 °C and high oxygen pressures up to 5 bars was investigated
[35]. Unidirectional IM7/977-2 composite specimens were aged at 150 °C under
atmospheric air and under oxygen pressure (1.7 bars and 5 bars). Degradation
phenomena was investigated through periodic tests after different aging times. The
thermo-oxidation-induced degradation strongly depends on aging time, distance
between fibers and partial oxygen pressure [35].
The chemical structure of ambient cured DGEBA/TEPA and thermal–mechanical
properties during thermo-oxidative aging were investigated. It was found to be dif-
ficult for this ambient cured DGEBA/TEPA system to cure completely even after a
long period. Dynamic Mechanical Thermal Analysis (DMTA) curves demonstrated a
post-cure reaction occurred in the early period of aging and then an additional tran-
sition peak emerged at a lower temperature, whose intensity increased with the aging
Effect of Thermo-oxidation on the Mechanical Performance … 89
time. The additional peak in DMTA curves were related to the lower molecule weight
compounds. X-ray Photoelectron Spectroscopy (XPS) results further demonstrated
that additional peak was formed due to the degradation of main chains near the sample
surface and the effect of oxidation increased with decreasing depth [36]. Vu et al.
reported [37] the effects of thermo-oxidation on matrix cracking in cross-ply [0/90]S
composite laminates. IM7/977-2 carbon/epoxy samples were firstly aged at 150 °C
under 1.7 bars of oxygen for 24, 48 and 96 h, respectively. Quasi-static tensile tests
were then carried out on un-aged and aged samples. The number of matrix cracks was
counted during the tensile tests to establish the evolution of the crack density with
respect to the applied stress. A numerical model was utilized to evaluate the critical
energy release rate of un-aged and aged laminates. A reduction of the critical energy
release rate of the aged samples was measured as compared to the un-aged samples
[37].
Fibre-reinforced polymers are subjected to the various ageing factors e.g. tem-
perature, pressure, oxygen or moisture during their service life, which generally
result in a decrease of their properties. Ammar-Khodja et al. [38] studied the
combined actions of two aging parameters such as temperature and oxygen.
Thermo-oxidation was analysed by ageing in air plain and multi-hole laminates for
9000 h. Since perforated panels had a greater surface exposed to the oxidative
environment the degradation due to oxygen was increased. Thermo-oxidative
ageing led to oxidation and cracking of the laminates surfaces, weight loss and
decrease of both compression and SBS failure strengths. The glass transition
temperature remained constant. Degradation was more prominent for the multi-hole
panels. Greater decrease of the physical and mechanical properties for these lam-
inates was observed [38]. High performance multifunctional composites can be
developed through the multi-scale hybridization of carbon nanotubes (CNTs) with
micro-particles in polymers. Li et al. [39] worked in this direction. In their work,
hybrid fillers comprised of CNTs directly grown on alumina micro-spheres by
chemical vapor deposition were incorporated into epoxy matrix that was then
reinforced with woven glass fibers. The hierarchical composites with 0.5 wt%
hybrid loading was observed to exhibit an improvement of 11 and 19 % in inter-
laminar shear strength and flexural modulus, respectively. Further, the glass tran-
sition temperature was increased by 15 °C and the storage modulus at 50 °C was
increased by 20 %. These are mainly attributed to the improvements of matrix
properties due to good dispersion of hybrids and their resistance towards the for-
mation and development of matrix cracks. This study revealed the potential of
multi-scale carbon hybrids in improving the mechanical and thermo-mechanical
properties of the fiber-reinforced composites [39].
Polymeric matrix composites should be properly designed to resist degradation
due to physical aging, chemical changes and thermo-oxidation for long term dura-
bility requirements at the elevated temperatures [40]. The interaction between oxi-
dation and damage during high temperature aging of polymeric matrix composites
was described by some researchers. They used carbon fiber-reinforced PMR-15
composites. The substantial oxidation growth was observed in the areas where dis-
crete cracking was present. Damage evolutions, the interaction of damage and oxygen
90 S. Ghosh
diffusivity are the critical factors, which must be considered for reduction of oxidation
growth in composite materials. A model-based analysis of the oxidation in com-
posites was presented to determine the relative effects of the matrix oxidation, role of
fiber and interface effects and that of the damage growth [40]. Gigliotti et al. [40]
carried out the modelling, simulation and experimental characterization of local
shrinkage strains and stresses induced by thermo-oxidation phenomena in the IM7/
977-2 carbon/epoxy composite material at elevated temperatures. A good agreement
was found between the simulated and measured profiles. Based upon the analysis of
the thermo-oxidation induced stress field it was understood that the environment has
an influence on the onset of damage in composite materials at elevated temperature
[41]. The thermo-oxidative degradation of polylactide (PLA) films was studied by
Rasselet et al. [42] between 70 and 150 °C. They have noted that the oxidative
degradation of PLA led to a random chain scission responsible for a reduction of the
molar mass. A correlation between molar mass and strain at break during oxidation
was established. PLA displays a brittle behavior when molar mass falls below
40 kg mol−1, which was in agreement with relationships linking the critical value for
embrittlement with the molar mass [42].
Researchers are trying to improve the physical properties of the CNT/epoxy
composites. Although carbon nanotubes (CNTs) have superior properties the
interfacial bonding between the CNTs and the polymer matrix is weak. Kim et al.
[43] treated CNTs by an acidic solution to remove impurities and subsequently by
amine treatment or plasma oxidation for the improvement of interfacial bonding and
dispersion of nanotubes in the epoxy matrix. The mechanical properties of the
modified CNT/epoxy composites and rheological properties of nanotube containing
epoxy resin were improved. This may be ascribed to the modification of CNTs,
which improved dispersion and interaction between the CNT and the epoxy resin
[43]. Latex mixing and co-coagulation approach followed by static hot-press and
twin roll mixing process was utilized to produce natural rubber (NR)-reduced
graphene oxide (rGO) composites. In this process, fine control of filler dispersion
was obtained and the composites exhibited a three-dimensional rGO network or
alternatively a homogeneous dispersion of single rGO platelets. The composites
with rGO segregated network had good resistance to oxygen and water vapor
permeation. As compared to pristine rubber and composites the mechanical prop-
erties were improved with the homogeneous dispersion of single rGO platelets. The
experimental results confirmed that the morphology of filler has a prominent
influence on the properties of natural rubber composites [44].
It is already established that thermal-oxidative degradation of the matrix can
strongly affect the apparent interfacial shear strength (IFSS) in glass fibre-poly-
propylene (GF–PP). Yang et al. [45] took different approaches to further investigate
this phenomenon. Strong dimensional dependence was noted in case of property
deterioration caused by the degradation. The degraded and non-degraded samples
were characterized in terms of the thermal mechanical properties and crystallinity in
order to determine the effect of polymer degradation on the measured IFSS.
Comparison of the degraded and non-degraded PP microbond samples for IFSS
clearly demonstrated the effect of thermal-oxidative degradation on adhesion [45].
Effect of Thermo-oxidation on the Mechanical Performance … 91
Dominkovics et al. [46] carried out several series of experiments to study the effect
of components on the stability of PP/layered silicate nanocomposites. The amount
of organophilic montmorillonite (OMMT) varied between 0 and 6 while that of
maleated polypropylene (MAPP) was between 0 and 50 vol%. The composites
were prepared in an internal mixer at 190 °C and mixing speed and time were
varied to investigate the effect of processing conditions on the stability. They
showed that both OMMT and MAPP accelerated degradation during processing
and deteriorated the properties of PP composites. Residual stability decreased
drastically with increasing amounts of both components while chain scission led to
the decrease of viscosity and inferior strength and deformability. The most probable
reason for decreased stability was the reaction of the components with the stabi-
lizers. Processing conditions has an influence on degradation considerably.
Increasing shear rate and longer residence times resulted in pronounced degrada-
tion. It can be said that the basic stabilization of commercial grade polypropylenes
is insufficient to protect the polymer against degradation. Additional stabilization
processing is required to obtain products with superior quality [46].
Bullions et al. [47] had reported the results of an investigation of thermal-oxidative
aging effects on the properties of a carbon fiber-reinforced high-performance phen-
ylethynyl-terminated poly(etherimide). Composite panels and neat resin samples
were aged at 204 °C in four different oxygen partial pressure environments such as 0,
2.84, 20.2, and 40.4 kPa with the aging time of 1750, 3500, and 5000 h. It was
observed that degradation was much less and minimal mass loss had taken place from
both composite and neat-resin specimens after the thermal-oxidative aging. However,
the transverse flexural strength decreased with increasing oxygen partial pressure and
aging time. The retention of transverse flexural strength was stated as a function of
oxygen partial pressure and aging time; retention was proportional to (aging time)0.29.
Profiles of Vickers Hardness across the cross sections of aged neat resin samples
showed severe degradation with increased oxygen partial pressure. It was noticed that
5000 h of aging led to increment of the glass transition temperature, which decreased
with increasing oxygen partial pressure [47].
4 Future Trends
polymer nanocomposites have been reported by the researchers [49]. The utilization
of modified graphene/graphene oxide in the fabrication of nanocomposites with
different polymer matrixes have been demonstrated. Different organic polymers
have been used to fabricate graphene filled polymer nanocomposites using various
methods. The percolation threshold can be achieved at very lower filler loading in
the case of modified graphene-based polymer nanocomposites [49].
Polybenzoxazine nanocomposites highly filled with nano-SiO2 particles were
investigated for their mechanical and thermal properties as a function of filler
loading. The nanocomposites were prepared by high shear mixing followed by
compression molding. Relatively high micro-hardness of the PBA-a/nano-SiO2
composites up to about 600 MPa was achieved. Finally, the significant increment in
the glass transition temperature (Tg) of the PBA-a/nano-SiO2 composites was also
observed with the ΔTg up to 16 °C at the nano-SiO2 loading of 30 wt%. The
resulting PBA-a/nano-SiO2 composite can be used as coating material in electronic
packaging or other related applications [50]. Aluminosilicates are important
materials for applications related to adsorbents, water softeners, catalysis and
mechanical and thermal reinforcement because of their high surface area, excellent
thermal and hydrothermal stability, high shape-selectivity and superior ion-
exchange capability. Recently, their use as polymer fillers has allowed their
application to innovative areas such as medical and biological fields as well as in
sensors, filtration membranes, energy storage and novel catalysis routes. Further,
wide versatility and tailoring possibilities of both filler and matrix indicates this area
to be promising technologies of the near future [51].
Single-polymer composites (SPCs) represent an emerging family within the
polymeric composite materials. SPCs are classified in respect to their composition
(one- and two-constituents), and preforms (non-consolidated and consolidated).
SPCs are composed of amorphous or semicrystalline matrices and semicrystalline
reinforcements. Methods to widen the temperature difference between the matrix-
and reinforcement-giving materials of the same polymer (one-constituent) or same
polymer type (two-constituent approach) have been investigated. The development
of SPCs is increased by the need of engineering parts in different applications
having low density and recyclability. Recently, development of SPCs is supported
by novel preform preparation, consolidation and production possibilities [52].
Research activities related to functionally graded materials (FGMs) are rapidly
increasing in recent years. The properties of carbon nanotubes such as high
strength, high stiffness, high aspect ratio and low density have made them an
excellent reinforcement for composite materials. Functionally graded carbon
nanotube reinforced composite (FG-CNTRC) materials are being focused now to
find out its prospect for future use [53].
Potential of nanocellulose has been established as the next generation renewable
reinforcement for the production of renewable high performance biocomposites by
the researchers. The tensile modulus and strength of most cellulose nanocomposites
has been reported linearly with the tensile modulus and strength of the cellulose
nanopaper structures. Uniform dispersion of individual cellulose nanofibres in the
polymer matrix may improve the composite properties [54]. In last few decades
Effect of Thermo-oxidation on the Mechanical Performance … 93
polymers due to their high modulus and potential for sustainable production. Xu
et al. [59] prepared CNC-based composites with a waterborne epoxy resin matrix
and characterized. The glass transition temperature (Tg) and modulus for the
composites increased with increasing CNC content. The tensile strength increased
from 40 to 60 MPa, suggesting good adhesion between epoxy and CNC surfaces
exposed to the matrix. Further, additional water content resulting from CNC
addition was not observed. Based on the experimental results it can be said that
CNCs can improve thermo-mechanical performance of waterborne epoxy poly-
mers. Thus, these polymer composites are promising as reinforcing fillers in
structural materials and coatings [59].
5 Conclusion
Acknowledgments The authors are grateful to Mr. K. Dasgupta, Director, CSIR–Central Glass
and Ceramic Research Institute (CSIR–CGCRI), Kolkata–700 032, India, for his kind permission
to publish this work.
References
1. Haque, M.H., Upadhyaya, P., Roy, S., Ware, T., Voit, W., Lu, H.: The changes in flexural
properties and microstructures of carbon fiber bismaleimide composite after exposure to a high
temperature. Compos. Struct. 108, 57–64 (2014)
2. La Mantia, F.P., Morreale, M.: Green composites: a brief review. Compos. A 42, 579–588
(2011)
3. Salavatian, M., Smith, L.: An improved analytical model for shear modulus of fiber reinforced
laminates with damage. Compos. Sci. Technol. 105, 9–14 (2014)
4. Yu, T., Jiang, N., Li, Y.: Functionalized multi-walled carbon nanotube for improving the flame
retardancy of ramie/poly(lactic acid) composite. Compos. Sci. Technol. 104, 26–33 (2014)
5. Srikanth, I., Padmavathi, N., Kumar, S., Ghosal, P., Kumar, A., Subrahmanyam, Ch.:
Mechanical, thermal and ablative properties of zirconia, CNT modified carbon/phenolic
composites. Compos. Sci. Technol. 1–7 (2013)
6. Bell, J.M., Goh, R.G.S, Waclawik, E.R., Giulianini, M., Motta, N.: Polymer-carbon nanotube
composites: basic science and applications. In: Cairney, J.M., Ringer, S.P., Wuhrer, R. (eds.)
Materials Forum, vol. 32, pp. 144–152 (2008)
7. Harle, S.M.: The performance of natural fiber reinforced polymer composites: review. Int.
J. Civ. Eng. Res. 5, 285–288 (2014)
8. Lee, B.L., Holl, M.W.: Effects of moisture and thermal cycling on in-plane shear properties of
graphite fibre-reinforced cyanate ester resin composites. Compos. A: Appl. Sci. Manuf. 27,
1015–1022 (1996)
9. Doh, G.-H., Lee, S.-Y., Kang, I.-A., Kong, Y.-T.: Thermal behavior of liquefied wood
polymer composites (LWPC). Compos. Struct. 68, 103–108 (2005)
Effect of Thermo-oxidation on the Mechanical Performance … 95
10. Hanu, L.G., Simon, G.P., Cheng, Y.-B.: Thermal stability and flammability of silicone
polymer composites. Polym. Degrad. Stab. 91, 1373–1379 (2006)
11. Elyashevich, G.K., Sidorovich, A.V., Smirnov, M.A., Kuryndin, I.S., Bobrova, N.V.,
Trchová, M., Stejskal, J.: Thermal and structural stability of composite systems based on
polyaniline deposited on porous polyethylene films. Polym. Degrad. Stab. 91, 2786–2792
(2006)
12. Xu, Y., Ray, G., Abdel-Magid, B.: Thermal behavior of single-walled carbon nanotube
polymer–matrix composites. Compos. A: Appl. Sci. Manuf. 37, 114–121 (2006)
13. Shebani, A.N., van Reenen, A.J., Meincken, M.: The effect of wood extractives on the thermal
stability of different wood-LLDPE composites. Thermochim. Acta 481, 52–56 (2009)
14. Cai, Y., Wei, Q., Huang, F., Lin, S., Chen, F., Gao, W.: Thermal stability, latent heat and
flame retardant properties of the thermal energy storage phase change materials based on
paraffin/high density polyethylene composites. Renew. Energy 34, 2117–2123 (2009)
15. Liu, T.X., Huang, S.: Morphology and thermal behavior of polymer/carbon nanotube
composites. Physical Properties and Applications of Polymer Nanocomposites, pp. 529–562.
Woodhead Publishing, Cambridge (2010)
16. Su, S.P., Xu, Y.H., China, P.R., Wilkie, C.A.: Thermal degradation of polymer–carbon
nanotube composites. Polymer–Carbon Nanotube Composites, pp. 482–510 (2011)
17. Chrissafis, D.B.: Can nanoparticles really enhance thermal stability of polymers? Part I: an
overview on thermal decomposition of addition polymers. Thermochim. Acta 523, 1–24
(2011)
18. Vadukumpully, S., Paul, J., Mahanta, N., Valiyaveettil, S.: Flexible conductive graphene/poly
(vinyl chloride) composite thin films with high mechanical strength and thermal stability.
Carbon 49, 198–205 (2011)
19. Sliwa, F., Bounia, N.E., Marin, G., Charrier, F., Malet, F.: A new generation of wood polymer
composite with improved thermal stability. Polym. Degrad. Stab. 97, 496–503 (2012)
20. Subramaniam, K., Das, A., Häußler, L., Harnisch, C., Stöckelhuber, K.W., Heinrich, G.:
Enhanced thermal stability of polychloroprene rubber composites with ionic liquid modified
MWCNTs. Polym. Degrad. Stab. 97, 776–785 (2012)
21. Boon, M.S., Serena Saw, W.P., Mariatti, M.: Magnetic, dielectric and thermal stability of Ni–
Zn ferrite-epoxy composite thin films for electronic applications. J. Magn. Magn. Mater. 324,
755–760 (2012)
22. Ray, S.S.: Thermal stability and flammability of environmentally friendly polymer
nanocomposites using biodegradable polymer matrices and clay/carbon nanotube (CNT)
reinforcements. Environmentally Friendly Polymer Nanocomposites, pp. 295–327. Woodhead
Publishing, Cambridge (2013)
23. Yang, D., Zhang, W., Yao, R., Jiang, B.: Thermal stability enhancement mechanism of poly
(dimethylsiloxane) composite by incorporating octavinyl polyhedral oligomeric
silsesquioxanes. Polym. Degrad. Stab. 98, 109–114 (2013)
24. de Oliveira, M.C.L., Ett, G., Antunes, R.A.: Corrosion and thermal stability of multi-walled
carbon nanotube-graphite-acrylonitrile-butadiene-styrene composite bipolar plates for polymer
electrolyte membrane fuel cells. J. Power Sources 221, 345–355 (2013)
25. Realinho, V., Haurie, L., Antunes, M., Velasco, J.I.: Thermal stability and fire behaviour of
flame retardant high density rigid foams based on hydromagnesite-filled polypropylene
composites. Compos. B Eng. 58, 553–558 (2014)
26. Jiang, S., Gui, Z., Shi, Y., Zhou, K., Yuan, B., Bao, C., Lo, S., Hu, Y.: Bismuth subcarbonate
nanoplates for thermal stability, fire retardancy and smoke suppression applications in
polymers: a new strategy. Polym. Degrad. Stab. 107, 1–9 (2014)
27. Lin, J., Zhang, P., Zheng, C., Wu, X., Mao, T., Zhu, M., Wang, H., Feng, D., Qian, S., Cai, X.:
Reduced silanized graphene oxide/epoxy-polyurethane composites with enhanced thermal and
mechanical properties. Appl. Surf. Sci. 316, 114–123 (2014)
28. Panaitescu, D.M., Vuluga, Z., Ghiurea, M., Iorga, M., Nicolae, C., Gabor, R.: Influence of
compatibilizing system on morphology, thermal and mechanical properties of high flow
polypropylene reinforced with short hemp fibers. Compos. B Eng. 69, 286–295 (2015)
96 S. Ghosh
29. Santos, T.F.A., Vasconcelos, G.C., de Souza, W.A., Costa, M.L., Botelho, E.C.: Suitability of
carbon fiber-reinforced polymers as power cable cores: galvanic corrosion and thermal
stability evaluation. Mater. Des. 65, 780–788 (2015)
30. Fitaroni, L.B., de Lima, J.A., Cruz, S.A., Waldman, W.R.: Thermal stability of
polypropylene–montmorillonite clay nanocomposites: limitation of the thermogravimetric
analysis. Polym. Degrad. Stab. 111, 102–108 (2015)
31. An, N., Tandon, G.P., Pochiraju, K.V.: Thermo-oxidative performance of metal-coated
polymers and composites. Surf. Coat. Technol. 232, 166–172 (2013)
32. Bian, L., Xiao, J., Zeng, J., Xing, S., Yin, C., Jia, A.: Effects of thermal treatment on the
mechanical properties of poly(p-phenylene benzobisoxazole) fiber reinforced phenolic resin
composite materials. Mater. Des. 230–235. Elsevier, Amsterdam (2014)
33. Minervino, M., Gigliotti, M., Lafarie-Frenot, M.C., Grandidier, J.C.: The effect of thermo-
oxidation on the mechanical behaviour of polymer epoxy materials. Polym. Testing 32, 1020–
1028 (2013)
34. Upadhyaya, P., Roy, S., Haque, M.H., Lu, H.: Influence of nano-clay compounding on
thermo-oxidative stability and mechanical properties of a thermoset polymer system. Compos.
Sci. Technol. 84, 8–14 (2013)
35. Vu, D.Q., Gigliotti, M., Lafarie-Frenot, M.C.: Experimental characterization of thermo-
oxidation-induced shrinkage and damage in polymer–matrix composite. Compos. A: Appl.
Sci. Manuf. 43, 577–586 (2012)
36. Li, K., Wang, K., Zhan, M., Xu, W.: The change of thermal–mechanical properties and
chemical structure of ambient cured DGEBA/TEPA under accelerated thermo-oxidative aging.
Polym. Degrad. Stab. 98, 2340–2346 (2013)
37. Vu, D.-Q., Gigliotti, M., Lafarie-Frenot, M.C.: The effect of thermo-oxidation on matrix
cracking of cross-ply [0/90]S composite laminates. Compos. A: Appl. Sci. Manuf. 44, 114–121
(2013)
38. Ammar-Khodja, I., Picard, C., Fois, M., Marais, C., Netchitaïlo, P.: Preliminary results on
thermo-oxidative ageing of multi-hole carbon/epoxy composites. Compos. Sci. Technol. 69,
1427–1431 (2009)
39. Li, W., Dichiara, A., Zha, J., Su, Z., Bai, J.: On improvement of mechanical and thermo-
mechanical properties of glass fabric/epoxy composites by incorporating CNT–Al2O3 hybrids.
Compos. Sci. Technol. 103, 36–43 (2014)
40. Pochiraju, K., Tandon, G.P.: Interaction of oxidation and damage in high temperature
polymeric matrix composites. Compos. A: Appl. Sci. Manuf. 40, 1931–1940 (2009)
41. Gigliotti, M., Olivier, L., Vu, D.Q., Grandidier, J.-C., Lafarie-Frenot, M.C.: Local shrinkage
and stress induced by thermo-oxidation in composite materials at high temperatures. J. Mech.
Phys. Solids 59, 696–712 (2011)
42. Rasselet, D., Ruellan, A., Guinault, A., Miquelard-Garnier, G., Sollogoub, C., Fayolle, B.:
Oxidative degradation of polylactide (PLA) and its effects on physical and mechanical
properties. Eur. Polymer J. 50, 109–116 (2014)
43. Kim, J.A., Seong, D.G., Kang, T.J., Youn, J.R.: Effects of surface modification on rheological
and mechanical properties of CNT/epoxy composites. Carbon 44, 1898–1905 (2006)
44. Yan, N., Buonocore, G., Lavorgna, M., Kaciulis, S., Balijepalli, S.K., Zhan, Y., Xia, H.,
Ambrosio, L.: The role of reduced graphene oxide on chemical, mechanical and barrier
properties of natural rubber composites. Compos. Sci. Technol. 102, 74–81 (2014)
45. Yang, L., Thomason, J.L., Zhu, W.: The influence of thermo-oxidative degradation on the
measured interface strength of glass fibre-polypropylene. Compos. A: Appl. Sci. Manuf. 42,
1293–1300 (2011)
46. Dominkovics, Z., Hári, J., Fekete, E., Pukánszky, B.: Thermo-oxidative stability of
polypropylene/layered silicate nanocomposites. Polym. Degrad. Stab. 96, 581–587 (2011)
47. Bullions, T.A., McGrath, J.E., Loos, A.C.: Thermal-oxidative aging effects on the properties
of a carbon fiber-reinforced phenylethynyl-terminated poly(etherimide). Compos. Sci.
Technol. 63, 1737–1748 (2003)
Effect of Thermo-oxidation on the Mechanical Performance … 97
48. Huang, W., Zou, B., Zhao, Y., Meng, X., Wang, C., Cao, X., Wang, Z.: Fabrication of novel
thermal barrier coating on polymer composites via the combined sol–gel/sealing treatment
process. Appl. Surf. Sci. 258, 9058–9066 (2012)
49. Kuilla, T., Bhadra, S., Yao, D., Kim, N.H., Bose, S., Lee, J.H.: Recent advances in graphene
based polymer composites. Prog. Polym. Sci. 35, 1350–1375 (2010)
50. Dueramae, I., Jubsilp, C., Takeichi, T., Rimdusit, S.: High thermal and mechanical properties
enhancement obtained in highly filled polybenzoxazine nanocomposites with fumed silica.
Compos. B Eng. 56, 197–206 (2014)
51. Lopes, A.C., Martins, P., Lanceros-Mendez, S.: Aluminosilicate and aluminosilicate based
polymer composites: present status, applications and future trends. Prog. Surf. Sci. 89, 239–
277 (2014)
52. Karger-Kocsis, J., Bárány, T.: Single-polymer composites (SPCs): status and future trends.
Compos. Sci. Technol. 92, 77–94 (2014)
53. Liew, K.M., Lei, Z.X., Zhang, L.W.: Mechanical analysis of functionally graded carbon
nanotube reinforced composites: a review. Compos. Struct. 120, 90–97 (2015)
54. Lee, K.-Y., Aitomäki, Y., Berglund, L.A., Oksman, K., Bismarck, A.: On the use of
nanocellulose as reinforcement in polymer matrix composites. Compos. Sci. Technol. 105,
15–27 (2014)
55. Kumar, A.P., Depan, D., Tomer, N.S., Singh, R.P.: Nanoscale particles for polymer
degradation and stabilization—trends and future perspectives. Prog. Polym. Sci. 34, 479–515
(2009)
56. Zandén, C., Luo, X., Ye, L., Liu, J.: A new solder matrix nano polymer composite for thermal
management applications. Compos. Sci. Technol. 94, 54–61 (2014)
57. Lee, K.-Y., Bismarck, A.: Creating hierarchical structures in cellulosic fibre reinforced
polymer composites for advanced performance. Natural Fibre Composites, pp. 84–102.
Woodhead Publishing, Cambridge (2014)
58. Yuan, B., Bao, C., Song, L., Hong, N., Liew, K.M., Hu, Y.: Preparation of functionalized
graphene oxide/polypropylene nanocomposite with significantly improved thermal stability and
studies on the crystallization behavior and mechanical properties. Chem. Eng. J. 237, 411–420
(2014)
59. Xu, S., Girouard, N., Schueneman, G., Shofner, M. L., Meredith, J.C.: Mechanical and
thermal properties of waterborne epoxy composites containing cellulose nanocrystals. Polymer
54, 6589–6598 (2013)
Analysis for Thermal Degradation
of a Polymer by Factor Analysis
Akifumi Uda
1 Introduction
A. Uda (&)
Advanced Technology Development Laboratory, Mizushima R&D Center,
Mitsubishi Chemical Corporation, Okayama, Japan
e-mail: [email protected]
In conventional analysis, one instance of analysis produces one data item, such as
single-value data (scalars) obtained by titration or weighing, or qualitative data
(category variables) obtained from a color reaction. Owing to advancements in
analysis instrumentation, vector data that indicate a series of profiles can be
obtained from one instance of analysis in chromatography or spectrometry.
Furthermore, matrix data are the result of processing in cases where hyphenated
analysis instruments are used or time-resolved spectral analysis is performed.
Deconvolution is the splitting of a single chromatograph (one-dimensional data) by
fitting multiple Gaussian functions, and the MCR method introduced here is a
technique for applying resolution to the analysis of two-dimensional matrix data.
sj ¼ ða1 ; a2 ; . . .; aN Þ ð1Þ
Fig. 2 XRD measured while providing perturbation that changes the crystal lattice layer spacing
Curve resolution techniques include soft modeling and hard modeling. Hard
modeling is an approach formularized to the problem of fitting data to a hypothe-
sized function system described by parameters. To clarify the difference from the
hard modeling approach, curve resolution techniques employing soft modeling,
sometimes called self-modeling curve resolution (SMCR), are used.
The first study on curve resolution, carried out by Kaiser [1] in 1958, proposed
the varimax method, wherein factor rotation was used in factor analysis. Studies by
Lawton and Sylvestre of Kodak clearly picked up on curve resolution technology as
a means of reaction analysis in chemistry (1971, 1974) [2]. The idea of employing
rotating matrices was first used in iterative target transformation factor analysis
Analysis for Thermal Degradation of a Polymer … 103
X ¼ X1 þ X2 þ þ Xk ð3Þ
Fig. 5 The diagrammatic of resolved column vectors (scores) and low vectors (loadings)
Analysis for Thermal Degradation of a Polymer … 105
difference between the observed spectra X and the reconstructed spectra Xrec . The
numerical summation in the case of k components is shown in Eq. (4):
X
k
X ¼ CST ¼ ci sTi ¼ c1 sT1 þ c2 sT2 þ þ ck sTk þ E
i¼1 ð4Þ
¼ X1 þ X2 þ þ Xk þ E ¼ Xrec þ E
To illustrate the approach described in Sect. 2.3, data from IR spectra measured in
the thermal degradation of PVA was applied to the model. PVA is one of the most
environmentally benign polymers due to its biodegradability and thermodegrada-
bility [9, 10], existing as a semicrystalline polymer with two different states:
crystalline and amorphous. The crystalline phase changes its specific volume at
both the glass transition temperature Tg and the melting point Tm, but this semi-
crystalline polymer does not possess a clearly defined melting point [9, 11]. The
results of applying various analytical techniques (Fourier transform infrared spec-
troscopy (FTIR), thermogravimetry (TG), mass spectrometry (MS), and differential
scanning calorimetry (DSC) [11–13]) to such samples has determined that the
thermal degradation of PVA in both the molten and solid state produces volatile
saturated and unsaturated aldehydes and ketones at random [11]. Perturbed-corre-
lation moving-window two-dimensional (PCMW2D) correlation spectroscopy [13,
14] can be applied to analyze the degradation behavior in three regions: C–H
deformation (1200–1500 cm−1), C=O stretching (1500–1900 cm−1), and O–H
stretching (3500–3700 cm−1), but the properties of each region are discussed
separately. Although the temperature-dependent spectra contain detailed molecular
information about the thermal perturbation, extracting useful information from the
observed spectra is problematic due to the mixture of components and the over-
lapping of their spectra. To circumvent such problems, the MCR technique is
applied to two-way data such as the IR spectra in this case.
The PVA in Fig. 6a used in this experiment was purchased from Nacalai Tesque, Inc.
and is atactic with a degree of polymerization of 2.0 × 103 and a degree of saponi-
fication of 99–100 mol%. As the polymer backbone of PVA is formed by the
polymerization of vinyl acetate (Fig. 6b) before saponification, the tacticity of PVA
106 A. Uda
Fig. 6 Chemical structures of a poly(vinyl alcohol) and b poly vinyl acetate (Source [17])
Fig. 7 Temperature-
dependent IR spectra of a
PVA film
Analysis for Thermal Degradation of a Polymer … 107
The spectra resolved by the OPA approach are shown in Fig. 10; four concen-
tration profiles c1 c4 are shown in Fig. 10a, while Fig. 10b presents four spectral
patterns, sT1 sT4 ; from the temperature-dependent spectra of the PVA film [17].
Each pairing of concentration profile and spectral pattern (c1 sT1 ; c2 sT2 ; c3 sT3 ,
and c4 sT4 , respectively) corresponds to the polymer phases 1, 2, 3, and 4, respec-
tively which were alluded to briefly in Fig. 5. The concentration matrix C includes the
column vectors c1 c4 , and spectral matrix S includes the row vectors. The product of
c1 (m × 1) and sT1 ð1 nÞ makes an (m × n) matrix X1 ð¼ c1 sT1 Þ for the first
chemical component. Using the same procedure, the remaining components
Fig. 10 a Concentration
profiles and b spectra patterns
obtained by MCR from the
temperature-dependent IR
spectra of the PVA film
(Reprinted from [17])
Analysis for Thermal Degradation of a Polymer … 109
Fig. 11 a Observed spectra, b resolved spectra, c reconstructed spectra and d residues (A part
reprinted from [17])
Fig. 12 (A) Spectrum, (B) concentration and (C) spectral changes in polymer phase 1
elimination of adjacent hydroxyl units. Two sharp peaks at 1141 and 1095 cm−1 in
the fingerprint region are associated with C–O stretching modes from the crystalline
and amorphous phases, respectively [18]. The absorbance ratio D1141/D1095 is well
known as an index for the degree of crystallinity [14, 19, 20]. As the ratio increases,
the density and the degree of crystallinity also increase. Furthermore, the ratio of
two peaks at 916 and 850 cm−1 (D916/D850) is used as an indicator for the amount of
syndiotacticity in the polymer structure [21]. To summarize the assignment of
spectrum s1: given (i) the broad O–H peak at ca. 3390 cm−1, (ii) no newly formed
C=O peaks, and (iii) the crystallinity and syndiotacticity, component 1 exhibits the
features of the crystalline structure of PVA as the polymer phase.
The spectra for the second component are presented in Fig. 13; the spectrum s2, the
concentration profile c2 and the 3D map of the generated matrix X2 ð¼ c2 sT2 Þ are
presented analogously to Fig. 12. Comparing spectrum s2 with spectrum s1 (shown
in Fig. 12), it can be seen that the O–H stretching band is shifted by 70 cm−1 to a
higher wavenumber and occurs at 3460 cm−1. Hydroxyl groups yield broad peaks
when they engage in strong hydrogen bonding, due to variations in strength of the
hydrogen bonds. As the hydrogen bonds weaken via the thermal degradation of
the polymer backbone, the O–H stretching peak becomes sharp when released from
Analysis for Thermal Degradation of a Polymer … 111
Fig. 13 (A) Spectrum, (B) concentration and (C) spectral changes in polymer phase 2
Spectrum s3 of the third chemical component can be seen in Fig. 14, showing the
concentration profile c3, together with the 3D map of the generated matrix
X3 ð¼ c3 sT3 Þ. The O–H stretching band in spectrum s3 is shifted to 3500 cm−1
and, in comparison with spectrum s1, the absorbance decreases to one-third of the
corresponding band. The CH2 bending band at 1430 cm−1 decreases further in
spectrum s3. Although the C–O stretching band at 1095 cm−1 (attributed to the
amorphous phase) does not change significantly in phase 2, it decreases almost
completely in phase 3. Conversely, the C=O stretching peak at 1713 cm−1
approximately doubles in intensity, while a new shoulder emerges at 1772 cm−1.
The features of spectrum s3 suggest the polymer backbone in the third phase is close
to collapse, resulting in the rapid and formation of C=O groups.
Spectrum s4 of the fourth chemical component is shown in Fig. 15, presenting the
concentration profile c4 and the 3D map of the generated matrix X4 ð¼ c4 sT4 Þ in
the same form as the three previous phases. In the fourth phase, the O–H stretching
band at 3500 cm−1 becomes very weak and the CH2 bending band at 1430 cm−1
decreases significantly. Conversely, the peak at 1772 cm−1 approximately doubles
in intensity compared with the corresponding peak in spectrum s3, while an intense
Fig. 14 (A) Spectrum, (B) concentration and (C) spectral changes in polymer phase 3
Analysis for Thermal Degradation of a Polymer … 113
Fig. 15 (A) Spectrum, (B) concentration and (C) spectral changes in polymer phase 4
new peak at 1740 cm−1 appears. These peaks imply the formation of a large number
compounds containing C=O groups, such as saturated aldehydes and ketones,
aromatic aldehydes and ketones [22, 23], and unsaturated aldehydes and ketones by
a combination of cross-linking and Diels-Alder cycloaddition reactions [11–13].
The band observed in spectra s2 and s3 at 1601 cm−1 increases by about three times
in spectrum s4.
Expanded spectra for s1 -s4 are shown for the 800–1900 and 2600–3700 cm−1
regions in Fig. 16a, b [17].
The vibrational modes based on the same atomic group are labeled with the same
character; for example, the OH bands are labeled J1, J2, J3, and J4. Similarly, the
CH bands are labeled with K1, K2, K3, K4, and K5; pyrolytic carbonyl C=O bands
with L1, L2, and L3; and C–O bands with M1, M2, M3, and M4 to group char-
acteristic peaks together.
Although the bands labeled J1–J3 are assigned to OH stretching modes, the
bands become very broad due to the intermolecular interactions of OH groups. The
three peaks, s1: J3 (3390 cm−1); s2: J2 (3460 cm−1); and s3: J1 (3500 cm−1)
gradually decrease in intensity and shift to a higher wavenumber, disappearing
entirely in phase 4. In this group J (Fig. 16a), it is noteworthy that peak sharpening
is not observed, while the shift to higher wavenumber due to a decrease in the
intermolecular hydrogen bonding of OH groups with temperature is observed. This
114 A. Uda
Fig. 16 Enlarged IR spectra from S1 to S4, a 3700–2600 and b 1900–1800 cm−1 regions (A part
modified from [17])
behavior suggests that the OH elimination from the polymer backbone occurs
before releasing from the H-bonding interaction. Peak J4 (1325 cm−1), assigned to
the OH bending mode, also decreases, which further corroborates OH elimination.
Group K arises due to saturated hydrocarbon CH units. Bands K1 (2940 cm−1)
and K2 (2908 cm−1) are derived from an adjacent hydrogen CH2 stretching mode.
Band K3 (1430 cm−1) corresponds to the CH2 bending mode, while band K4
(1376 cm−1) is assigned to the CH bending mode. These modes K1–K4 possess
vibrations characteristic of hydrogen bonded directly to the polymer backbone.
Analysis for Thermal Degradation of a Polymer … 115
Figure 20a shows the ordinal relationship between the specific volume and the
crystalline melting point, crystalline phase, and amorphous phase of the polymer.
Figure 20b [17] plots the crystallinity estimated every 5 °C by IR spectra [13]. From
195 °C, the crystallinity decreases rapidly, indicating the onset of melting; the
figure shows that the bulk of the material was transformed into the amorphous
phase at ca. 220 °C. Figure 20c [17] is the same concentration matrix C (shown in
Fig. 10a) resolved by MCR from 140 to 280 °C. The c1 profile in Fig. 20c
resembles the decreasing crystallinity profile in Fig. 20b, and the peak temperature
of c2 fits the point where the crystallinity rapidly decreases at ca. 195 °C. The
profile c3 increases above 195 °C (the point the crystallinity begins to fall) before
decreasing after passing a peak at 240 °C. Although profile c4 increases at ca.
220 °C, the temperature is consistent with the ending of the transition to the
Analysis for Thermal Degradation of a Polymer … 117
Fig. 20 a Specific volume, b crystallinity, c MCR profile, and d stacked profiles (Reprinted
from [17])
amorphous state (shown in c1). From these results, the temperature of 220 °C
implies the melting point, Tm (Fig. 20a).
Figure 20d [17] presents the stacking of profiles c1–c4 shown in Fig. 20c. The
stacking ratio of c1 at 140 °C is about 55 % (=1.273/2.312 × 100), consistent with
the crystallinity in Fig. 20b implying that the c1 profile represents the polymer prior
to the decomposition of the solid state (crystalline phase). As the thermal motion
increases with temperature, the crystalline phase is changed into the amorphous
phase of the rubber state, caused by the release of intramolecular interactions.
Shortly afterward, the amorphous phase becomes a fluid state, before the gradual
onset of thermal degradation. Comparing the similar or dissimilar peaks in spectra
s2 and s3 with the corresponding profiles c2 and c3, phases 2 and 3 are suggested to
be in rubber (amorphous) and molten states, respectively. It is clear that phase 4 is
consistent with polymer thermal degradation residues. A semicrystalline polymer
adopts a mixed phase structure containing both crystalline and amorphous phases.
When each phase possesses a different degradation time by melting, they evolve
into states of coexistence. In an ordinal approach, only examining a mixture of
peaks is possible. When MCR is utilized, the mixture of peaks is resolved into the
inherent components, and the four essential outlines emerge. The difference in the
stacked amounts between the beginning and end is due to the formation of volatile
degradation products at the expense of the semicrystalline starting material.
118 A. Uda
Group M in Fig. 16b has previously described two bands, M1 (1141 cm−1, derived
from the crystalline phase) and M2 (1095 cm−1, derived from the amorphous
phase). Two other bands, M3 (916 cm−1) and M4 (850 cm−1) are useful for esti-
mating the structural arrangement of PVA. As shown in Fig. 21a, PVA can adopt
three tacticities: (i) isotactic, (ii) syndiotactic, and (iii) atactic. It is known that the
absorbance ratio D916/D850 can estimate the amount of syndiotactic structure
[12, 19–21], as estimated by Eq. (5) [21]. By using the combination of the coef-
ficient range 72.4 ± 1.09 and the index range 0.430 ± 0.006, Fig. 21c [17] shows
four plots concerning the amount of syndiotactic structure.
Fig. 21 a Tacticity of PVA, b concentration profiles on four polymer phase and c change range of
the amount of syndiotactic structure (Reprinted from [17])
Analysis for Thermal Degradation of a Polymer … 119
M4 band (850 cm−1) disappears in the last stages of decomposition, whereupon the
absorbance ratio D916/D850 cannot capture the properties of the crystalline state.
4 Summary
References
21. Murahashi, S., Nozakura, S., Washimi, M., Yuuki, H., Hata, S.: J. Polym. Sci. Part B: Polym.
Phys. 4, 65 (1966)
22. Gilbert, J.B., Kipling, J.J.: Fuel 12, 249–260 (1962)
23. Tsuchiya, Y., Sumi, K.: J. Polym. Sci. Part A: Plym. Chem. 7 (1969)
Radiation Effects on Polymer-Based
Systems
Traian Zaharescu
Abstract The applications of the radiation processing involve the deep modifica-
tions in the irradiated materials starting with molecular scissions. The specific
answers illustrate the progress of chemical changes onto the foreseen goals, which are
related to the exposure parameters: dose, dose rate, environment. The type of bonds
influences the radiation resistance by their energies and the reactivities of interme-
diates are the main criterion on which the selection of technological purpose is based.
The initial structure of radiation processed material, the radiation stability of main
component, the proposed formulation or the manufacture conditions are responsible
for the amplitude of conversion or for the process yields. The essential aspects of
radiochemical behavior of processed polymers are related to the followed mecha-
nisms, which have particular features provided by material functionality. The main
processes involving radiation effects: crosslinking and grafting as well as degradation
are analyzed on different polymer structures, on various irradiation parameters, on the
material availabilities to high modification levels under high energy radiation
exposure. The radiation processing of polymers by their exposure to different types of
irradiation sources is presented for the illustration of general possibilities offered by
industrial applications. This review is relevant for the extension of applications which
can be adapted to several conditions. The presented examples are start points for
further studies in which raw materials can be changed as well as blend formulations.
The open directions are available based on the provided information.
1 Introduction
High energy radiation induces the “clean” modifications and efficient modification
source of many applications. Along the time, several books and reviews presenting
the effects induced during high energy irradiation were issued [1–11]. The energy
T. Zaharescu (&)
Department of Radiation Processing, National Institute or Electrical Engineering
(INCDIE ICPE CA), 313 Splaiul Unirii, P. O. Box 149, 030138 Bucharest, Romania
e-mail: [email protected]; [email protected]
Fig. 2 Penetration of
accelerated electrons versus
energy
• demi penetration L 50 (the distance on which the final dose is half of inlet
dose):
• demi penetration L50e (the distance on which local dose is half of inlet dose):
The formation of radical intermediates influences not only the chemical state
of irradiated polymers, but it brings also about physical characteristics: solu-
bility, fusion enthalpy, heat capacity, crystallinity, mechanical features, elec-
trical properties: permittivity, dielectric loss, breakdown tension, thermal
conductivity. The new formed structures may be unlike in comparison with
initial material, because intermolecular bridges, new organic functions
appeared on macromolecular backbones, general molecular order or free
volumes attain other values.
The formation of radical intermediates influences not only the chemical state
of irradiated polymers, but it brings also about physical characteristics: solu-
bility, fusion enthalpy, heat capacity, crystallinity, mechanical features, elec-
trical properties: permittivity, dielectric loss, breakdown tension, thermal
conductivity. The new formed structures may be unlike in comparison with
initial material, because intermolecular bridges, new organic functions
appeared on macromolecular backbones, general molecular order or free
volumes attain other values.
(4) dose conditions. The choice of dose values must be the result of material
stability. According with the formulation, with the state of stabilization, with
the chemistry of irradiation atmosphere, with the sample composition, with the
type of pretreatments, with the dose rate, the modifications occurred in
polymer substrate attains certain level, which is the consequence of simulta-
neous actions of experimental factors. Figure 3 proves the differences that
exist between the effect of dose rate. The increase of crosslinking starts from a
certain dose named gel dose. It keeps characteristic values. For example,
LDPE presents start gelation under irradiation at about 10–15 kGy, while
ethylene-propylene elastomers have measurable gel fraction from 5–8 kGy.
The presence of additives or crosslinkers modifies essentially the progress in
the radiolytical modification of polymers.
Fig. 4 Modification in oxidation rates of polymer systems (EPDM:PP), (white) EPDM, (light
grey) EPDM:PP = 80:20, (dark grey) EPDM:PP = 60:40, (black) EPDM:PP = 40:60, (hachured)
EPDM:PP = 20:80
γ-irradiation, even the dose rate is at an acceptable level (10 kGy h−1) [26]. Though
electron accelerators suppose a large investment for the start, the further utilization
satisfies the technological requirements.
The great troublesome problem in the electron beam (EB) irradiation is the depth
of penetration [27], which depends not only by the incident particle energy, but also
on the material density. This problem can be solved by double face irradiation,
when exposure dose can be considered uniform along profundity [28]. The main
problem in the selection of the type of accelerator is the nominal power, which must
be rigorously correlated with its applications [29]. The factors that influence the
choice of accelerators are output power, energy of EB, room temperature for
accomplishment of process, number of passes and rate of conveyer [30]. A variety
of industrial electron accelerators can now provide electron energies from 0.3 MeV
to more than 10 MeV with average beam power capabilities up to 300 kW.
The monitoring of dose can be performed with different techniques: chemical
systems (Fricke and ceric solutions [31]), radiochromic compounds (dyes [32, 33]),
polymeric tapes (polyethylene [34], poly(vinyl chloride) [35, 36], poly(methyl
methacrylate) [37–40], epoxy resin [41]), radiation thermoluminescence phosphors
[42, 43]. Several requirements are imposed for a proper dosimeter: similarity with
processed material in respect with linear energy transfer, reproducibility, sensitivity,
lack of the influence of humidity, stability after irradiation, easy to calibrate,
appropriate dose range and dose rate, linearity and independency on the type of
radiation, the response being constant in time, lack of post-irradiation modification.
Each dosimeter has a certain dose range, on which the specificity recommends it
as proper system for accurate dose measurement [44]. Due to their easy availability,
handling and processing, polymers may be preferred [45]. For comparison, some
practical aspects of X-rays and gamma rays, such as product penetration, dose
uniformity, utilization efficiency and processing capacity were reported [46].
Industrial scale of radiation processing is accomplished also on the sterilization
of polymeric medical wear [47], food packaged in polymer bags [48] or electrical
insulation of wires and cables [49, 50]. The radiation technologies are based on the
possibility of attaining improved properties and extension of service life is attained.
2.1 Crosslinking
Starting from the crosslinking of polyethylene [51] the improvement in the functional
characteristics of polymers by crosslinking keeps various aspects. The general
overview on the involvement of free radicals that are formed during radiolysis
concerns the reactions of intermediates to each other or with oxygen [52]. The
accumulation of cured fraction or oxygen-containing products depends on the
reactivity of radicals. The accumulation of insoluble fraction, which consists of three
128 T. Zaharescu
where S is the soluble fraction that can be calculate for the abstraction of gelated
mass from total sample weight, P0 and Q0 represent the radiochemical yields of
scission and crosslinking, respectively, Pn,0 is the initial polymerization degree and
D is irradiation dose expressed in kGy. The ratio between radiochemical yield of
scission and radiochemical yield of crosslinking illustrates the availability of
polymers for crosslinking or degradation [52].
The content of gel fraction will influence material properties. The theoretical
approach starts with the the evaluation of radiochemical crosslinking yield:
where Gn(crosslinked units) represents the number of crosslinked units per 100 eV
absorbed energy, q0 is susceptibility of polymeric system to be crosslinked and w is
the average gravimetric weight of polymer. It is defined as the proportion of
crosslinked monomer for dose unit. Because the bridging takes place involving two
units, the radiochemical crosslinking yield is:
The last relationship can be used for the calculation of radiochemical yield of
crosslinking based on the measurement of average weight molecular weight.
The most commercialized polymer is polyethylene, which present a very good
stability under irradiation. Because there are manufactured different sorts of poly-
ethylene, they present unlike radiochemical strength.
The processability of polyolefins can be improved by the irradiation in
the presence of crosslinker, for example TAIC [53]. Many other polymers can
form efficiently increased amounts of insoluble fraction in the presence of vari-
ous functional crosslinkers: ethylene–vinyl alcohol copolymer with TAIC,
DEGDA, NPGDA and TMPTA [54] at maximum 65 % gel fraction at 200 kGy,
Radiation Effects on Polymer-Based Systems 129
intermediate maximum value, 10 % obtained at 30 kGy [68]. Even the total dose
increases at 70 kGy, the amount of insoluble fraction remained constant for the
studied formulation, PET/HDPE = 80/20. The best mechanical properties were
measured at this limit dose, 30 kGy. It was supposed that further irradiation of
crosslinked PET/HDPE systems the degradation by scission of new formed bonds
occurred. This behaviour can be found in the cases of components with different
structures and polarities.
The radiation technology applied for the modification of crystalline or semi-
crystalline polymers allows manufacturing crosslink shape-memory products [69].
The exposure to high energy radiation promotes crosslinking of cylindrical tubes at
certain dimensions. After heating the stain appears. This radiation processing can be
applied successfully to natural rubber [70, 71], polyethylenes [72–74], ethylene
vinyl acetate copolymer [75], poly(ε-caprolactone) [76]. The efficient crosslinking
of this kind of smart materials is attained, if the formulation contains a sensitizer
[77] or a multifunctional additive [78]. The applied dose in the systems consisting
of modifying polymer and additive is significantly lower than the nonmodified
compound, because the higher gel content is obtained much easier and the number
of crosslinks is higher. Consequently, the charge with which material presses inner
body is corresponding greater. The applications of SMPs cover different areas, for
example: medical treatment (tight immobilisation of tissues or bones, sterilisation),
electrical engineering (joint cables for continuous connection, electro-active sen-
sors, encapsulation of electronic parts), mechanical engineering (temperature
markers, assembling different equipment parts, fabrication of geometric structures),
handling and preservation of food, smart textiles [79, 80]. The shrinkability, the
accumulation of gel fraction, the convenient mechanical properties, the chemical
stability against oxidation are some features that must be shown by an appropriate
SMP [81].
In the medical praxis, UHMWPE have been used successfully as one half of the
bearing couple (against metallic alloys or ceramics) in total hip and total knee joint
replacements crosslinked under irradiation [82]. Even γ-irradiated UHMWPE at
doses higher than 100 kGy presents the incipient fracture development [83], the
alkyl macroradicals are involved in crosslinking and in a smaller proportion they
promote oxidation [84, 85]. The prosthesis manufactures by the irradiation of
UHMWPE have long durability, because the application of radiation treatment
induces an increased crystallinity and promotes sterilization in the whole volume of
material.
The functional properties of polymers can be ameliorated by the irradiation of
their nanocomposites [86, 87]. The addition of MWCNT to low density polyeth-
ylene increases the radiation resistance in comparison to the pure LDPE, which was
dependent on the MWCNT content [88]. WCNT nanocomposites were gamma
irradiated at 90 kGy to improve the interaction between MWCNTs and the polymer
matrix [89]. The irradiation produced a 38 % decrease in the toughness of neat
UHMWPE. The incorporation of MWCNTs did not significantly affect the melting
point of the neat UHMWPE but decreased the degree of crystallinity of the raw
UHMWPE, which was related to a reduction in the UHMWPE lamellar density.
Radiation Effects on Polymer-Based Systems 131
The tensile tests showed a 38 % increase in the Young’s modulus in the reinforced
nanocomposites and a small decrease in toughness (5 %). The addition of carbon
nanotubes in polypropylene brings about conductivities of the order of 10−2 S/cm,
but its scavenger effect reduces the number of radicals generated by irradiation,
lessening the strain hardening effect [90]. The presence of CB and silica in the
formulation of NBR/CSM blends at maximum concentration of 30 phr changed
satisfactorily polymer properties: 152 % increase in tensile strength, 116 %, in
elongation at break and 142 % modulus at 100 % elongation according to syner-
gistic effect between the fillers [91]. Ethylene-vinyl acetate copolymer (EVA) flame
retarded by a combination of intumescent flame retardants (IFR) and organically
modified montmorillonite (OMMT) crosslinked by EB irradiation shows a syner-
gistic effect of IFR and OMMT on the flame retardancy. With the addition of 1 wt%
OMMT and 24 wt% IFR, the LOI value of EVA/IFR/OMMT nanocomposite
increased from 30.5 to 33.5 % [92]. The reinforcement of polypropylene with 5 %
POSS after g-irradiation at 50 kGy showed improved thermal stability due to the
formation of crosslinked network between PP and POSS by radiation [93]. The
mixing carboxyl-terminated butadiene-acrylonitrile (CTBN) with nano-clay to
improve the toughness and mechanical strength of bisphenol A type epoxy fol-
lowed by further γ-irradiation at high doses (500, 1000 and 1500 kGy) has pointed
out the contribution of nanofiller to the stabilization by intercalation of macro-
molecules into clay layers [94].
Nanocomposites of two different kinds of rubber (acrylonitrile-butadiene rubber
NBR and styrene butadiene rubber SBR)/organo-montmorillonite nanocomposites
modified by hexadecyltrimethyl ammonium bromide have a remarkable resistance
when they are radiochemically processes in the presence of TMPTMA [95]. Similar
results were reported on epoxy resin modified with titania presents a very good
resistance to the thermal oxidation after receiving 50 kGy γ-dose [96]. The oxi-
dation in neat material starts quickly and progresses with a great oxidation rate. By
the addition of titania nanoparticles, the host resin presents a decreased oxidation
rates at filler concentrations up to 10 %. A very smooth oxidation takes place in
irradiated epoxy resin/titania hybrids because inorganic phase acts as efficient
adsorbent agent relative to the radicals formed during radiolysis.
One largely commercialized elastomer, EPDM, can attain improved tensile
strength, when it is irradiated as hybrid composites with nanoclay particles [97].
The reinforcement of filler in the case of ATH induced a de-cohesion inside
polymers with direct consequences on [98]. Moreover, at room temperature, i.e.
below the melting temperature, all the consequences of ageing by gamma irradia-
tion are strongly attenuated by the presence of a semi-crystalline microstructure, the
morphology of which is not too strongly modified by irradiation. The content of
silica nanoparticles modifies the kinetics of the degradation of EPDM substrate
through the complex modification of the filler–filler and filler–matrix interactions
involved in the mechanical properties of the filler network.
The differences that exist between polyolefins, namely LDPE, PP and EPDM in
the presence of various concentrations of silica demonstrate the structural contri-
butions of branching and unsaturation to the durability of this kind of
132 T. Zaharescu
Fig. 5 Transfer reactions caused by radiolytic hydroxyl radicals which are the start of hydrogel
formation
134 T. Zaharescu
(37 °C) following the mechanism described in Fig. 5. The macroradicals can appear
by the scission of C–H bonds of carbon atoms composing vinyl methyl ether
monomer. When system receives 10.5 kGy the average weight molecular weight
increases from 57.103 g mol−1 to about 106 g mol−1 [114].
The applications of hydrogels in the production of medical items, resulting
materials must have several features, which recommends them: non-toxicity,
functionability, sterilizability, biocompatibility [115]. These characteristics are
requires for wound dressings, drug delivery systems, transdermal systems, inject-
able polymers, implants, dental and ophthalmic applications, stimuli-responsive
systems, hydrogel hybrid-type organs.
Radiation processed PVA–polysaccharides hydrogels can be prepared at maxi-
mum dose of 30 kGy [116]. Using concentration of polysaccharides as low as 0.5–
2 % resulted in increase of tensile strength from 45 to 411 g cm−2, elongation from
30 to 410 % and water uptake from 25 to 157 % with respect to PVA gel without
polysaccharides. Formulations containing 7–9 % PVA, 0.5–1.5 % carrageenan and
0.5–1 % agar gave highly effective usable hydrogel dressings.
A series of antibacterial hydrogels were fabricated from an aqueous solution of
AgNO3, gelatine and carboxymethyl chitosan (CM-chitosan) by radiation-induced
reduction and crosslinking at ambient temperature [117]. For the total dose of
30 kGy, the gel fraction was situated around 75 % invariant relative to the concen-
tration of AgNO3, and diameter of particles was between 2 and 5 nm. The swelling
ratio is higher (90–100 %) at the concentrations of silver nitrate exceeding 1 %.
Hydrogel wound dressings have been prepared using the gamma rays irradiation
technique. The dressings are composed of poly(vinyl pyrrolidone) (PVP), poly
(ethylene glycol) (PEG) and agar [118, 119]. At 50 kGy the stress at break increases
with 40 %, while swelling degree is enhanced significantly with the concentration of
PEG and with the time of immersion. Interpenetrating polymer networks (IPNs) can
be synthesized by irradiating acrylonitrile solutions of poly(N-vinyl-2-pyrrolidone)
with Co-γ rays [120]. Thermal gravimetric analysis of resulting IPNs has proved the
enhancement in the stability of materials, which can be related to the intermolecular
bonds formed during irradiation. Polyvinyl alcohol and polyvinyl pyrrolidone
(PVA–PVP) blended hydrogel for wound dressing has been prepared by using
gamma rays irradiation. WVTR values of PVA–PVP blended hydrogel are around
80–200 g m−2 h−1, which place these radiation processed systems qualitatively above
commercial products [121].
The hydrogelmatrix can be obtained by γ-irradiation, which induces crosslinking
simultaneously with the in situ reduction of Ag+ ions initiated by the products of
water radiolysis (e−aq, OH−, H., H+, H2, H2O2). For the radiochemical gelation of
vinyl pyrrolidone two radical entities are involved in different proportion (Fig. 6).
The stress/strain representations are linear PVP and PVP/Ag+ hydrogels.
Obtained values of the effective crosslink density in the range of 52.8–54.0 mol m−3
and those corresponding to the molar mass between crosslinks in the range of 15.5–
15.9 kg mol−1 for pure PVP hydrogel prove the development of good hydrogel
Radiation Effects on Polymer-Based Systems 135
material. Similar results were reported for the hydrogel containing simultaneous
silver and gold ions for the increasing in the antibacterial activity [122].
The polyphenol trans-resveratrol is a natural phytoalexin, which is found in red
wine and in a wide variety of plant species. Resveratrol displays a wide array of
biological activities, such as modulation of lipid metabolism, anti-inflammatory and
antioxidant activities. The results of gel fraction and swelling degree were
approximately 90 and 1600 %, respectively for applied dose not exceeding 1 kGy
[123]. The swelling degree attains maximum value after about 6.5 h. These
information concerning the resveratrol stability suggest that it has showed no
structural decomposition by the primary and secondary radicals of water radiolysis.
The polymeric matrix composed by PVP, PEG and agar showed suitable physical
and chemical characteristics to resveratrol immobilization to compose a hydrogel
dressing for dermatological use.
Protein-crosslinking whether done by enzymatic or chemically induced path-
ways increases the overall stability of proteins. Papain, a proteolytic enzyme (EC
3.4.22.2) of biotechnological and biomedical relevance was selected for the
delivery of papain under γ-irradiation as globular crosslinked protein [124, 125].
The size of papain particles enlarges due to the radiation processing from 172 nm in
the case of nonirradiated ethanol solution to 910 nm after receiving 40 kGy. The use
of ethanol combines the protein aggregation, essential for the involved process and
radioprotection due to its intrinsic scavenger property, capturing specific radicals
generated by water radiolysis, known to cause a deep impact on protein integrity.
The applications of hydrogel in the retention of metal ions were intensively
studied [126]. pH-sensitive hydrogels based on poly(N-vinyl-2-pyrrolidon) (PVP),
acrylic acid (AAc) and styrene (Sty) were prepared by gamma irradiation [127].
PVP/(AAc-co-Sty) hydrogels were subjected to radiation modification to use them
as adsorbent materials for removal of heavy metal ions from aqueous solution. Effect
of functionalization of hydrogels by sulfonation (Sf), partial hydrolysis with alkaline
solution (NaOH) and treated with the two processes (NaOH/Sf) on metal ion uptake
was evaluated, and it results in appreciable uptake of Co2+, Cu2+ and Fe3+ ions from
aqueous solution.
In the same category of reports the drug delivery hydrogels can be considered
[128–133]. They must show some characteristics, which get them proper for foreseen
goals [134, 135]: the lack of homopolymer, the highest absorption capacity (maxi-
mum equilibrium swelling) in saline, desired rate of absorption (preferred particle
size and porosity) depending on the application requirement, the highest absorbency
under load and reasonable remote rate the highest durability and stability in the
136 T. Zaharescu
swelling environment and during the storage., the highest biodegradability without
formation of toxic species following the degradation, pH-neutrality after swelling in
water, colorlessness, odorlessness, and absolute non-toxic, photo stability, re-wetting
capability (if required) the hydrogel has to be able to give back the imbibed solution
or to maintain it; depending on the application requirement (e.g., in agricultural or
hygienic applications), low production price. The adequate usage of these hydrogels
in the post-operatory application is the adhesive features for easy withdrawing from
surgery intervention site [136].
The recycling of polymers receives a large attention because it solves two
problems, one is the economy of raw materials, and the other is the decrease of
environmental pollution. A review on the contribution of radiation processing to the
reclaiming polymer wastes were published previously [137]. The effects of an
electron radiation dose (up to 300 kGy) and compatibilizer on the Charpy impact
strength (σc) and tensile-impact strength (σt) of composites made of the following
recycled polymers: low-density polyethylene (LDPE), high-density polyethylene
(HDPE), polypropylene (PP), polystyrene (PS), and poly(ethylene terephthalate)
(PET) indicate the processing potential of radiation treatment applied to polymers
[138]. Styrene–ethylene/butylene–styrene elastomer grafted with maleic anhydride
(SEBS-g-MA) and trimethylol propane trimethacrylate (TMPTA) were used as the
compatibilizers, added at 10 and 1 wt%, respectively. It was found that, under the
influence of SEBS-g-MA, the values of σc and σt for the studied composites
increased by over three and almost five times, respectively. The electron radiation
and TMPTA had no noticeable effect on these quantities, which might be due to the
protective properties of aromatic rings included in the macromolecules of PS and
PET. It was demonstrated that the inclusion of SEBS-g-MA enabled achievement of
satisfactory impact strength of composites made of recycled polyolefins, PS and
PET, while it was not necessary to use the electron radiation and TMPTA.
Basically, the recovery of polymer wastes is based on the compatibilization,
when radiation acts as the radical formatting agent [64]. The radiation compatibi-
lization of high-density polyethylene (HDPE)/ethylene–vinyl acetate (EVA)
copolymer blends can be achieved, because the vinyl acetate content of EVA was
beneficial to radiation crosslinking [139]. The gel content has a maximum value at
30 kGy for all relative concentrations of components. The compatibility checked by
TGA investigations as well as mechanical properties showed that the two plastics
coexist homogeneously due to the intermolecular bridges appeared during irradi-
ation. At higher doses like 500 kGy, degradation of blends takes place.
Recycled and pristine low-density polyethylene samples were crosslinked by
60
Co gamma rays in the presence of two commercial sensitizers: trimethylolpro-
panetriacrylate (TMPTA) and trimethylolpropane trimethacrylate (TMPTMA), and
another laboratory-synthesized sensitizer, hexakisalylaminocyclotriphosphazatrine
(HAAP) [140]. The measurement of gel fraction revealed a light difference between
virgin and recycled LDPE, this discrepancy being duet to the accumulation of
degrading compounds. PET/HDPE blends can be processed by γ-ray irradiation
combined with using a cross-linking agent, TMPTA [68]. The specificity of this
process consists of the new structure, HDPE-g-PET proved by FTIR records. When
Radiation Effects on Polymer-Based Systems 137
the weight ratio of PET/HDPE blend was 80/20, the content of TMPTA was 1 wt%
and the absorbed dose was 30 kGy, the tensile strength, elongation at break and
impact strength of irradiated blends were improved greatly compared with non-
irradiated blends. Blends of high-density polyethylene (HDPE) can be crosslinked
by radiation processing with recycled and pristine polyethylene terephthalate (PET)
[141]. PET contains aromatic groups, which are effective at dissipation of the
energy of the ionizing radiation during γ-radiolysis forming a copolymer capable of
improving the compatibility of the blend HDPE/PET. The gel content differs for
one composition to the other, when PET loading varies from 50 to 30 %. The initial
lower amount of PET in the raw blend favorizes an advanced crosslinking level.
Radiation-induced compatibility behaviour of SBR–EPDM blends of different
composition was studied for intimate compatibilizing components [66]. The results
have shown that at a threshold dose of 10 kGy exists and good interaction between
the components of the blends was achieved. Higher radiation doses lead to for-
mation of crosslinked three-dimensional copolymer network, whose swelling
depends on the radiation dose imparted. The anomalous diffusion of solvent into the
gels was confirmed by rigorous treatment of the swelling data. Permeation data
agreement with the series model indicated that in SBR–EPDM blends EPDM exists
as continuous phase and SBR as dispersed phase.
The γ-processing of IIR gives the possibility of an efficient recycling of this
material. The sharp drop of weight average molecular weight (Fig. 7) is an eco-
nomical way for the manufacture of rubber ingredient used for toughening tire raw
materials [17].
The EB treatment of the GTR containing LDPE and EVA matrix blends showed
significant benefits. The 200 kGy EB absorbed dose (in air) resulted in a better
tensile strength and increased elongation at break, without changing the tensile
modulus, which provides more rubber-like properties [142]. The modest change in
hardness proves the cross-linking effect caused by the EB treatment in all cases. The
dynamic mechanical analysis confirmed the compatibilization effect of EVA and
2.2 Grafting
The association of new monomer onto macromolecules, which allows it, represents
the grafting process [150]. The great advantages of radiation processing in grafting
polymers are the initiation without catalyst and the simplicity of treatment, which
can be conducted in connection with the reactivities of monomer and substrate. The
connection of this outside structure brings different functional properties, with
which the application area can be enlarged. The incidental radiation provides
energy for the generation of reactive sites. Synthetic materials obtained by grafting
are proper alternative to blended polymers, which may satisfy the practice
requirements imposed in any certain service. High energy radiation substitute
chemical reagents, which creates active positions on macromolecules. Some
example of this kind of reactivity stimuli are ferrous ions in redox medium, cereous
ions, manganate ions in acid environment and many others. Their involvement in
redox processes causes the transfer of one electron for each ion from polymer
molecule and, consequently, the formation of free radicals, with carry on the
attachment of grafting entity.
Grafted copolymers can be obtained by several ways [1, 151–153]:
• the polymerization by addition of vinyl monomer M on polymer RR′,
• the reaction of two macroradicals appeared from two different polymer com-
ponents RR′ and R1R2,
• polycondensation of two macromolecules RR′ and R1R2, which have functional
groups that can react:
– direct grafting of vinyl monomer on polymer macromolecule,
– grafting catalysed by peroxyl structure appeared during radiolysis,
– initial grafting of trapped radicals,
– co-crosslinking of two different polymers by linking one type of macro-
molecule to other molecule from the second component.
Synthetic view on these routes is presented in Fig. 9. The application of grafting
procedure, one polymer substrate gains supplementary features, which allow it to be
used in particular conditions of operation. The new structure is regarded as a
combination between the two initial configurations, but the basic material exhibits
predominant characteristics. The grafted units correct some of undesirable prop-
erties, which are turned to the favourable behaviour. If grafting takes place in
solution, the participation of solvent molecules increases the conversion yield,
because they act as transporters of energy between radiation and irradiation envi-
ronment [154]. The pre-irradiation plays also an important role, because it forms
radicals, which become the process initiators.
The modification of polyethylene and cellulose by grafting of styrene and
acrylonitrile simultaneously present in polymer bulk allows the attaining of maxi-
mum grafting percentage at about 30 kGy by γ-irradiation [155]. In the samples
grafted with styrene no crosslinking were obtained. It could be concluded that when
the yield of grafting is very high in acrylonitrile, its termination occurs via the
140 T. Zaharescu
Fig. 10 Mechanistic scheme for the grafting of HEMA, GMA and DEM
and moderate doses, which interact with proton releasing units and provide suitable
concentration of charge carriers. The increase in the polymer stability and functionality
can be achieved by the grafting of various monomers, which induce a delocalization of
electrons to create new structures with less reactivities. The grafting of styrene on the
molecular configuration of polypropylene by gamma exposure [167] or EB treatment
[168], starch [169], PTFE [170], cellulose [171] makes possible to enlarge application
ranges onto the most aggressive conditions, because the benzene scavenge energy and
does not release it on the entire molecules. The initial concentration of styrene influ-
ences the rate of grafting. The preirradiation or the presence of monomer capable to
bind more efficiently styrene leads to high conversion of neat polymer, which must
contain an optimal concentration of 30 % styrene. The localization of energy on
benzene ring is also favourable to the compatibilization with different polymer struc-
tures that are less miscible with pristine polymer.
The high thermal stable polymers, fluorinated compounds, can be modified by
grafting under irradiation [172, 173]. The modification of PTFE, FEP and PFA with
styrene can be achieved at room temperature by the EB exposure in two steps. The
first irradiation was accomplished at high temperatures (385 °C for PTF, 350 °C for
PFA and 290 °C for FEP) for initiating grafting, where polymers were brought in
liquid state in nitrogen atmosphere. The next step was EB irradiation at 50 kGy for
the accomplishment of process. The maximum grafting yields were attained for
high preirradiation dose (500 kGy). The order of the increasing efficiency for these
polymers was PFA > PTFE > FEP because of their structures. For the proton
exchange membranes (PEM) PTFE was grafted by styrene under γ-irradiation in air
at room temperature. After the immersion in styrene, the grafting process was
performed at different temperatures. The grafting yields reached different levels
after 20 h of reaction: 76 % for 60 °C, 57 % at 80 °C, 22 % at 100 °C and 17 % at
120 °C. It seems that the lower temperature hinders the formation of homopolymer.
142 T. Zaharescu
Fig. 12 Changes in absorbances of carbonyl () and hydroxyl () bands recorded for EPDM/PP
blends. Blending ratios: a 80:20, b 60:40 and c 40:60
energies involved in radiation degradation follow similar trend, because the process
enthalpies are directly correlated with molecular sizes (Fig. 15).
The addition of nanoparticles in the material formulations represents the key of
polymer modification [193], which brings about the attaining upgraded perfor-
mances simultaneously with the compatibilization of various blends. The features
of polymer nanocomposites can be converted by high energy exposure and their
application can be extended due to the favorable adjustment.
4 Conclusion
fields: automotive industry, from interior and exterior car parts to tyres, sporting
goods, packaging, coatings, wire and cables, fuel cells, biomedical. The common
feature is the long term stability investigated by accelerated degradation under
irradiation. The interaction between basic polymer material and nanofiller compo-
nent turns the functional characteristics onto the foreseen behavior, but the level of
reinforcement depends strongly on the radiation stability of macromolecules.
Radiation processing is a tremendous way on which the filler is tightly incor-
porated in cured material. The main challenge in fabrication of these polymer
nanocomposites for industrial applications is uniform dispersion of nanoparticles in
the polymer matrix. For synthesis procedures, the scission of monomer promotes
the promising adjustment of stabilization. In contrast, the decomposition/degrada-
tion of polymer phase creates new structures, which are able to be adsorbed onto the
nanoparticle surface or they change the material properties to the unpredicted shift.
However, the radiation treatment allows the proper preparation of ameliorated
material in respect with conventional practice. During irradiation the basic aspects
of stability and functionality are the dose thresholds, over which the proportion of
degradation becomes evident.
The investigation achieved on the effect of nanofillers on the material durability
must consider the impact of degradation on environmental health and safety. The
post-irradiation stage of polymer hybrids pursues the long term operation under
optimal parameters. The research effort on radiation processed polymer nanocom-
posites emerges to beneficial applications even for nuclear industry that develops
crucial diminishment of degradation.
References
1. Chapiro, A.: Radiation Chemistry of Polymer Materials. Wiley Interscience Publishers, New
York (1962)
2. Clough, R.L.: Radiation-resistant polymers. In: Encyclopedia of Polymer Science and
Engineering, pp. 667–708, 2nd edn. Wiley, New York (1988)
3. Bhattacharya, A.: Radiation and industrial polymers. Prog. Polym. Sci. 25, 371–401 (2000)
4. Clegg, D.W., Collyer, A.A. (eds.): Irradiation Effects on Polymers. Elsevier Applied Science,
London (1999)
5. Woods, R.J.: Applied Radiation Chemistry: Radiation Processing. Wiley Interscience
Publishers, New York (1994)
6. Clough, R.L.: High-energy radiation and polymers. A review of commercial processes and
emerging applications. Nucl. Instrum. Meth. Phys. Res. B 185, 8–33 (2001)
7. Spinks, J.W.T., Woods, R.J. (eds.): Introduction to Radiation Chemistry, 3rd edn. Wiley,
New York (1990)
8. Dawes, K., Glover, L.C., Vroom, D.A.: The effects of electron beam and γ-irradiation on
polymer materials. In: Mark, J.E. (ed.) Physical Properties of Polymer, Handbook, 2nd edn.
Springer, New York (2007)
9. Makuuchi, K., Chang, S. (eds.): Radiation Processing of Polymer Materials and Its Industrial
Applications. Wiley, New York (2012)
Radiation Effects on Polymer-Based Systems 147
10. Zaharescu, T., Jipa S.: Radiochemical modifications in polymers. In: Arndt, K.F., Lechner M.
D. (eds.) Landolt-Börnstein Series, vol. VIII/6 C2, Polymer Solids and Polymer Melts,
pp. 95–184. Springer (2013)
11. Drobny, J.G.: Ionizing Radiation and Polymers: Principles, Technology, and Applications.
Elsevier, PDL Handbook Series (2012)
12. Cleland, M.R., Park, L.A., Chang, S.: Applications for radiation processes of material. Nucl.
Instrum. Meth. Phys. Res. B 208, 66–73 (2003)
13. Zaharescu, T.: Irradiation effects on ethylene-propylene elastomers in aqueous environment.
Polym. Test. 15, 69–74 (1996)
14. Gillen, K.T., Clough, R.L.: Polymer ageing insights available from modulus profiling data.
Polym. Eng. Sci. 29, 29–35 (1989)
15. Ershov, B.G., Gordeev, A.V.: A model for radiolysis of water and aqueous solutions H2,
H2O2, O2. Radiat. Phys. Chem. 77, 928–935 (2008)
16. Zaharescu, T., Giurginca, M., Setnescu, R.: The radiation stability of the ethylene-propylene
type rubbers during their gamma ray ageing. Rev. Roum. Chim. 40, 181–190 (1995)
17. Zaharescu, T., Jipa, S., Setnescu, R., Setnescu, T.: Radiation processing of polyolefin blends.
Part IV. Spectroscopic investigation on EPDM/PP blends. Nucl. Instrum. Meth. Phys. Res. B
265, 260–264 (2007)
18. Gehring, J.: With radiation crosslinking of polyolefin engineering plastics into the next
millennium. Radiat. Phys. Chem. 57, 361–365 (2000)
19. Chmielewski, A.G., Haji-Saeid, M.: Radiation technologies: past, present and future. Radiat.
Phys. Chem. 71, 16–20 (2004)
20. Chmielewski, A.G., Haji-Saeid, M.: IAEA Program in the field of radiation technology.
Nucl. Instrum. Meth. Phys. Res. B 236, 38–43 (2005)
21. Haji-Saeid, M., Sampa, M.H., Ramamoorthy, N., Güven, O., Chmielewski, A.G.: The role of
IAEA in coordinating research and transferring technology in radiation chemistry and
processing of polymers. Nucl. Instrum. Meth. Phys. Res. B 265, 51–57 (2007)
22. Haji-Saeid, M., de Sampa, M.H.O., Chmielewski A.G.: Radiation treatment for sterilization
of packaging materials. Radiat. Phys. Chem. 76, 1353 (2007)
23. Haji-Saeid M., Safrany, A., de Sampa, M.H.O., Ramamoorthy, N.: Radiation processing of
natural polymers: the IAEA contribution. Radiat. Phys. Chem. 79, 255–260 (2010)
24. Chmielewski, A.G., Al-Sheikhly, M., Berejka, A.J., Cleland, M.R., Antoniak, M.: Recent
developments in the application of electron accelerators for polymer processing. Radiat.
Phys. Chem. 94, 147–150 (2014)
25. Berejka, A.J., Cleland, M.R., Walo, M.: The evolution of challenges for industrial radiation
processing—2012. Radiat. Phys. Chem. 94, 141–146 (2014)
26. Berejka, A.J.: Radiation response of industrial materials: dose rate and morphology
implications. Nucl. Instrum. Meth. Phys. Res. B 261, 86–89 (2007)
27. Nablo, S.V., Chrusciel, J., Cleghorn, D.A., Rangwalla, I.: Factors influencing equipment
selection in electron beam processing. Nucl. Instrum. Meth. Phys. Res. B 208, 90–101 (2003)
28. Miller, A.: Approval and control of radiation processing, EB and gamma. Radiat. Phys.
Chem. 31, 385–393 (1988)
29. Cleland, M.R., Park, L.A.: Medium and high-energy electron beam radiation processing for
commercial applications. Nucl. Instrum. Meth. Phys. Res. B 208, 74–89 (2003)
30. Barnard, J.W.: Factors influencing equipment selection in electron beam processing. Nucl.
Instrum. Meth. Phys. Res. B 208, 98–101 (2003)
31. Charlesby, A. (ed.): Atomic Radiation and Polymers. Pergamon Press, New York (1960)
32. Farah, K., Kuntz, F., Kadri, O., Ghedira, L.: Investigation of the effect of some irradiation
parameters on the response of various types of dosimeters to electron irradiation. Radiat.
Phys. Chem. 71, 337–341 (2004)
33. Lavalle, M., Corda, U., Fuochi, P.G., Caminati, S., Venturi, M., Kovács, A., Baranyai, M.,
Sáfrány, A., Miller, A.: Radiochromic film containing methyl viologen for radiation
dosimetry. Radiat. Phys. Chem. 76, 1502–1506 (2007)
148 T. Zaharescu
34. Abdel-Fattah, A.A., Ebraheem, S., Ali, Z.Y., Abdel-Rehim, F.: Ultraviolet and infrared
spectral analysis of irradiated polyethylene films: correlation and possible application for
large-dose radiation dosimetry. J. Appl. Polym. Sci. 67, 1837–1851 (1998)
35. Castañeda Facio, A., Benavides, R., Martinez Pardo, M.E., Uribe, R.: Electron beam
crosslinking of non-lead PVC formulations. Radiat. Phys. Chem. 76, 1720–1723 (2007)
36. Peimel-Stuglik, Z., Fabisiak, S.: A comparison of the performance characteristics of four film
dosimeters in a 10-MeV electron beam. Appl. Radiat. Isot. 66, 346–352 (2008)
37. Whittaker, B., Watts, M.F.: Influence of dose rate, ambient temperature and time on the
radiation response of Harwell PMMA dosimeter. Radiat. Phys. Chem. 60, 101–110 (2001)
38. Seito, H., Ichikawa, T., Kaneko, H., Sato, H., Watanabe, Y., Kojima, T.: Characteristics
study of clear polymethylmethacrylate dosimeter, Radix W, in several kGy range. Radiat.
Phys. Chem. 78, 356–359 (2009)
39. Khan, H.M., Ahmad, G., Sattar, A., Durrani, S.K.: Radiation dosimetry using clear PMMA
and PVC in the range of 5-45 kGy. J. Anal. Nucl. Chem. 125, 127–134 (1988)
40. Yang, B., Lu, Q., Wang, S., Townsend, P.D.: Studies on the thermoluminescence spectra and
thermal stability of LiF:Mg, Cu, LiF:Mg, Cu, Na and LiF:Mg, Cu, Si. Nucl. Instrum. Meth.
Phys. Res. B 239, 171–178 (2005)
41. Hosni, F., Farah, K., Kaouach, H., Louati, A., Chtourou, R., Hamzaoui, A.H.: Effect of
gamma-irradiation on the colorimetric properties of epoxy-resin film. Potential use in
dosimetric application. Nucl. Instrum. Meth. Phys. Res. B 311, 1–4 (2013)
42. de Magalhães, C.M.S., Macedo, Z.S., Valerio, M.E.G., Hernandes, A.C., Souza, D.N.:
Preparation of composites of topaz embedded in glass matrix for applications in solid state
thermoluminescence. Nucl. Instrum. Meth. Phys. Res. B 218, 277–282 (2004)
43. Necmeddin Yazici, A., Bedir, M., Sibel Sökücü, A.: The analysis of dosimetric
thermoluminescenty glow peak of CaF2: Mn after β-irradiation. Nucl. Instrum. Meth.
Phys. Res. B 259, 955–965 (2007)
44. McLaughlin, W., Desrosiers, M.F.: Dosimetric systems for radiation processing. Radiat.
Phys. Chem. 46, 1163–1174 (1995)
45. Thalacker, V.P., Simpson, O.T., Postma, N.B.: Electron beam dosimeters for radiation
processing. Radiat. Phys. Chem. 31, 473–479 (1988)
46. Cleland, M.R., Pageau, G.M.: Comparisons of X-ray and gamma-ray sources for industrial
processes. Nucl. Instrum. Math. Phys. Res. B 24/25, 967–972 (1987)
47. Saylor, M.C., Parks, L.A., Herring, C.H.: Technical and regulatory for radiation sterilization
facilities using electron beam accelerators. Nucl. Instrum. Meth. Phys. Res. B 79, 875–878
(1993)
48. Pilette, L.: Effects of ionizing treatments on packaging—food simulant combinations.
Packag. Technol. Sci. 3, 17–20 (1990)
49. Zimek, Z., Przybytniak, G., Nowicki, A., Mirkowski, K., Roman, K.: Optimization of
electron beam crosslinking for cables. Radiat. Phys. Chem. 161–165 (2014)
50. Bartoníček, B., Plaček, V., Hnát, V.: Comparison of degradation effects induced by gamma
radiation and electron beam radiation in two cable jacketing materials. Radiat. Phys. Chem.
76, 857–863 (2007)
51. Charlesby, A.: Crosslinking of polyethylene. Proc. Royal Soc. (London), A 215, 187–188
(1952)
52. Chapiro, A.: Chemical modifications in irradiated polymers. Nucl. Instrum. Meth. Phys. Res.
B 32, 111–114 (1988)
53. Cheng, S., Phillips, Ed, Parks, L.: Processability improvement of polyolefins through
radiation-induced branching. Radiat. Phys. Chem. 79, 329–334 (2010)
54. Deng, P.Y., Liu, M.H., Zhang, W.X., Sun, J.Z.: Preparation and physical properties of
enhanced radiation induced crosslinking of ethylene-vinyl alcohol copolymer (EVOH). Nucl.
Instrum. Meth. Phys. Res. B 258, 357–361 (2007)
55. Yoshii, F., Suhartini, M., Sagasawa, N., Mitomo, H., Kume, T.: Modification of
biodegradable polymers by radiation crosslinking technique with polyfunctional
monomers. Nucl. Instrum. Meth. Phys. Res. B 208, 370–373 (2003)
Radiation Effects on Polymer-Based Systems 149
56. Dadbin, S., Frounchi, M., Goudarzi, D.: Electron beam induced crosslinking of nylon 6 with
and without the presence of TAC. Polym. Degrad. Stab. 89, 436–441 (2005)
57. Mitomo, H., Kaneda, A., Quynh, T.M., Nagasawa, N., Yoshii, F.: Improvement in heat
stability of poly(l-lactic acid) by radiation-induced crosslinking. Polymer 46, 4695–4703
(2005)
58. Nagasawa, N., Kasai, N., Yagi, T., Yoshii, F., Tamada, M.: Radiation-induced crosslinking
and post-processing of poly(l-lactic acid) composite. Radiat. Phys. Chem. 80, 145–148
(2011)
59. Murray, K.A., Kennedy, J.E., McEvoy, B., Vrain, O., Ryan, D., Cowman, R., Higginbotham,
C.L.: The effects of high energy electron beam irradiation in air on accelerated ageing and on
the structure property relationships of low density polyethylene. Nucl. Instrum. Meth. Phys.
Res. B 297, 64–74 (2013)
60. Miličević, D., Trifunović, S., Popović, M., Vukašinović, T., Milić, Suljovrujić, E.: The
influence of orientation on the radiation-induced crosslinking/oxidative behavior of different
PEs. Nucl. Instrum. Meth. Phys. Res. B 260, 603–612 (2007)
61. Yoshiga, A., Otaguro, H., Parra, D.F., Lima, L.F.C.P., Lugao, A.B.: Controlled degradation
and crosslinking of polypropylene induced by gamma radiation in acetylene. Polym. Bull.
63, 397–409 (2009)
62. Zaharescu, T., Feraru, E., Podină, C.: Thermal stability of ethylene propylene-diene
monomer/divinylbenzene systems. Polym. Degrad. Stab. 87, 11–16 (2005)
63. Gillen, K.T., Clough R.L.: In: Clough, R.L., Shalaby, S.W. (eds.) ACS Symp Series 475, ch.
28. ACS, Washington DC, (1991)
64. Zaharescu, T., Jipa, S., Setnescu, R., Setnescu, T.: Radiation processing of polyolefin blends.
Part I. Crosslinking of EPDM/PP blends. J. Appl. Polym. Sci. 77, 982–987 (2000)
65. Zaharescu, T., Jipa, S., Giurginca, M.: Radiochemical processing of EPDM/NB blends.
J. Macromol. Sci. Pure Appl. Chem. A 35, 1093–1102 (1998)
66. Dubey, K.A., Bhardwaj, Y.K., Chaudhari, C.V., Sabharwal, S.: Radiation-processed styrene–
butadiene-co-ethylene– propylene diene rubber blends: compatibility and swelling studies.
J. Appl. Polym. Sci. 99, 3638–3649 (2006)
67. Chowdhury, R.: Electron-beam-induced crosslinking of natural rubber/acrylonitrile–
butadiene rubber latex blends in the presence of ethoxylated pentaerythritol tetraacrylate
used as a crosslinking promoter. J. Appl. Polym. Sci. 103, 1206–1214 (2007)
68. Xiang, Z.I., Liu, H.R., Deng, P.Y., Liu, M.H., Yin, Y., Ge, X.W.: The effect of irradiation on
morphology and properties of the PET/HDPE blends with trimethylolpropane trimethacrylete
(TMPTA). Polym. Bull. 63, 587–597 (2009)
69. Voit, W., Ware, T., Gall, K.: Radiation crosslinked shape-memory polymers. Polymer 51,
3551–3559 (2010)
70. Banik, I., Bhowmick, A.K.: Effect of electron beam irradiation on the properties of
crosslinked rubbers. Radiat. Phys. Chem. 58, 293–298 (2000)
71. Haque, M.E., Dafader, N.C., Akhtar, F., Ahmad, M.U.: Radiation dose required for the
vulcanization of narural rubber latex. Radiat. Phys. Chem. 48, 505–510 (1996)
72. Kurtz, S.M., Muratoglu, O.K., Evans, M., Edidin, A.A.: Advances in the processing,
sterilization and crosslinking of ultra-high molecular weight polyethylene for total joint
arthroplast. Biomaterials 20, 1659–1688 (1999)
73. Rezanejad, S., Kokab, M.: Shape memory and mechanical properties of cross-linked
polyethylene/clay nanocomposites. Eur. Polym. J. 43, 2856–2865 (2007)
74. Mahapram, S., Poompradub, S.: Preparation of natural rubber (NB) latex/low density
polyethylene (LDPE) blown film and its properties. Polym. Test. 30, 716–725 (2011)
75. Chattopadhyay, S., Chaki, T.K., Bhowmick, A.K.: Heat shrinkability of electron-beam-
modified thermoplastic elastomeric films from blends of ethylene vinylacetate copolymer and
polyethylene. Radiat. Phys. Chem. 59, 501–505 (2000)
76. Zhu, G., Liang, G., Xu, Q., Yu, Q.: Shape-memory effects of radiation crosslinked poly(ε-
caprolactone). J. Appl. Polym. Sci. 90, 1589–1595 (2003)
150 T. Zaharescu
77. Ware, T., Voit, W., Gall, K.: Effects of sensitizer length on radiation crosslinked shape-
memory polymers. Radiat. Phys. Chem. 79, 446–453 (2010)
78. Tikku, V.K., Biswas, G., Despande, R.S., Majali, A.B., Chaki, T.K., Bhowmick, A.K.:
Electron beam initiated grafting of trimethylol propane trimethacrylate onto polyethylene—
structure and properties. Radial. Phys. Chem. 45, 829–833 (1995)
79. Gall, K., Dunn, M.L., Liu, Y.P., Finch, D., Lake, M., Munshi, N.A.: Shape-memory polymer
nanocomposites. Acta Mater. 50, 5115–5126 (2002)
80. Hu, J.L., Zu, Y., Huang, H.H., Lu, J.: Recent advances in shape-memory polymers: structure,
mechanism, functionality, modeling and applications. Prog. Polym. Sci. 37, 1720–1763
(2012)
81. Mishra, J.K., Chang, Y.W., Lee, B.C., Ryu, S.H.: Mechanical properties and heat
shrinkability of electron beam crosslinked polyethylene-octene copolymer. Radiat. Phys.
Chem. 77, 675–679 (2008)
82. Rimnac, C.M., Kurtz, S.M.: Ionizing radiation and orthopaedic prostheses. Nucl. Instrum.
Meth. Phys. Res. B 236, 30–37 (2005)
83. Miguez Suarez, J.C., de Biasi, R.S.: Effect of gamma irradiation on the ductile-to-brittle
transition in ultra-high molecular weight polyethylene. Polym. Degrad. Stab. 82, 221–227
(2003)
84. Brunella, V., Bracco, P., Carpentieri, I., Paganini, M.C., Zanetti, M., Costa, L.: Lifetime of
alkyl macroradicals in irradiated ultra-high molecular weight polyethylene. Polym. Degrad.
Stab. 92, 1498–1503 (2007)
85. Costa, L., Carpentieri, I., Bracco, P.: Post electron-beam irradiation oxidation of orthopaedic
UHMWPE. Polym. Degrad. Stab. 93, 1695–1703 (2008)
86. Chmielewski, A.G., Chmielewska, D.K., Michalik, J., Sampa, M.H.: Prospects and
challenges in application of gamma electron and ion beams in processing of
nanomaterials. Nucl. Instrum. Meth. Phys. Res. B 265, 339–346 (2007)
87. Chmielewski, A.G., Michalik, J., Buczkowski, M., Chmielewska, D.K.: Ionizing radiation in
naotechnology. Nucl. Instrum. Meth. Phys. Res. B 236, 329–332 (2005)
88. Jung, C.H., Lee, D.H., Hwang, I.T., Im, D.S., Shin, J.W., Kang, P.H., Choi, J.H.: Fabrication
and characterization of radiation-resistant LDPE/MWCNT nanocomposites. J. Nucl. Mater.
438, 41–45 (2013)
89. Martínez-Morlanes, M.J., Castell, P., Martínez-Nogués, V., Martinez, M.T., Alonso, P.J.,
Puértolas, J.A.: Effects of gamma-irradiation on UHMWPE/MWNT nanocomposites.
Compos. Sci. Technol. 71, 282–288 (2011)
90. Huegun, A., Fernández, M., Muñoz, M.E., Santamaría, A.: Rheological properties and
electrical conductivity of irradiated MWCNT/PP nanocomposites. Compos. Sci. Technol. 72,
1602–1607 (2012)
91. Marković, G., Marinović-Cincović, M.S., Jovanović, V., Samaržija-Jovanović, S., Budinski-
Simendić, J.: Gamma irradiation aging of NBR/CSM rubber nanocomposites. Compos. Part
B- Eng. 43, 609–615 (2012)
92. Wang, B.B., Song, L., Hong, N.N., Tai, Q.L., Lu, H.D., Hu, Y.: Effect of electron beam
irradiation on the mechanical and thermal properties of intumiscent flame retarded ethylene-
vinyl acetate copolymer/orcanically modified montmorillonite compositions. Radiat. Phys.
Chem. 80, 1275–1281 (2011)
93. Choi, J.H., Jung, C.-H., Kim, D.K., Suh, D.H., Nho, Y.C., Kang, P.H., Ganesan, R.:
Preparation of polymer/POSS nanocomposites by radiation processing. Radiat. Phys. Chem.
78, 517 (2009)
94. Lee, K.Y., Kim, K.Y., Hwang, I.R., Choi, Y.S., Hong, C.H.: Thermal, tensile and
morphological properties of gamma-ray irradiated epoxy-clay nanocomposites toughened
with a liquid rubber. Polymer. Test. 29, 139–142 (2010)
95. Mohamed, R.M.: Radiation induced modification of NBR and SBR montmorillonite
nanocomposites. J. Ind. Eng. Chem. 19, 80–86 (2013)
96. Crăciun, E., Jitaru, I., Zaharescu, T., Jipa, S.: Qualification of epoxy resin by radiochemical
ageing. Optoelectr. Adv. Mater. Rapid Commun. 4, 1819–1822 (2010)
Radiation Effects on Polymer-Based Systems 151
97. Ahmadi, S.J., Huang, Y.D., Ren, N.Q., Mohaddespour, A., Ahmadi-Brooghani, S.Y.: The
comparison of EPDM/clay nanocomposites and conventional composites in exposure of
gamma irradiation. Compos. Sci. Technol. 69, 997–1003 (2009)
98. Planes, E., Chazeau, L., Vigier, G., Fournier, J., Stevenson-Royaud, I.: Influence of filler on
mechanical properties of ATH filled EPDM during ageing by gamma irradiation. Polym.
Degrad. Stab. 95, 1029–1038 (2010)
99. Zaharescu, T., Pleşa, I., Jipa, S.: Kinetic effects of silica nanoparticles on thermal and
radiation stability of polyolefins. Polym. Bull. 70, 2981–2994 (2014)
100. Zaharescu, T., Jipa, S., Adrian, M., Supaphol, P.: Nanostructured isotactic polypropylene—
TiO2 systems. J. Optoelectr. Adv. Mater. 10, 2205–2209 (2008)
101. Zaidi, L., Bruzaud, S., Kaci, M., Bourmaud, A., Gautier, N., Grohens, Y.: The effect of
gamma irradiation on the morphology and properties of polylactyide/Cloisite 30B
nanocomposites. Polym. Degrad. Stab. 98, 348–355 (2013)
102. Ciuprina, F., Zaharescu, T., Pleşa, I.: Effect of γ-radiation on dielectric properties of LDPE-
Al2O3 nanocomposites. Radiat. Phys. Chem. 84, 145–150 (2013)
103. Khalid, M., Ismail, A.F., Ratnam, C.T., Faridah, Y., Rashmi, W., Al Khatib, M.F.: Effect of
radiation dose on the properties of natural rubber nanocomposite. Radiat. Phys. Chem. 79,
1279–1285 (2010)
104. Choi, J.H., Jung, C.H., Kang, D.W., Hwang, I.T., Choi, J.H.: Preparation and
characterization of crosslinked poly(ε-caprolactone)/polyhedral oligomeric silsesquioxane
nanocomposites by electron beam irradiation. Nucl. Instrum. Meth. Phys. Res. B 287,
141–147 (2012)
105. Choi, J.H., Jung, C.H., Kim, D.K., Ganesan, R.: Radiation-induced grafting of inorganic
particles onto polymer backbone: a new method to design polymer-based nanocomposite.
Nucl. Instrum. Meth. Phys. Res. B 266, 203–206 (2008)
106. Janowski, B., Pielichowski, K.: Thermo(oxidative) stability of novel polyurethane/POSS
nanohybrid elastomers. Thermochim. Acta 478, 51–53 (2008)
107. Abou Zeid, M.M.: Radiation effect on properties of carbonblack filled NBR/EPDM rubber
blends. Eur. Polym. J. 43, 4415–4422 (2007)
108. Thomas, J.K.: Fundamental aspects of the radiolysis of solid polymers, crosslinking and
degradation. Nucl. Instrum. Meth. Phys. Res. B 265, 1–7 (2007)
109. Olejniczak, J., Rosiak, J., Charlesby, A.: Gel/dose curves for polymers undergoing
simultaneous crosslinking and scission. Radiat. Phys. Chem. 37, 499–504 (1991)
110. Hill, D.J.T., Whittaker, A.K., Zainuddin, : water diffusion into radiation crosslinked PVA-
PVP network hydrogel. Radiat. Phys. Chem. 80, 213–218 (2011)
111. Kadłubowski, S., Henke, A., Ulański, P., Rosiak, I.: Hydrogels of poly(vinylpyrrolidone)
(PVP) and poly(acrylic acid) (PAA) synthesized by radiation-induced crosslinking of
homopolymers. Radiat. Phys. Chem. 79, 261–266 (2010)
112. Adb El-Mohdy, H.L., Safrany, A.: Preparation of fast response superabsorbent hydrogel by
radiation polymerization and crosslinking of isopropylacrylamide in solution. Radiat. Phys.
Chem. 77, 273–279 (2008)
113. von Sonntag, C., Bothe, E., Ulanski, P., Adhikary, A.: Radical transfer reactions in polymers.
Radiat. Phys. Chem. 55, 599–603 (1999)
114. Schmidt, T., Querner, C., Arndt, K.-F.: Characterization methods for radiation crosslinked
pol(vinyl methyl ether) hydrogels. Nucl Instrum. Meth. Phys. Res. B 208, 331–335 (2003)
115. Rosiak, J.M., Ulanski, I.P., Pajewski, L.A., Yoshii, F., Makuuchi, K.: Radiation formation of
hydrogel for biomedical purposes. Some remarks and comments. Radiat. Phys. Chem. 46,
161–168 (1995)
116. Varshney, L.: Role of natural polysaccharides in radiation formation of PVA-hydrogel
wound dressing. Nucl Instrum. Meth. Phys. Res. B 255, 343–349 (2007)
117. Zhou, Y., Zhao, Y.H., Wang, L., Xua, L., Zhai, M.L., Wei, S.C.: Radiation synthesis and
characterization of nanosilver/gelatin/carboxymethyl chitosan hydrogel. Radiat. Phys. Chem.
81, 553–560 (2012)
152 T. Zaharescu
118. Lugão, A.B., Machado, L.D.B., Mirandal, L.F., Alvarez, M.R., Rosiak, J.M.: Study of
wound dressing structure and hydration/dehydration properties. Radiat. Phys. Chem. 52,
319–322 (1998)
119. Ajji, Z., Othman, I., Rosiak, J.M.: Production of hydrogel wound dressing using gamma
radiation. Nucl. Instrum. Meth. Phys. Res. B 229, 375–380 (2005)
120. Şahiner, N., Pekel, N., Güven, O.: Radiation synthesis, characterization and amidoximation
of N-vinyl-2-pyrrolidone/acrylonitrile interpenetrating polymer network. React. Funct.
Polym. 39, 139–146 (1999)
121. Razzak, M.T., Darwis, D., Zainuddin, Z., Sukirno, S.: Irradiation of polyvinyl alcohol and
polyvinyl pyrrolidone blended hydrogel for wound dressing. Radiat. Phys. Chem. 62, 107–
113 (2001)
122. Kan, C.X., Wang, C.S., Zhu, J.J., Li, H.C.: Formation of gold and silver nanocomposites
within polyvinylpyrrolidone (PVP) gel. J. Solid State Chem. 183, 858–865 (2010)
123. Momesso, R.G.R.A.P., Moreno, C.S., Rogero, S.O., Rogero, J.R., Spencer, P.J., Lugão, A.
B.: Radiation stability of resveratrol in immobilization on poly(vinyl pyrrolidone) hydrogel
for dermatological use. Radiat. Phys. Chem. 79, 283–285 (2010)
124. Ferraz, C.C., Varca, G.H.C., Lopes, P.S., Mator, M.B., Lugão, A.B.: Radiation-synthesized
polyacrylamide hydrogels for proteins release. Radiat. Phys. Chem. 94, 186–189 (2014)
125. Varca, G.H.C., Ferraz, C.C., Lopes, P.S., Mathor, M.B., Grasselli, M., Lugão, A.B.:
Radiation-synthesized protein-based nanoparticles for biomedical purposes. Radiat. Phys.
Chem. 94, 181–185 (2014)
126. Abd El-Mohdy, H.L., Hegazy, E.A., El-Nesr, E.M., El-Wahab, M.A.: Metal sorption
behavior of poly(N-vinyl-2-pyrrolidone)/(acrylic acid-co-styrene) hydrogels synthesized by
gamma radiation. J. Environ. Chem. Eng. 1, 328–338 (2013)
127. Radiation synthesis of stimuli-responsive membranes, hydrogels and adsorbents for
separation purposes, IAEA-TECDOC 1465 (2005)
128. Gottlieb, R., Schmidt, T., Arndt, K.-F.: Synthesis of temperature-sensitive hydrogel blends
by high-energy irradiation. Nucl. Instrum. Meth. Phys. Res. B 236, 371–376 (2005)
129. Bhunia, T., Goswami, L., Chattopadhyay, D., Bandyopadhyay, A.: Sustained transdermal
release of diltiazem hydrochloride through electron beam irradiated different PVA hydrogel
membranes. Nucl. Instrum. Meth. Phys. Res. B 269, 1822–1828 (2011)
130. Burillo, G., Briones, M., Adem, E.: IPN’s of acrylic acid and N-isopropylacrylamide by
gamma and electron beam irradiation. Nucl. Instrum. Meth. Phys. Res. B 265, 104–108
(2007)
131. Casimiro, M.H., Gil, M.H., Leal, J.P.: Drug release assays from new chitosan/pHEMA
membranes obtained by gamma irradiation. Nucl. Instrum. Meth. Phys. Res. B 265, 406–409
(2007)
132. Safrany, A.: Macroporous gels with fast response prepared by e-beam crosslinking of poly
(N-isopropylacrylamide) solution. Nucl. Instrum. Meth. Phys. Res. B 236, 587–593 (2005)
133. Jipa, I.M., Stroescu, M., Stoica-Guzun, A., Dobre, T., Jinga, S., Zaharescu, T.: Effect of
gamma irradiation on biopolymer films of poly(vinyl alcohol) and bacterial cellulose. Nucl.
Instrum. Meth. Phys. Res. B 278, 82–87 (2012)
134. Ahmed, E.M.: Hybrid composites prepared from industrial wastes: mechanical and swelling
behavior. J. Adv. Res. doi:10.1016/j.jare.2013.12.002
135. Safrany, A.: Radiation processing: synthesis and modification of biomaterials for medical
use. Nucl. Instrum. Meth. Phys. Res. B 131, 376–381 (1997)
136. Nho, Y.C., Lee, J.H.: Radiation of postsurgical adhesion formation with hydrogels
synthesized by radiation. Nucl. Instrum. Meth. Phys. Res. B 236, 277–282 (2005)
137. Burillo, G., Clough, R.L., Czvikovszky, T., Guven, O., Le Moel, A., Liu, W.W., Singh, A.,
Yang, J.T., Zaharescu, T.: Polymer recycling: potential application of radiation technology.
Radiat. Phys. Chem. 64, 41–51 (2002)
138. Żenkiewicz, M., Dzwonkowski, J.: Effects of electron radiation and compatibilizers on
impact strength of composites of recycled polymers. Polym. Test. 26, 903–907 (2007)
Radiation Effects on Polymer-Based Systems 153
139. Dalai, S., Wenxiu, C.: Radiation effects on HDPE/EVA blends. J. Appl. Polym. Sci. 86,
553–558 (2002)
140. Burillo, G., Galicia, M., del Pilar Carreo, M., Vázquez, M., Adem, E.: Crosslinking of
recycled polyethylene by gamma irradiation in the presence of sensitizers. Radiat. Phys.
Chem. 60, 73–78 (2001)
141. Burillo, G., Herrera-Franco, P., Vazquez, M., Adem, E.: Compatibilization of recycled and
virgin PET with radiation-oxidized HDPE. Radiat. Phys. Chem. 63, 241–244 (2002)
142. Mészáros, L., Bárány, T., Czvikovszky, T.: EB-promoted recycling of waste tire rubber with
polyolefins. Radiat. Phys. Chem. 81, 1357–1360 (2012)
143. Karaağaç, B., Şen, M., Deniz, V., Güven, O.: Recycling of gamma irradiated inner tubes in
butyl based rubber. Nucl. Instrum. Meth. Phys. Res. B 265, 290–293 (2005)
144. Sonnier, R., Leroy, E., Clerc, L., Bergeret, A., Lopez-Cuesta, J.M.: Compatibilisation of
polyethylene/ground tyre rubber blends by γ-irradiation. Polym. Degrad. Stab. 91,
2375–2379 (2006)
145. Zaharescu, T., Feraru, E., Podină, C., Jipa, S.: Modifications of EPDM by gamma irradiation
in hydrocarbon environment. Polym. Degrad. Stab. 89, 373–381 (2005)
146. Jones, R.A., Groves, D.J., Ward, I.M., Taylor, D.J.R., Stepto, R.F.T.: Gel fraction and chain
reactions in irradiated polyethylenes. Nucl. Instrum. Meth. Phys. Res. B 151, 213–217
(1999)
147. Scagliusi, R.S., Cardoso, E.C.L., Lugão, A.B.: Radiation-induced degradation of butyl
rubber vulcanized by three different crosslinking systems. Radiat. Phys. Chem. 81, 991–994
(2012)
148. Scagliusi, R.S., Cardoso, E.C.L., Lugão, A.B.: Effect of gamma radiation on chlorobutyl
rubber vulcanized by three crosslinking systems. Radiat. Phys. Chem. 81, 1370–1373 (2012)
149. Zaharescu, T.: Degradation of ethylene-propylene copolymer in the presence of phenolic
antioxidants. J. Mater. Sci. Lett. 14, 923–925 (1995)
150. Bhattacharya, A., Misra, B.N.: Grafting: a versatile means to modify polymers: techniques,
factors and applications. Prog. Polym. Sci. 29, 767–814 (2004)
151. Garnett, J.L.: Grafting. Radiat. Phys. Chem. 14, 79–99 (1979)
152. Stannett, V.T.: Radiation grafting—state-of-the art. Radiat. Phys. Chem. 35, 82–87 (1990)
153. Moura, E., Somessari, E.S.R., Silveira, C.G., Paes, H.A., Souza, C.A., Fernandes, W.,
Manzoli, J.E., Geraldo, A.B.C.: Influence of physical properties on mutual polymer grafting
by electron beam irradiation. Radiat. Phys. Chem. 80, 175–181 (2011)
154. Ranogajec, F.: Effect of solvent on radiation grafting and crosslinking of polyethylene.
Radiat. Phys. Chem. 76, 1381–1384 (2007)
155. Hassanpour, S.: Radiation grafting of styrene and acrylonitrile to cellulose and polyethylene.
Radiat. Phys. Chem. 55, 41–45 (1999)
156. Catarí, E., Albano, C., Karam, A., Perera, R., Silva, P., González, J.: Grafting of a LLDPE
using gamma irradiation. Nucl. Instrum. Meth. Phys. Res. B 236, 338–342 (2005)
157. Legocka, I., Zimek, Z., Mirkowski, K., Nowicki, A.: Preliminary study on the application PE
filler modified by radiation. Radiat. Phys. Chem. 57, 411–416 (2000)
158. Li, Z.R., Wang, H.L.: Radiation-induced grafting of glycidyl methacrylate onto high density
polyethylene (HDPE) and radiation lamination of HDPE. J. Appl. Polym. Sci. 96, 772–779
(2005)
159. Ferreira, L.M., Falcão, A.N., Gil, M.H.: Modification of LDPE molecular structure by
gamma irradiation for bioapplications. Nucl. Instrum. Meth. Phys. Res. B 236, 513–520
(2005)
160. Gwon, S.J., Choi, J.H., Sohn, J.Y., An, S.J., Ihm, Y.E., Nho, Y.C.: Radiation grafting of
methyl methacrylate onto polyethylene separators for lithium secondary batteries. Instrum.
Meth. Phys. Res. B 266, 3387–3391 (2008)
161. Abdel-Hady, E.E., El-Toony, M.M., Abdel-Hamed, M.O.: Grafting of glycidyl methacrylate/
styrene onto polyvinyl fluoride membranes for proton exchange fuel cell. Electrochim. Acta
103, 32–37 (2013)
154 T. Zaharescu
162. Souzy, R., Ameduri, B.: Functional fluoropolymers for fuel cell membranes. Prog. Polym.
Sci. 30, 644–687 (2005)
163. Gubler, L., Slaski, M., Wallasch, F., Wokaun, A., Scherer, G.G.: Radiation grafted fuel cell
membranes based on co-grafting of a-methylstyrene and methacrylonitrile into a
fluoropolymer base film. J. Membr. Sci. 339, 68–77 (2009)
164. Li, J.Y., Matsuura, A., Kakigi, T., Miura, T., Oshima, A., Washio, M.: Performance of
membrane electrode assemblies based on proton exchange membranes prepared by pre-
irradiation induced grafting. J. Power Sources 161, 99–105 (2006)
165. Chen, J.H., Li, D.R., Koshikawa, H., Asano, M., Maekawa, Y.: Crosslinking and grafting of
polyetheretherketone film by radiation techniques for application in fuel cell. J. Membr. Sci.
362, 488–494 (2010)
166. Sherazi, T.A., Ahmad, S., Akram Kashmiri, S., Kim, D.S., Guiver, M.D.: Radiation-induced
grafting of styrene onto ultra-high molecular weight polyethylene powder for polymer
electrolyte fuel cell application. II. Sulfonation and characterization. J. Membr. Sci. 333,
59–67 (2009)
167. Nho, Y.C., Chen, J., Jin, J.H.: Grafting polymerization of styrene onto preirradiated
polypropylene fabric. Radiat. Phys. Chem. 54, 317–322 (1999)
168. Vahdat, A., Bahrami, H., Ansari, N., Ziaie, F.: Radiation grafting of styrene onto
polypropylene fibers by a 10 MeV electron beam. Radiat. Phys. Chem. 76, 787–793 (2007)
169. Sheikh, N., Akhavan, A., Ataeivarjovi, E.: Radiation grafting of styrene on starch with high
efficiency. Radiat. Phys. Chem. 85, 189–192 (2013)
170. Yu, H.Y., Shi, H., Zeng, X.M., Bao, M., Zhao, X.Q.: A proton-exchange membrane prepared
by the radiation grafting of styrene and silica into polytetrafluoroethylene films. Radiat. Phys.
Chem. 78, 497–500 (2009)
171. Barsbay, M., Güven, O., Davis, T.P., Barner-Kowollik, C., Barner, L.: RAFT-mediated
polymerization and grafting of sodium 4-styrenesulfonate from cellulose initiated via
gamma-radiation. Polymer 50, 973–982 (2009)
172. Lappan, U., Geissler, U., Uhlmann, S.: Radiation-induced grafting of styrene into radiation
modified fluoropolymer films. Nucl. Instrum. Meth. Phys. Res. B 236, 413–419 (2005)
173. Sato, K., Ikeda, S., Iida, M., Oshima, A., Tabata, Y., Washio, M.: Studyon poly-electrolyte
membrane of crosslinked PRFE by radiation grafting. Nucl. Instrum. Meth. Phys. Res. B
208, 424–428 (2003)
174. Katsuma, Y.: Radiation induced degradation of polymers-an approach by using liquid
paraffins as a model system. Angew. Makromol. Chem. 252, 89–101 (1997)
175. Zaharescu, T., Jipa, S., Supaphol, P.: Thermal stability of isotactic polypropylene modified
with CaCO3 nanoparticles. Polym. Bull. 64, 783–790 (2010)
176. Seguchi, T., Tamura, K., Ohshima, T., Shimada, A., Kudoh, H.: Degradation mechanism of
cable insulation materials during radiation-thermal ageing in radiation environment. Radiat.
Phys. Chem. 80, 268–273 (2011)
177. Celina, M.: Review of polymer oxidation and its relationship with material performances and
lifetime prediction. Polym. Degrad. Stab. 98, 2419–2429 (2013)
178. Zaharescu, T., Cazac, C., Jipa, S., Setnescu, R.: Radiation processing of polyisobutylene.
Nucl. Instrum. Meth. Phys. Res. B 185, 360–364 (2001)
179. Burillo, G., Tenorio, L., Bucio, E., Adem, E., Lopez, G.P.: Electron beam irradiation effects
on poly(ethylene terephtalate). Radiat. Phys. Chem. 76, 1728–1731 (2007)
180. Zaharescu, T., Giurginca, M., Jipa, S.: Radiochemical oxidation of ethylene-propylene
elastomers in the presence of some phenolic antioxidants. Polym. Degrad. Stab. 63, 245–251
(1999)
181. Pandey, J.K., Raghunatha Reddy, K., Pratheep Kumar, A., Singh, R.P.: An overview on the
degradability of polymer nanocomposites. Polym. Degrad. Stab. 88, 234–250 (2005)
182. Kim, S.K., Kwen, H.D., Choi, S.H.: Radiation-induced synthesis of vinyl copolymer based
nanocomposites filled with reactive organic montmorillonite clay. Radiat. Phys. Chem. 81,
519–523 (2012)
Radiation Effects on Polymer-Based Systems 155
183. Kharazmi, A., Saion, E., Faraji, N., Hussin, R.M., Yunus, W.M.M.: Structural, optical and
thermal properties of PVA/CdS nanocomposites synthesized by radiolytic method. Radiat.
Phys. Chem. 97, 212–216 (2014)
184. Krklješ, A.N., Marinović-Cincović, M.T., Kacarević-Popović, Z.M., Nedeljković, J.M.:
Radiolytic synthesis and characterization of Ag-PVA nanocomposites. Eur. Polym. J. 43,
2171–2176 (2007)
185. Xu, X.L., Yin, Y.D., Ge, X.W., Wu, H.K., Zhang, Z.H.: γ-Radiation synthesis of poly(acrylic
acid)—metal nanocomposites. Mater. Lett. 37, 354–358 (1998)
186. Abou Taleb, M.F., Hegazy, D.E., Ismail, S.A.: Radiation synthesis, characterization and dye
adsorption of alginate-organophilic montmorillonite nanocomposite. Carbohydr. Polym. 87,
2263–2269 (2012)
187. Robinette, E.J., Palmese, G.R.: Synthesis of polymer-polymer nanocomposites using
radiation grafting techniques. Nucl. Instrum. Meth. Phys. Res. 236, 216–222 (2005)
188. Ni, Y.H., Ge, X.W., Zhang, Z.C.: Fabrication of CdS/polyacrylonitrile nanocomposites by
γ-irradiation in an ethanol solution. Mater. Sci. Eng. B 130, 61–65 (2006)
189. Dintcheva, N.Tz., Alessi, S., Arrigo, R., Przybytniak, G., Spadaro, G.: Influence of the e-
beam irradiation and photo-oxidation aging on the structure and properties of LDPE-OMMT
nanocomposite films. Radiat. Phys. Chem. 81, 432–436 (2012)
190. Misheva, M., Djourelov, N., Zamfirova, G., Gaydarov, V., Cerrada, M.L., Rodríguez-Amor,
V., Pérez, E.: Effect of compatibilizer and electron irradiation on free-volume and
microhardness of syndiotactic polypropylene/clay nanocomposites. Radiat. Phys. Chem.
77, 138–145 (2008)
191. Masellini-Varlot, K., Vigier, G., Vermogen, A., Gauthier, C., Cavaille, J.Y.: Quantitative
structural characterization of polymer-clay nanocomposites and discussion of an ideal
microstructure, leading to the highest mechanical reinforcement. J. Polym. Sci., Part B
Polym. Phys. 45, 1243–1251 (2007)
192. Yidirim, Y., Oral, A.: The influence of γ-ray irradiation on the thermal stability and
molecular weight of poly(L-Lactic acid) and its nanocomposites. Radiat. Phys. Chem. 96,
69–74 (2014)
193. Jovanović, Z., Jovanović, Ž., Krklješ, A., Stojkovska, J., Tomić, S., Obradović, B.,
Mišković-Stanković, V., Kačarević-Popović, Z.: Synthesis and characterization of silver/
polyvinyl 2-pyrrolidone hydrogel nanocomposite obtained in situ radiolytic method. Radiat.
Phys. Chem. 80, 1208–1215 (2011)
Thermal Degradation of Synthetic Rubber
Nanocomposites
Abstract In recent years, synthetic rubbers nanocomposites have captured and held
the attention of scientists because are the materials for the future, which have
improved resistance to thermal degradation and stability of the nanocomposite.
Commonly fillers like layered silicates, carbonaceous nanofillers (carbon nanotubes,
carbon naanofibers and exfoliated nanographite), spherical particles (Silica, TiO2,
ZnO, CaSO4, CaCO3, ZnFe2O4) and polyhedral oligomeric silsesquioxane (POSS)
are used for reinforcing elastomers. This new materials exhibit enhanced properties at
very low filler level, usually ≤5 wt%. The properties of rubber nanocomposites
strongly depend on the dispersion state of fillers and method of preparation. The
effect to different nanoparticles on rubber properties is studied with thermal stability.
This is mainly studied using TGA, TGA-MS, TGA-FTIR and other techniques. The
thermal degradation mechanism of the rubber synthetic nanocomposites is generally
considered to be related to the kind of used nanoparticles and its amount, the inter-
actions between inorganic nanoparticles and polymer reactive group. Rubber syn-
thetic nanocomposites play an important role in engineering, automotive, aerospace,
construction, packaging and medical devices applications due to is possible to design
new materials with unprecedented and improvements in their physical properties,
particularly from the perspective of applications.
1 Introduction
The words nanocomposites and nanofillers are fairly recent, but have been in use
since 1904 for example, carbon black is being used as a reinforcing filler in rubbers
and apparently always existed in nature (in minerals and vegetation) [1, 2].
1.1 Nanofillers
is the simplest atomic geometric pattern, which is enough for duplicating the
crystalline network, by repeating itself indefinitely in the three directions. Table 1
presents the various natural and synthetic nanoclays available and used as fillers in
rubbers.
Thermal Degradation of Synthetic Rubber Nanocomposites 161
that are available in latex form. Most rubbers are available in latex form. Latex is a
more or less stable aqueous dispersion of fine rubber particles (in the submicron-
micron range). The related particle size distribution strongly depends on the
manufacturing. So, mixing of the latex with layered silicates followed by coagu-
lation (coprecipitation) is a promising way to produce rubber nanocomposites. This
technique has been used for NR [46], SBR [47], carboxilated NBR [48], NBR [49],
polyurethane (PUR) [50] and polychloroprene (CR).
Use of internal mixers offers a direct and environment friendly technique for
preparation of nanocomposites. A two-step mixing in an internal mixer followed by
addition of curative on a two roll mill for preparation of elastomer-layered silicate
nanocomposites [51]. In the study on the effect of processing conditions (mixer
type, mixing temperature) and formulations on the properties of EPDM nano-
composites, it has been shown that open two roll mill mixing results in inadequate
dispersion of the nanofiller in the elastomer matrix compared to compounding in an
internal mixer. Melt compounding with layered silicates has been reported for NR
[52], ENR [46], SBR [53], NBR [54], EPDM [55] and PU [56] systems.
fluoride) indicated that the effect of oxygen can lead to changes in both reaction rate
and kinetic order of reaction [58]. Inabi’s work in particular has resulted in the
development of models for the kinetics of general random chain scission thermal
decomposition [59], as well as for the thermal decomposition of thermoplastics
[60]. There are a number of general classes of chemical mechanisms important in
the thermal decomposition of polymers: 1 random-chain scission, in which chain
scissions occur at apparently random locations in the polymer chain. The chain
reaction is terminated by recombination reactions with the formation of stable
compounds, such as, for instance, the constitution of C–C or C–O–C bonds from
two radicals tantamount to an increase in crosslinking density; 2 end-chain scission,
in which individual monomer units are successively removed at the chain end; 3
chain-stripping, in which atoms or groups not part of the polymer chain (or
backbone) are cleaved; and 4 cross-linking, in which bonds are created between
polymer chains.
At the same time the thermo-oxidation generally occurs quite slowly at ambient
temperatures, but may have serious consequences as the temperature is increased.
Oxidation of rubbers can involve the reaction of free radicals present in the rubber
with molecular oxygen. The free radicals can be formed by decomposition of
hydroperoxides, which are present in the rubber in minute amounts after processing.
These reactions then lead to chain scission and/or additional crosslinking,
depending on the type of rubber. For instance, oxidation of synthetic rubber is
initially dominated by chain scission, which causes the rubber to soften. This
softening is followed by an increase in crosslinking, which then leads to hardening.
Both processes results in a weaker, brittle polymer. At ambient temperatures the
main degradation process involves the presence of oxygen from the atmosphere.
The reaction with oxygen leads to chain scission and the formation of polymeric
peroxides, which can also increase the rate of thermo-oxidation [61] The presence
of double bonds and branching in the macromolecular chains of the polymer
increases the oxidation rate, even if a stabilization agent is present [62]. Changes in
the properties of polymers depend on the extent of such reactions [63].
Curing systems can influence the thermal degradation of rubber nanocomposites.
Accelerated sulphur curing systems are commonly used in vulcanizing the elasto-
mers. The crosslink density and type of crosslink networks significantly influence the
mechanical properties of the rubber vulcanisates. In general, the vulcanisates cured
with efficient and conventional systems predominantly contain monosulphide,
disulphide networks and polysulphide networks [64]. As an alternative, the peroxide
curing system has been used to overcome this problem. The thermal stability of C–C
linkages improves the ageing properties of elastomer compounds [65].
Rubber is material with important applications in different areas, highlighting the
automotive area, due to chemical and physical property, especially their structure
composition, this material is considered an elastomer within the classification of
polymeric materials.
Synthetic rubbers are a highly elastic material that enhances the quality of
modern life. It is a unique material polymeric in that it stretches many times it is
length without breaking, and it recovers to its original shape, “memory”, is
166 A.C. Facio et al.
indispensable for many key applications such as automobiles tire, conveyor belts,
gloves, and many more [66].
Nowadays, synthetic rubber, has the characteristics of being able to be com-
bined, mixed or modified with different type of fillers, organic and or inorganic,
may be of different size, morphology and chemical nature. An important area to
explore in the implementation and use of nanocomposites is degradation, which
may be by different methods: chemical, enzymatic [67], thermal, etc. highlighting
the thermal degradation as an important method that could occur during the use of
polymeric nanocomposites. Below are some examples of polymer nanocomposites
degradation.
With respect to UV degradation, Arantes et al., reported the photodegradation of
styrene–butadiene rubber (SBR)/TiO2 nanocomposites. Nanocomposites films were
obtained by solution mixing. The study was conducted by monitoring cross-linking
reactions between the polymer chains during the degradation process by nuclear
magnetic resonance spectroscopy (NMR) in the solid state with magic angle
spinning (MAS), when the material becomes crosslinked becomes more rigid and
less soluble in organic solvents [68].
The electron beam irradiation is other type of energy that could produce deg-
radation, in 2012 Tonny and Nemr reported the degradation of acrylonitrile/buta-
diene/silica nanocomposite, the materials were electron beam irradiated at 25 and
100 kGy, finding that during the electron beam the thermal and thermo oxidative
degradation are the principal reaction that occur confirmed by the fragments C–C of
the polymer and volatiles as CO, CO2, CH4, H2O, etc. [69].
The thermal degradation has been amply studied by researches, meanwhile
Chayan et al. in 2012, reported the study of Nitrile rubber/silica nanocomposites
prepared with surface modified silica nanoparticles. They observed that the first
weight loss occur at the temperature range 350–490 °C is due to degradation of the
rubber component. The next weight loss at the temperature range 520–640 °C is
due to the decomposition of carbonaceous residue. The temperature at maximum
weight loss (Tmax) was determined from the peaks obtained in Derivative Ther-
mogravimetry (DTG). It is observed that the value is higher for the composites
containing surface modified silica particles indicating greater thermal stability for
them over that of composite containing unmodified silica [70, 71]. Presence of
silane coupling agents in silica nano particles are detected Improvement in thermal
stability [70].
In 2011 Mohomane et al., prepared nanocomposites from polychloroprene
rubber (PCP) as the matrix and organically modified montmorillonite clays (Cloisite
15A, 20A, 25A, 10A and 93A) as fillers by two-roll mill, with clays contents of 2.5,
5 and 10 phr., The results for Cloisite 93A and Cloisite 15A depicted an exfoliated
structure and a well-dispersed morphology in the polymer matrix at all filler con-
tents, while complete exfoliation was not observed for the other clays, especially at
higher clay contents. The initial stage of thermal degradation was accelerated with
the incorporation of organoclays. The TGA results show that degradation occurs in
two stages. The first weight loss takes place around 300 °C and was attribute to the
elimination of HCl molecule, leaving behind the polyene chains. This is followed
Thermal Degradation of Synthetic Rubber Nanocomposites 167
by a gradual decrease in weight between 300 and 450 °C. Also condensation
reactions occur above 500 °C, demonstrating the stability by incorporating
organically modified montmorillonite and that clays have a significant influence on
the PCP degradation mechanism, even at low clay contents.
Introduction of the organic modified clay generally reduces the onset of the
decomposition temperature of the PCP rubber. On the other hand, the degradation
of the nanocomposite samples is slowed down in the first stage of decomposition.
The former effect was most pronounced in the case of the Cloisite 93A and Cloisite
15A nanoclays, where it is observed at low clay contents. As the filler content
increased, this effect was also observed in the other PCP nanocomposites [72].
Is important to emphasize that the fillers in the polymer matrix have as effect an
increase in the thermal stability of the nanocomposite. Interactions between polymer
and inorganic filler materials are powerful and increase the molecular cohesion energy
and hence the heat needed to activate the mechanism of thermal degradation [73].
Synthetic rubbers are characterized by good thermal stability due to its structure,
for this reason the rubbers have very important applications. The nitrile rubber
(NBR) is a polymer used in applications requiring resistance to high temperatures
of oil. Balachandran et al. reported behavior NBR-nanoclay nanocomposites,
showing that the temperature at which degradation occurs is increased by adding
the nanoclays [74].
platelets which were homogeneously distribute in the EVA matrix. They explained
that EG presented greater surface area can lead to higher interaction between the
platelets and rubber matrix [87, 88]. The main parameter responsible for the good
dispersion quality in the nanocomposite is the compatibility of the nanoparticle with
the polymeric matrix [83].
At the same time inorganic nanoparticles are important component in synthetic
rubber nanocomposites, this type of nanoparticles are less reactive than organic
nanoparticles, because they are not involved in thermal degradation reactions.
Inorganic nanoparticles can be subjected to high temperature, due of natural
chemical, are considered an excellent choice as reinforcement in polymer matrix,
has been reported that using this type of nanoparticles improve the thermal stability
of nanocomposite.
The group of Gu Z. in the 2009, reported the behavior of styrene butadiene/
rubber/organo-bentonite nanocomposite prepared from latex dispersion, content
was lower than 12 mass%. The results showed were that presence of organo-
bentonite in the nanocoposite affects direct in the thermo stability, mechanical
properties and swelling behavior, which was attribute to the good barrier properties
of the dispersed nanoparticles. The dispersion is an important factor that can affect
various properties such as thermal stability [81].
In 2012 Rybinski et al., reported the study of butadiene-styrene-rubber (SBR)
nanocomposite with montmorillonite, found that the nanofillers used do not explicitly
influence in the thermal stability of the nanocomposite but they decrease the thermal
decomposition rate of these material under thermo-oxidative conditions [89].
Other interesting kind of nanoparticle are silice, Li et al. studied the properties of
vulcanized rubber nanocomposite filled with nanokaolin and precipitated silica,
demonstrating that the presence of nanokaolin improve the thermal stability, this
due to the good interfacial interaction between the nanokaolin and the chains of
rubber in the nanocomposite [90].
Decomposition Mechanism
The most common reaction mechanism involves the breaking of bonds in the
main polymer chain. These chain scissions may occur at the chain end or at random
locations in the chain. End chain scissions result in the production of monomer, and
the process is often known as unzipping. Random-chain scissions generally result in
the generation of monomers and oligomers (polymer units with 10 or fewer
monomer units) as well as a variety of other chemical species. The type and
distribution of volatile products depend on the relative volatility of the resulting
molecules.
Cross-linking is another reaction involving the main chain. It generally occurs
after some stripping of substituents and involves the creation of bonds between two
adjacent polymer chains. This process is very important in the formation of chars,
since it generates a structure with a higher molecular weight that is less easily
volatilized. The main reaction types involving side chains or groups are elimination
reactions and cyclization reactions.
In elimination reactions, the bonds connecting side groups of the polymer chain
to the chain itself are broken, with the side groups often reacting with other
eliminated side groups. The products of these reactions are generally small enough
to be volatile. In cyclization reactions, two adjacent side groups react to form a
bond between them, resulting in the production of a cyclic structure [91].
Synthetic rubber or polyisoprene decomposes by random-chain scission with
intramolecular hydrogen transfer. This, of course, gives small yields of monomer.
Other polydienes appear to decompose similarly though the thermal stability can be
considerably different. The average size of fragments collected from isoprene
decomposition is 8–10 monomer units long. This supports the theory that random-
chain scission and intermolecular transfer reactions are dominant in the decom-
position mechanism. In nitrogen, decomposition begins at 200 °C. At temperatures
above 400 °C, increases in monomer yield are attributable to secondary reaction of
volatile products to form monomer. Between 200 and 300 °C, low molecular
weight material is formed, and the residual material is progressively more insoluble
and intractable. Preheating at between 200 and 300 °C lowers the monomer yield at
higher temperatures. Decomposition at less than 300 °C results in a viscous liquid
and, ultimately, a dry solid. The monomer is prone to dimerize to dipentene as it
Thermal Degradation of Synthetic Rubber Nanocomposites 171
Addition of small amount of nanofillers may improve the properties of rubber and
thermoplastics. In the polymer industry, polymer-filler nanocomposites are a
promising class of material that offers the possibility of developing new hybrid
materials with desired set of properties. Properties of rubbers and thermoplastics
which have shown substantial improvements due to the incorporation of nanopar-
ticles, are mechanical properties, decreased permeability to gases, water and
hydrocarbons, thermal stability and heat distortion temperature, flame retardancy
and reduced smoke emissions, chemical resistance, surface appearance, electrical
and thermal conductivity, optical clarity in comparison to conventionally filled
polymers [107].
Polychloroprene is a family of synthetic rubbers, exhibits good chemical sta-
bility, and maintains flexibility over a wide temperature range. It is used in a wide
variety of applications, such as laptop sleeves, orthopedic braces, electrical insu-
lation, liquid and sheet applied elastomeric membranes or flashings, and automotive
fan belts, and others. Subramaniam et al. studied the thermal degradation of
polychloroprene rubber composites based on unmodified and ionic liquid modified
multi-walled carbon nanotubes (MWCNTs), in aerobic and anaerobic conditions.
They found that the polychloroprene rubber and its composite exhibit three and four
174 A.C. Facio et al.
stage degradation in nitrogen and air respectively [29]. The second and third stages
of degradation were predominant as the main degradation of the elastomer occurs.
They found that the presentence of unmodified CNTs alone does not improve the
thermal stability of the nanocomposite, however when modified CNTs ionic liquid
a reasonable enhancement is observed, they attributed to the interfacial interactions
of ionic liquid modified CNTs with polychloroprene rubber, also they found better
dispersion of the modified CNTs than the unmodified ones. The activation energy
was calculated form degradation kinetics studies, founding to be high for modified
CNTs–polychloroprene rubber nanocomposites.
Recently Iqbal et al. [28] incorporated four diverse loadings of pristine multi-
walled carbon nanotubes (MWNTs) in a silicon rubber (SR) matrix using dispersion
kneader and two roller mixing mill to disperse the nanotubes evenly in the polymer
matrix. The SR nanocomposite (1 wt% filler contents) has 28 % better thermal
stability and 100 % improvement in the ultimate tensile strength is achieved as
compared with the pristine polymer matrix counterpart. TGA of their nanocom-
posite showed thermal degradation with temperature evolution up to 850 °C. They
observed % weight loss at 300, 500, 650, and 800 °C during the TGA for all SR
nanocomposite and demonstrated an improved thermal stability. They found that
the maximum thermal degradation in the range 400–600 °C for all nanocomposites
as the polymer pyrolysis of SR matrix is usually analyzed within this temperature
range. Thermal stability and heat quenching ability of the SR nanocomposites were
gradually augmented with increasing filler loadings in the polymer matrix. Li et al.
[108] also, investigated the effect of the interfacial interaction on the thermal oxi-
dative stability of chemically modified carbon nanotubes (CNTs)/SR composites
and of nanoparticle-attached CNTs/SR composites, poly(dimethylsiloxane)-grafted
CNTs and iron(III)-oxide-attached CNTs were prepared and embedded into a SR
matrix, respectively. They found that the effect of interfacial interactions of poly
(dimethylsiloxane)-grafted CNTs/SR composite was damaged at 250 % strain. The
interfacial interaction of iron (III)-oxide-attached CNTs/SR composites was dam-
aged at 100 % strain. After the thermal oxidative aging, the mechanical properties
of the poly(dimethylsiloxane)-grafted CNTs/SR composites decreased sharply due
to the damaged interface and also the thermal stability was reduced. However,
similar damages did not affect the thermal stability of the iron (III)-oxide-attached
CNTs/SR composites.
In addition, SR/GO nanocomposites has been prepared for Wang et al. [109] via
a solution intercalation method. The thermal behavior of the nanocomposites
characterized by TGA showed that that the addition of graphite oxide is beneficial
to improve the thermal stability of the nanocomposites at high temperature. They
found that the initial decomposition temperature of the filled rubber was decreased
compared with the pure SR. They argued that the decreasing of the initial
decomposition temperature with the GO may be due to the degradation of GO.
When further heated, they observed that the incorporation of GO into SR improves
thermal stability remarkably. The degradation of siloxane chains occurs in two
ways: degradation of siloxane chains initiated by the terminal group and degra-
dation of the main chains of siloxane. GO contains polar OH and COOH groups,
Thermal Degradation of Synthetic Rubber Nanocomposites 175
and silicone rubber backbones consist of polar Si–O units. The graphite oxide easily
absorbs polar Si–O bond, resulting in formation of physical crosslinking points.
This increases the rigidity of siloxane chains, and thus hinders the degradation of
siloxane chains. In addition, SR filled with conductive carbon black has better
thermal stability than that of SR without any filler. Also, SR filled with conductive
carbon black has better thermal stability than that of silicone rubber filled with the
same amount of silica [5].
Also, it is reported in the literature [110] that Cellulose nanocrystals (CNs) can
be used to obtain nitrile rubber (NBR)/CNs nanocomposites, by mixing a water
suspension of CNs and the NBR latex directly. In this study is reported that
mechanical performance showed that CNs have a good reinforcing effect on NBR.
The results showed of DMA demonstrated that the glass transition temperature (Tg)
of the composites was shifted from 10.8–17.2 °C with CNs content increasing to
20 phr and the storage modulus increased simultaneously. TGA result shows that
the degradation corresponding to CNs in NBR/CNs nanocomposites is much higher
than the degradation temperature of pure CNs. The thermogram of NBR/CNs
nanocomposites show two degradation stages: the first region at a temperature
range of 340–390 °C is probably due to the degradation of CNs, and the weight loss
is in accordance with the CNs content; the second stage occurred at around
400–480 °C and is due to the degradation of NBR. Cao et al. [110] found that the
degradation corresponding to CNs in NBR/CNs nanocomposites is much higher
than the degradation temperature of pure CNs. This significant enhancement of
thermal resistance by the presence of NBR matrix can be attributed to the formation
of a confined structure in the NBR/CNs nanocomposites. That is, the CNs is pro-
tected by NBR matrix, indicating the strong interaction between the CNs and NBR
molecules.
The effect of organoclay (OC) on the performance of styrene–butadiene rubber
(SBR)/phenolic resin (PH) blend prepared by two-roll mill was investigated by
Shojaei and Faghihi [111]. They showed through the XRD analysis that dispersion
state of OC is improved by incorporation of PH possibly due to the better inter-
action of PH (present in SBR) with OC. Analysis of cure behavior revealed that
both OC and PH increase the cure rate and crosslinking density. In addition, tensile
and DMTA results showed that the mechanical properties increase by addition of
OC in both SBR and SBR/PH systems, however, the extent of enhancement is
higher for the SBR compared to SBR/PH blend. This was attributed to the pro-
nounced reinforcing efficiency of PH in the system, which dominates the overall
performance of the ternary hybrid and reduces the flexibility of the SBR chains by
enhancing the crosslinking density. Their TGA revealed that the OC increases the
thermal stability of SBR. The incorporation of OC along with PH results in higher
value of thermal degradation rate, which can be indicative of catalytic role of OC in
presence of PH.
In order to minimize the oxidative degradation of SBR at high temperature, He
et al. [112] prepared SBR/clay/carbon black (CB) nanocomposites, then the effects
of nano-clay on the properties of SBR nanocomposites were investigated. They
found that the two fillers were uniformly dispersed in the SBR matrix at nano-scale,
176 A.C. Facio et al.
and the nano-dispersed clay layers can provide the SBR/clay/CB nanocomposites
excellent thermal aging resistance and heat resistance. In addition, they proposed a
heat resistant mechanism; the incorporation of the layered silicate could hinder the
rubber from generating oxygen-containing groups in its surface during high tem-
perature aging. Then the changes of Tg between the rubber outer layer and inner
layer is lowered down, which keep the rubber macromolecular chains flexible, so as
to improve the bending resistance of the high temperature aging nanocomposites.
They predicted that the rubber/clay nanocomposites could be exposed to high
temperature occasions and most likely be used to produce heat-resistant products,
for example, heat-resisting conveyor belt.
Hwang et al. [113] synthesized via in situ polymerization high-impact poly-
styrene (HIPS)/organically modified montmorillonite (organoclay) nanocomposites.
X-ray diffraction and TEM experiments revealed that intercalation of polymer
chains into silicate layers was achieved, and the addition of nanoclay led to an
increase in the size of the rubber domain in the composites. In comparison with neat
HIPS, they found that the HIPS/organoclay nanocomposites exhibited improved
thermal stability as well as an increase in both the complex viscosity and storage
modulus, and they may have been influenced by a competition between the
incorporation of clay and the decrease in the molecular weight of the polymer
matrix.
The bromobutyl rubber (BIIR), modified from butyl rubber (IIR) with bromine,
is known to have faster cure reactivity and better adhesion than unmodified IIR.
Meanwhile, BIIR retains the excellent impermeability and mechanical property of
IIR. It has been used in a wide variety of commercial products, such as tire inner
liners, pharmaceutical closures and protection materials. Nevertheless, the stability
of BIIR has always been a major concern. BIIR is known to be thermally unstable
due to the formation of double bonds, which could be generated by HBr elimination
from its backbone [114]. Recently Xiong et al. demonstrated that both the thermal
stability and the thermal conductivity of BIIR nanocomposites could be improved
by incorporating the ionic liquids (ILs) modified graphene oxide (GO-ILs) using a
solution compounding method. They found by X-ray diffraction analysis of GO-ILs
that ILs had been effectively intercalated into the interlayer of GO, which be able to
raise the exfoliation degree of GO. The increased exfoliation degree facilitated a
good dispersion of GO-ILs in the BIIR matrix observed bay SEM images. The
successful incorporation of GO-ILs in BIIR matrix was found to be able to raise the
Tg of GO-ILs/BIIR nanocomposites due to the attractive interactions of the polymer
chains with the large surface area of the GO-ILs. Most importantly, the thermal
stability of BIIR nanocomposites was enhanced by adding GO-ILs. Their calculated
the thermal degradation kinetic parameters of BIIR nanocomposites demonstrate
that the increased activation energy (Ea) with the addition of GO-ILs was observed
in both methods. In addition, they found that adding 4 wt% GO-ILs, the thermal
conductivity of GO-ILs/BIIR nanocomposites had 1.3-fold improvement compared
with that of the unfilled BIIR [30].
Thermal Degradation of Synthetic Rubber Nanocomposites 177
Hydrogenated nitrile rubber (HNBR) has been developed to improve thermal sta-
bility of nitrile butadiene rubber (NBR). During hydrogenation of NBR, a small
number of double bonds and all the cyano groups are kept unhydrogenated for
subsequent sulphur vulcanization and oil resistance. This elastomer is known for its
physical strength and retention of properties after long term exposure to heat, oil,
and chemicals. Addition of small amount of nanofillers may improve the properties
of this rubber. Choudhury and coworkers incorporate different kind of clays into
HNBR by solution dispersion in order to study the effect of these nanofilleres in the
thermal, mechanical and dynamical mechanical proprieties of the nanocomposites.
They used organically modified and unmodified layered silicates such as Cloisite
NA, Cloisite 30B and Cloisite15A, rod-like sepiolite and spherical nanosilica. They
found that on addition of only 4 phr of silica nanofiller to neat HNBR, the tem-
perature at which maximum degradation took place (Tmax) increased by 4–16 °C,
this is attributed to the high thermal stability of A300 particles. These particles have
a tendency to form agglomeration because of the presence of active silanol group on
its surface for which the mechanical properties drop, in contrast, they found that
30B has undergone full exfoliation within the bulk of the matrix, and thus provides
highest tensile strength, excellent storage modulus and very good thermal stability.
In addition, they observed that Sepiolite because of its fibrous nature, high aspect
ratio and uniform dispersion gives rise to excellent improvement in modulus at
100 % elongation and storage modulus and provides very good thermal stability to
the matrix. The nanocomposite based on 15A clay exhibited intercalated structure,
they claimed that is responsible for intermediate thermal, mechanical and dynamic
mechanical property to the matrix. On other hand an unmodified NA particles, they
observed form XDR and TEM microphotograph agglomeration on addition to the
rubber matrix, and thus NA has the least effect on the thermal and mechanical
properties of the elastomer. They increased up 8 phr the nannofiller lading in the
nanocposite, these increase the thermal as well as mechanical properties of HNBR-
filler nanocomposites [6].
Kong et al. [115] synthesized by melt-intercalation silicone rubber (SR)/clay
nanocomposites using synthetic Fe-montmorillonite (Fe-MMT) and natural Na-
MMT which were modified by cetyltrimethylammoniumbromide, surfactant. They
obtained exfoliated and intercalated nanocomposites. With TGA and mechanical
performance found that with the presence of iron significantly increased the onset
temperature of thermal degradation in SR/Fe-MMT nanocomposites. In addition, the
thermal stability, gel fraction and mechanical property of SR/Fe-MMT were different
from the SR/Na-MMT nanocomposites, so the iron not only in thermal degradation
but also in the vulcanization process acted as an antioxidant and radicals trap. A new
flame-retardant system, SR/Fe-OMT based on an EVA matrix, was examined Fang
et al. [116]. The experimental analyses showed that the exfoliated Fe-OMT had better
dispersion in the EVA matrix than Na-OMT, and it was more effective in improving
178 A.C. Facio et al.
the flame retardancy, thermal stability, and mechanical properties of EVA nano-
composites. Their TGA also showed that EVA/SR/Fe-OMT had the maximum
amount of char residue at 700 °C and had a higher thermal stability on the deacet-
ylated polymer than EVA/SR/Na-OMT. From the tensile tests, they found that the
addition of OMT, especially Fe-OMT, improved the tensile strength and elongation
at break of the nanocomposites. They claimed that OMT could serve as a compati-
bilizer of EVA and SR.
Liu et al. [117] present a very interesting research about different kind of rubbers
filled with nanokaolin or precipitated silica. The fillers were introduced in styrene
butadiene rubber (SBR), natural rubber (NR), butadiene rubber (BR) and ethylene–
propylene diene methylene (EPDM). Their results showed that nanokaolin could
greatly improve the vulcanizing process by shortening the time to optimum cure
and prolonging the setting-up time of cross-linked rubbers, which improves pro-
duction efficiency and operational security. In addition, they found that the rubber
composites filled with nanokaolin have good mechanical properties, they suggest
that these result are by the suitable modification of nanokaolin can make kaolinite
platelets dispersed in rubber matrix in directional parallel arrangements, with
20–50 nm in thickness. The tightly linked interface at the nanoscale range between
the kaolin sheets and rubber molecules is the main reason for the improvements of
mechanical properties and thermal stability. As compared with the rubber com-
posites filled with precipitated silica, they found an increase of onset weight loss
temperature of that filled with nanokaolin is between 3.5 and 126.8 °C in ther-
mogravimetric tests, and were especially good in SBR and BR. In addition, the
stable weight loss temperature for nanokaolin composite can increase 50–90 °C
over that of a precipitated silica composite. Their shows that nano kaolin has not
ably improved thermal the stability of the rubber composites.
In other hand, Shimpi et al. [105] synthesized by solution spray calcium car-
bonate (CaCO3) nanoparticles of three different diameters 9, 15, and 21 nm to form
polybutadiene rubber (PBR) nanocomposites with variations in wt% loading (4, 8,
and 12 %). Their results of PBR nanocomposites were compared with commercial
CaCO3 (40 lm) and fly ash (75 lm) filled PBR microcomposites. They observed that
the incorporation of nano CaCO3 in PBR with reduced size shows better thermal
stability as compared to commercial CaCO3 and fly ash filled PBR. They found at
12 wt% of nano CaCO3 (21, 15, and 9 nm) filled in PBR shows decomposition
temperature at 491, 483, and 472 °C, respectively, while for commercial CaCO3
and fly ash decomposition temperature were observed to be 459 and 461 °C for
same wt% of filler loading. At 4 wt% loading of filler, decomposition temperature
were observed to be 488, 480, 450 °C for nano CaCO3 (21, 15, and 9 nm),
respectively. They argued that this enhancement in thermal stability is due to
uniform dispersion of nano CaCO3 throughout the matrix that keeps the rubber
chains intact on crosslinking, which prevent out diffusion of the volatile decom-
position product [106]. The presence of nanoinorganic particles in between the
rubber chains is responsible for preventing the diffusion of the volatile
Thermal Degradation of Synthetic Rubber Nanocomposites 179
decomposition products from the rubber nanocomposites at same time. From the
above results of rubber nanocomposites, it is clear that nanoinorganic filler provides
better thermal stability as compared with commercial micron size filler.
In recent years, synthetic rubber nanocomposites are of great interest for both
academic researches and industrial applications because they frequently exhibit
unexpected properties synergistically derived from the two or more components.
The properties of elastomeric materials as thermal stability and chemical resistance
are of relevant importance considering both economic and ecologic impacts in
many different areas.
There are two types of rubber polymers: natural rubber and synthetic rubber.
Synthetic rubber is one type of artificial elastomer mainly synthesized from
petroleum byproducts. It has good mechanical property, thermal stability, and
compatibility with petroleum products.
Acrylonitrile rubbers are elastomers of butadiene and acrylonitrile copolymers of
special applications. They are used in applied hydraulics and pneumatics, the
percentage proportion determines their resistance to oil and freeze. Nitrile vulca-
nizates show high elasticity and tensile strength, oil resistance and a low permanent
compressive strain. Prochon et al. reported the influence of keratin, recovered from
the tanning industry, on the thermal and mechanical properties of vulcanizates with
synthetic rubber acrylonitrile-butadiene rubber NBR. The addition of waste protein
to NBR vulcanizates influences the improvement of resistance at high temperatures
and mechanical properties like tensile strength and hardness. The introduction of
keratin to the mixes of rubber previously blended with zinc oxide (ZnO) before
vulcanization process leads to an increase in the cross-linking density of vulca-
nizates. It is present a clear influence of protein on the formation of spatial lattice of
elastomers between protein, zinc oxide, and the elastomer matrix. The polymer
materials received including addition of proteins will undergo biodecomposition in
natural conditions. In that aerobic environment, microorganisms, bacteria, and
fungus digested better polymer materials containing natural additives [118].
The development of nanoparticles with different sizes and shapes, including
spherical particles such as silica, platelets such as layered silicates, and carbon
nanotubes have been used as fillers in elastomeric matrices to improve their
properties like mechanical and barrier. The interaction of the polymer chains with
the filler particles is also crucial in controlling the performance of nanocomposites.
Moreover Ponomarenko et al. reported the melt‐compounded composites of
synthetic styrene–co–butadiene rubber (BUNA SL18) and silica particles (Silica
VN3, Degussa). They showed that at low elongations, silica particles provided a
considerably weaker reinforcement effect of the rubber matrix when compared to
organoclay nanoparticles. The overall thermoelastic behavior of both the rubber/
silica composites and the rubber/organoclay nanocomposites could be quantitatively
180 A.C. Facio et al.
accounted for by a model that explicitly assumed the contributions of local strain
amplification for the rubber matrix and of successive decay of a spatial network of
filler particles with increasing strain, generating the exothermal effects of external
friction between particles. Significantly more intensive heat generation, concomitant
to higher amplitudes of stress relaxation in the rubber/silica composites at high
uniaxial extensions as compared to the rubber/organoclay nanocomposites, was
regarded as evidence for a lower mechanical strength of a spatial network of silica
particles [119].
Furthermore Li et al. reported the use of a novel method (Two-Step Method,
TSM) to investigate the modification process in preparation of rubber, silica, and
bis(3-triethoxysilylpropyl) tetrasulfide (TESPT). The TSM modification indicated
that the TESPT hydrolyzed firstly to generate the silanol (Si–OH), and the silanol
reacted with the hydroxyl groups on the surface of silica. The properties of modified
silica were studied and results exhibited the advantages of TSM, and also revealed
that 8 % TESPT amount was suitable than 12 and 15 % TESPT amount [120].
Mean while Scotti et al. reported the preparation of silica/styrene butadiene
rubber (SBR) nanocomposites by blending method using shape-controlled spherical
and rod-like nanoparticles with different aspect ratios as filler for the rubber rein-
forcement. The influence of the particle morphology on the reinforcing effect
independently of the silica surface chemistry and considering the aspect ratio as the
only geometrical variance. Spherical and anisotropic rod-like particles, dispersed in
the nanocomposites, formed a network of particles bridged by thin rubber layers
throughout the SBR matrix [121].
At the same time Bala et al. studied the filler effects of organomodified dodecyl
alkylammonium intercalated montmorillonite (12C-MNT) for natural rubber (NR)
and styrene butadiene rubber (SBR). The results showed that tensile strength,
modulus, and elongation at break increased significantly as compared to pure
vulcanized NR and SBR when 4 wt% of 12C-MNT was used as filler. In the case of
NR, these properties decreased drastically for 1 wt% of pure Na-MNT [122].
In recent years, lamellar nanofillers have been established as the most important
filler type for barrier and mechanical reinforcement. Dal Point et al. reported a novel
nanocomposite series based on styrene–butadiene rubber (SBR latex) and alpha-
zirconium phosphate (α-ZrP) lamellar nanofillers. The use of surface modified
nanofillers improvement the mechanical properties. However, no modification of
the gas barrier properties is observed. The addition of bis(triethoxysilylpropyl)
tetrasulfide (TESPT) as coupling agent in the system is discussed on the nanofiller
dispersion state and on the filler-matrix interfacial bonding. Simultaneous use of
modified nanofillers and TESPT coupling agent is found out with extraordinary
reinforcing effects on both mechanical and gas barrier properties [123].
Polymer nanocomposites are one of the highly discussed research topics in
recent time. Yehia et al. reported the preparation and the properties of different
nanoclays based on sodium montmorillonite (bentonite) and some organic amines
of varying chain lengths (dodecylamine, hexadecylamine and octadecylamine)
beside amine-terminated butadiene-acrylonitrile copolymer (ATBN) The nano-
composite clays were incorporated in natural and synthetic rubbers (NR, SBR and
Thermal Degradation of Synthetic Rubber Nanocomposites 181
0.83 MPa when 10 wt% functionalized CNTs was added. With the addition of 1 wt%
reinforcement, a peak value of 4.1 kJ energy absorption was obtained. The
homogenous dispersion of CNT-Phenol is thought to be responsible for the con-
siderable enhancement in the reported properties [127].
As can be seen an important aspect in material development is to achieve good
combination of properties. The performance of a composite material depends on
several factors including formulation, dispersion of filler in the polymer matrix and
adhesion between the filler and the matrix. The properties of nanocomposites
depend on the type of nanofiller used and its interaction with the polymer matrix.
delivery systems can improve the disadvantage of orally taken drugs. Commonly,
many drugs taken via the oral route are ineffective because of the first pass
metabolism and drug degradation in the gastrointestinal tract. There must be sig-
nificant controlled drug release into the systemic blood circulation to target organs
via the skin. Suksaeree et al. reported the use of rubber polymers for transdermal
drug delivery systems, including materials for transdermal drug delivery systems
such as styrene-isoprene-styrene (SIS) block copolymer, acrylic rubber hybrid, PIB,
and silicone rubber. For example, capsaicin is commonly used in topical skin
preparations to relieve pain. The SIS block copolymer, in combination with resin
and plasticizer, is used in transdermal drug delivery systems to produce capsaicin-
matrix patches Silicone rubber, a rubber-like material, is an elastomer composed of
silicon together with carbon, hydrogen, and oxygen. The matrix-type patches are
made from silicone rubber containing lidocaine hydrochloride. These matrix-type
patches can be applied to control the rapid release of active principle. The authors
concluded that rubber polymers as important drug carriers have made a great impact
on the advancement of drug delivery science and technology in pharmaceutical
sciences and medical applications [133].
9 Future Trends
10 Conclusions
important reviser type, chemical natural, morphology of nanoparticle used for the
preparation the nanocomposite with synthetic rubber, it is important to be subjected
to high temperature, leading to different reaction secondary factor.
The designing and compounding are key factors in obtaining the intercalated–
exfoliated structure of the clay minerals in the rubber matrix, which ultimately
governs the final physical properties of the composites.
In conclusion the addition of nanoparticles can lead to thermal stabilisation effect
of polymer during their decomposition. However in this sense the effect of nano-
particles content is very crucial due at higher concentration nanoparticles can form
aggregates and the effective area of nanoparticles in contact with polymer macro-
molecular is lower. The thermal stability enhancement takes place at low loading of
nanoparticle.
References
1. Donnet, J.B.: Nano and microcomposites of polymers elastomers and their reinforcement.
Compos. Sci. Technol. 63, 1085–1088 (2003)
2. Yehia, A.A., Akelah, A.M., Rehab, A., El-Sabbagh, S.H., Nashar, D.E., Koriem, A.A.:
Evaluation of clay hybrid nanocomposites of different chain length are reinforcement agent
for natural and synthetic rubbers. Mater. Des. 33, 11–19 (2012)
3. Periadurai, T., Vijayakumar, C.T., Balasubramanian, M.: Thermal decomposition and flame
retardant behaviour of SiO2-phenolic nanocomposite. J. Anal. Appl. Pyrol. 89, 244–249
(2010)
4. Rybiński, P., Janowska, G., Jóźwiak, M., Jóźwiak, M.: Thermal properties and flammability
of nanocomposites based on nitrile rubbers and activated halloysite nanotubes and carbon
nanofibers. Thermochimica Acta 549, 6–12 (2012)
5. Zhang, Y., Liu, Q., Xiang, J., Frost, R.L.: Thermal stability and decomposition kinetics of
styrene-butadiene rubber nanocomposites filled with different particles sized kaolinites. Appl.
Clay Sci. (2014) http://dx.doi.org/10.1016/j.clay.2014.04.002
6. Choundhury, A., Bhowmick, A.K., Ong, C.: Effect of different nanoparticles on thermal,
mechanical and dynamic mechanical properties of hydrogenated nitrile butadiene rubber
nanocomposites. J. Appl. Polym. Sci. 116, 1428–1441 (2010)
7. Sahoo, N.G., Rana, S., Chob, J.W., Li, L., Chan, S.H.: Polymer nanocomposites based on
functionalized carbon nanotubes. Prog. Polym. Sci. 35, 837–867 (2010)
8. Paul, D.R.; Robeson, L.M.: Polymer nanotechnology: nanocomposites. Polymer 49, 3187–
3104 (2008)
9. Mark, J.E.: Ceramic-reinforced polymers and polymer-modified ceramics. Polym. Eng. Sci.
36(24), 2905–2920 (1996)
10. Wen, J., Wilkes, G.L.: Organic/inorganic hybrid network materials by the sol-gel approach.
Chem. Mater. 8(8), 1667–1681 (1996)
11. von Werne, T., Patten, T.E.: Preparation of structurally well-defined polymer nanoparticle
hybrids with controlled/living polymerization. J. Am. Chem. Soc. 121, 7409–7410 (1999)
12. Calvert, P.: Carbon Nanotubes, Ebbesen, T.W. (ed.) CRC Press, Boca Raton (1992)
13. Dresselhaus, M.S., Dresselhaus, G., Avouris, P.: Carbon Nanotubes: Synthesis, Structure,
Properties and Applications, Topics of Applied Physics, vol. 80. Springer, Heidelberg (2001)
14. Luo, J.J., Daniel, I.M.: Characterization and modeling of mechanical behavior of polymer/
clay nanocomposites. Compos. Sci. Technol. 63, 1607–1616 (2003)
186 A.C. Facio et al.
15. Messermith, P.B., Giannelis, E.P.: Polymer layered silicate nanocomposites: in situ
intercalative polymerization of ε-caprolactone in layered silicates. Chem. Mater. 5, 1064–
1066 (1993)
16. Giannelis, E.P.: Polymer layered silicate nanocomposites. Adv. Mater. 8, 29–35 (1996)
17. Komarneni, S.: Nanocomposites. J. Mater. Chem. 2, 1219–1230 (1992)
18. Ruiz-Hitzky, E.: Conducting polymer intercalated in layered solids. Adv. Mater. 5, 334–340
(1993)
19. Hoffman, U., Endell, K., Wilm, D.: Kristallstruktur und Quellung von Montmorillonit. (Das
Tonmineral der Bentonite). Zeitschrift fur Kristallografie Mineral Petrografie Abteilung A 86,
340–348 (1993)
20. Okada, A., Kawasumi, M., Usuki, A., Kujima, Y.: Nylon 6-clay hybrid. Mater. Res. Soc.
Symp. Proc. 171, 45–50 (1990)
21. Lan, T., Kaviratna, P.D., Pinnavaia, T.J.: Mechanism of clay tactoid exfoliation in epoxyclay
nanocomposite. Chem. Mater. 7, 2144–2150 (1995)
22. Abdallah, W., Yilmazer, U.: Preparation and Characterization of thermally stable
phosphonium organoclays and their use in poly (ethylene terephthalate) nanocomposites.
J. Appl. Polym. Sci. 128, 4283–4293 (2013)
23. Gu, Z., Gao, L., Song, G., Liu, W., Li, P., Shan, C.: Octadecylammonium montmorillonite/
natura rubber/cis-1,4-polybutadiene nanocomposites. Appl. Clay Sci. 50, 143–147 (2010)
24. Oberlin, A., Endo, M., Koyama, T.: Filamentous growth of carbon through benzene
decomposition. J. Cryst. Growth 32(3), 335–349 (1976)
25. Endo, M., Koyama, T., Hishiyama, Y.: Structure improvement of carbon fibers prepared
from benzene. Jpn. J. Appl. Phys. 15(11), 2073–2076 (1976)
26. Iijima, S.: Helical microtubules of graphitic carbon. Nature 354(6348), 56–58 (1991)
27. Prado, LASdA, Kopyniecka, A., Chandrasekaran, S., Broza, G., Roslaniec, Z., Schulte, K.:
Impact of filler functionalization on the crystallinity, thermal stability and mechanical
properties of thermoplastic elastomer/crbon nanotube nanocomposites. Macromol. Mater.
Eng. 298, 359–370 (2013)
28. Iqbal, N., Bilal, M., Sagar, A., Maqsood, A.: Fabrication and characterization of multiwalled
carbon nanotubes/silicon rubber composites. J. Appl. Polym. Sci. 128(4), 2439–2446 (2013)
29. Subramaniam, K., Das, A., Häuẞler, L., Harnisch, C., Werner, K.S., Heinrich, G.: Enhanced
thermal stabity of polycloroprene rubber composites with ionic liquid modified MWCNTs.
Polym. Degrad. Stab. 97, 227–287 (2012)
30. Xiong, X., Wang, J., Jia, H., Fang, E., Ding, L.: Structure, thermal conductivity, and thermal
stability of bromobutyl rubber nanocomposites with ionic liquid modified graphene oxide.
Polym. Degrad. Stab. 98, 2208–2214 (2013)
31. Kim, H., Abdala, A., Macosko, C.: Graphene/polymer nanocomposites. Macromolecules 43,
6515–6530 (2010)
32. Peng, C.C., Gӧpfert, A., Drechsler, M., Abetz, V.: Smart silica-rubber nanocomposites in
virtue of hydrogen bonding interaction. Polym. Adv. Technol. 16, 770–782 (2005)
33. Kickelbick, G.: Concepts for the incorporation of inorganic building blocks into organic
polymers on a nanoscales. Polymer 28, 83–114 (2003)
34. Piña, H., Flores, V., del Castillo, L., Dominguez, O.: Processing and mechanical properties of
natural rubber-ZnFe2O4 nanocomposites. J. Mater. Eng. Perform. 16, 470–476 (2007)
35. Sahoo, S., Bhowmick, A.K.: Influence of ZnO nanoparticles on the cure characteristics and
mechanical properties of carboxylate nitrile rubber. J. Appl. Polym. Sci. 106, 3077–3083
(2007)
36. Mishra, S. Shimpi, N.G.: Effect of the variation in the weight percentage of the loading and
reduction in the nanosizes of CaSO4 on the mechanical and thermal properties of styrene-
butadiene rubber. J. Appl. Polym. Sci. 104, 2018–2016 (2007)
37. Zhang, Y., Lee, S., Yoonessi, M., Liang, K., Pittman, C.U.: Phenolic resin trisilanolphenyl
polyhedral oligomeric silsesquioxane (POSS) hybrid nanocomposites: structure and
properties. Polymer 47, 2984–2996 (2006)
Thermal Degradation of Synthetic Rubber Nanocomposites 187
38. Iyer, S., Schiraldi, D.A.: Role of specific interactions and solubility in the reinforcement of
bisphenol-A polymers with polyhedral oligomeric silsesquioxanes. Macromolecules 40,
4942–4952 (2007)
39. Hanssen, R.W.J.M., van Santen, R.A., Abbenhuis, H.C.L.: the dynamic status quo of
polyhedral silsesquioxane coordination chemistry. Eur. J. Inorg. Chem. 2004, 675–683
(2004)
40. Sengupta, R., Chakraborty, S., Bandyopadhyay, S., Dasgupta, S., Mukhopadhyay, R.,
Auddy, K., Deuri, A.S.: A short review on Rubber/Clay nanocomposites with emphasis on
mechanical properties. Polym. Eng. Sci. 47(11), 1956–1974 (2007)
41. Ganter, M., Gronski, W., Semke, H., Zilg, T., Thomann, R., Mülhaupt, R.: Surface-
compatibilized layered silicates—a novel class of nanofillers for rubbers with improved
mechanical properties. Kautsch. Gummi Kunstst. 54(4), 166–171 (2001)
42. Pramanik, M., Srivastava, S.K., Samantaray, B.K., Bhowmick, A.K.: Rubber-clay
nanocomposite by solution blending. J. Appl. Polym. Sci. 87, 2216–2220 (2003)
43. Lim, Sk, Lim, S.T., Kim, H.B., Chin, I., Choi, H.J.: Preparation and physical characterization
of polyepichlorohydrin elastomer/clay nanocomposites. J. Macromol. Sci. B Phys. B 42(6),
1197–1199 (2003)
44. Wu, C.M., Hwang, W.G., Tien, K.C., Chang, Y.C., Fu H.L.: 11th National Conference on
Science and Technology of National Defense, Taipei, Taiwan (2003)
45. Jeon, H.S., Rameshwaram, J.K., Kim, G.: Structure-property relationships in exfoliated
polyisoprene/clay nanocomposites. J. Polym. Sci. B Polym. Phys. 42, 1000–1009 (2004)
46. Varghese, S., Karger-Kocsis, J.: Natural rubber-based nanocomposites by latex compounding
with layered silicates. Polymer 44, 4921–4927 (2003)
47. Zhang, L., Wang, Y., Wang, Y., Sui, Y., Yu, D.: Morphology and mechanical properties of
clay/styrene butadiene rubber nanocomposites. J. Appl. Polym. Sci. 78, 1873–1878 (2000)
48. Wu, Y., Jia, Q., Yu, D., Zhang, L.: Structure and properties of nitrile rubber (NBR)-clay
nanocomposites by co-coagulating NBR latex and clay aqueous suspension. J. Appl. Polym.
Sci. 89, 3855–3858 (2003)
49. Wu, Y.P., Zhang, L.Q., Wang, Y.Q., Liang, Y., Yu, D.S.: Structure of carboxylated
acrylonitrile-butadiene rubber (CNBR)–clay nanocomposites by co-coagulating rubber latex
and clay aqueous suspension. J. Appl. Polym. Sci. 82(11), 2842–2848 (2001)
50. Varghese, S., Gatos, K.G., Apostolov, A.A., Karger-Kocsis, J.: Morphology and mechanical
properties of layered silicate reinforced natural and polyurethane rubber blends produced by
latex compounding. J. Appl. Polym. Sci. 92, 543–551 (2004)
51. Balachandran, M., Bhagawan, S.S.: Studies on acrylonitrile—butadiene copolymer (NBR)
layered silicate composites: mechanical and viscoelastic properties. J. Compos. Mater. Sept.
45, 2011–2022 (2011)
52. Varghese, S., Karger-Kocsis, J.: Melt-compounded natural rubber nanocomposites with
pristine and organophilic layered silicates of natural and synthetic origin. J. Appl. Polym. Sci.
91, 813–819 (2004)
53. Mousa, A., Karger-Kocsis, J.: Rheological and thermodynamical behavior of styrene/
butadiene rubber-organoclay nanocomposites. Macromol. Mater. Eng. 286, 260–266 (2001)
54. Kojima, Y., Fukumori, K., Usuki, A., Okada, A., Kurauchi, T.: Gas permeabilities in rubber
clay hybrid. J. Mater. Sci. Lett. 12, 889–890 (1993)
55. Zheng, H., Zhang, Y., Peng, Z., Zhang, Y.J.: Influence of the clay modification and
compatibilizer on the structure and mechanical properties of ethylene-propylene-diene
rubber/montmorillonite composites. J. Appl. Polym. Sci. 92, 638–646 (2004)
56. Mishra, K., Kim, Il, Chang-Sik., Ha: New millable polyurethane/organoclay nanocomposite:
preparation characterization and properties. Macromol. Rapid Commun. 24, 671–675 (2003)
57. ASTM E 176, Standard Terminology of Fire Standards. In: Annual Book of ASTM
Standards. American Society for Testing and Materials. 4.07 West Conshohocken, PA
58. Hirschler, M.M.: Effect of oxygen on the thermal decomposition of poly(vinylidene fluoride).
Eur. Polym. J. 18, 463–467 (1982)
188 A.C. Facio et al.
59. Inabi, A., Kashiwagi, T.: A calculation of thermal degradation initiated by random scission,
unsteady radical concentration. Eur. Polym. J. 23(11), 871–881 (1987)
60. Steckler, K.D., Kashiwagi, T., Baum, H.R., Kanemaru, K.: Analytical model for transient
gasification of noncharring thermoplastic materials. In: Cox, G., Langford, B. (eds.)
Proceedings of Third International Symposium on Fire Safety Science, London (1991)
61. Sommers, A.E., Bastow, T.J., Burgar, M.I., Forysth, M., Hill, A.J.: Quantifying rubber
degradation using NMR. Polym. Degrad. Stab. 2000(70), 31–37 (2000)
62. Ranby, B., Rabek, J.F.: Photodegradation, photooxidation and photostabilization of
polymers. Wiley, London (1975)
63. Stephen, R., Jose, S., Joseph, K., Thomas, S., Ommen, Z.: Thermal stability and ageing
properties of sulphur and gamma radiation vulcanized natural rubber (NR) and carboxylated
styrene butadiene rubber (XSBR) latices and their blends. J. Polym. Degrad. Stab. 91,
1717–1725 (2006)
64. Choi, S., Han, D.H., Ko, S.W., Lee, H.S.: Thermal aging behaviors of elemental sulfur-free
polyisoprene vulcanisates. Bull. Korean Chem. Soc. 26, 1853–1855 (2005)
65. Akiba, M., Hashim, A.S.: Vulcanization and crosslinking in elastomers. Prog. Polym. Sci. 22
(3), 475–521 (1997)
66. Gehani, R.: National innovation system and disruptive innovations in synthetic rubber and
tire technology. J. Thechnol. Manag. innov. 2, 55–72 (2007)
67. Bhatt, R., Shah, D., Patel, K.C., Trivedi, U.: PHA-rubber blends: synthesis, characterization
and biodegradation. Bioresour. Technol. 99, 4615–4620 (2008)
68. Arantes, T., Leao, K., Tavares, M., Ferreira, A.: NMR study of styrene-butadiene rubber
(SBR) and TiO2 nanocomposites. Polym. Testing 28, 490–494 (2009)
69. Tonny, M.M., Nemr, K.F.: Application of acrylonitrile butadiene rubber for management of
industrial waste silica. Mater. Sci. Eng. 1, 1–6 (2012)
70. Chayan, Das, Bharat, K.: Preparation and studies of nitrile rubber nanocomposites with silane
modified silica nanoparticle. Research Journal of Recent Sciences 1, 357–360 (2012)
71. Chaichua, B., Prasassaraki, P., Poompradub, S.: In situ silica reinforcement of natural rubber
by sol-gel process via rubber solution. J. Sol-Gel Sci. Technol. 52, 219–227 (2009)
72. Mohomane, S.M., Djokovic, V., Thomas, S., Luyt, A.S.: Polychloroprene nanocomposite
filled with different organically modified clays: Morphology, thermal degradation and stress
relaxation behavior. Polym. Testing 30, 585–593 (2011)
73. Popovic, I., Katsikas, L.: The characterization of polymer composite by thermogravimetry.
Mater. Compos. 40, 7–12 (2006)
74. Balachandran, M., Bhagawan, S.: Mechanical, thermal and transport properties of nitrile
rubber (NBR)-nanoclay composite. J. Polym. Res. 19, 2–10 (2012)
75. Bourbigot, S., Gilman, J.W., Wilkie, C.A.: Kinetic analysis of the thermal degradation of
polystyrene montmorillonite nanocomposite. Polym. Degrad. Stab. 84(3), 483–492 (2004)
76. Peeterbroeck, S., Lepoittevin, B., Pollet, E., Benali, S., Broekaert, C., Alexandre, M.,
Bonduel, D., Viville, P., Lazzaroni, R., Dubois, P.: Polymer layered silicate/carbon nanotube
nanocomposites: the catalyzed polymerization approach. Polym. Eng. Sci. 46, 1022–1030
(2006)
77. Gamlin, C., Markovic, G., Dutta, K., Choudhury, R., Matisons, J.G.: Structural effects on the
decomposition kinetics of EPDM elastomers by high-resolution TGA and modulated TGA.
J. Therm. Anal. Calorim. 591, 319–336 (2000)
78. Carretero, G.J., Verdejo, R., Arroyo, M., López, M.M.A.: Nuevos avances en el desarrollo de
nanocompuestos elastoméricos. Suplemento de la Revista Latinoamericana de Metalurgía y
Materiales S2(1), 33–34 (2009)
79. Zhang, J., Wang, L., Zhao, Y.: Improving performance of low-temperature hydrogenated
acrylonitrile butadiene rubber nanocomposites by using nano-clays. Mater. Des. 50, 322–331
(2013)
80. Sadaka, F., Campistron, I., Laguerre, A., Pilard, J.F.: Telechelic oligomers obtained by
metathetic degradation of both polyisoprene and styrene-butadiene rubbers. Appl. Recycl.
Waste Tire Rubber 98, 736–742 (2013)
Thermal Degradation of Synthetic Rubber Nanocomposites 189
81. Gu, Z., Song, G., Liu, W., Li, P., Gao, L., Li, H., Hu, X.: Preparation and propertied of
styrene butadiene rubber /natural rubber/ organo-bentonite nancomposite prepared from latex
dispersion. Appl. Clay Sci. 46, 241–244 (2009)
82. Yehia, A.A., Akelah, A.M., Rehab, A., Sabbagh, S.H., Nashar, D.E., Koriem, A.A.:
Evaluation of clay hybrid nanocoposite of different chain length as reinforcing agent for
natural and synthetic rubbers. Mater. Des. 33, 11–19 (2012)
83. Cerin, O., Fontaine, G., Duquesne, S., Bourbigot, S.: Thermal stability of synthetic rubber
nanocomposites. In: Mittal. V. (ed.) Recent Advance in Elastomeric Nanocomposites.
Springer, Berlin, Heidelberg (2011)
84. Malas, A., Pal, P., Das, ChK: Effect of expanded graphite and modified graphite flakes on the
physical and thermo-mechanical properties of styrene butadiene rubber/polybutadiene rubber
(SBR/BR) blends. Mater. Des. 55, 664–673 (2014)
85. Cabello, Ch., Saénz, A., López, Ll, Pérez, C., Barajas, L., Ávila, C.: Modificación superficial
de (MWCNT) con H2SO4/HNO3 mediante ultrasonido. Afinidad 68, 370–374 (2012)
86. Inukai, S., Niihara, K.-I., Noguchi, T., Ueki, H., Magario, A., Yamada, E., Inagaki, S., Endo,
M.: Preparation and properties of multiwall carbon nanotubes/ polystyrene-block-
polybutadiene-block-polystyrene-composite. Ind. Eng. Chem. Res. 50, 8016–8022 (2011)
87. Gerorge, J.J., Bhowmick, A.K.: Influence of matrix polarity on the properties of ethylene
vinyl acetate-carbon nanofiller nancomposite. Nanoscale Res. Lett. 4, 655–664 (2009)
88. Gerorge, J.J., Bhowmick, A.K.: Ethylene vinyl acetate/expanded graphite nancomposite by
solution intercalation: preparation, characterization and properties. J. Mater. Sci. 43, 702–708
(2009)
89. Rybinski, P., Janowska, G., Jozwiak, M., Pajak, A.: Thermal stability and flammability of
butadiene-styrene rubber nanocomposites. J. Therm. Anal. Calorim. 109, 561–571 (2012)
90. Liu, Q., Zhang, Y., Xu, H.: Properties of vulcanized rubber nanocomposite filled with
nanokaolin and precipitated silica. Appl. Clay Sci. 42, 232–237 (2008)
91. Madorsky, S.L.: Thermal Degradation of Polymer, Reprinted by Robert E. Kreiger, New
York (1976)
92. Jang, L.W., Kang, C.M., Lee, D.C.: A new hybrid nanocomposite prepared by emulsion
copolymerization of ABS in the presence of clay. J. Polym. Sci. Part B Polym. Phys. 39,
719–727 (2001)
93. Choi, Y.S., Xu, M.Z., Chung, I.J.: Synthesis of exfoliated acrylonitrile–butadiene–styrene
copolymer (ABS) clay nanocomposites: role of clay as a colloidal stabilizer. Polym. Degrad.
Stab. 46, 531–538 (2005)
94. Karahaliou, E.-K., Tarantili, P.A.: Preparation of poly(acrylonitrile–butadiene–styrene)/
montmorillonite nanocomposites and degradation studies during extrusion reprocessing.
J. Appl. Polym. Sci. 113, 2271–2281 (2009)
95. Pourabbas, B., Azimi, H.: Indirect synthesis of ABS/clay nanocomposites, comparison and
thermal properties. J. Compos. Mater. 42, 2499–2522 (2008)
96. Wang, S.F., Hu, Y., Song, L., Wang, Z.Z., Chen, Z.Y., Fan, W.C.: Preparation and thermal
properties of ABS/montmorillonite nanocomposite. Polym. Degrad. Stab. 77, 423–426
(2002)
97. Wang, S., Hu, Y., Lin, Z., Gui, Z., Wang, Z., Chen, Z., Fan, W.: Flammability and thermal
stability studies of ABS/montmorillonite nanocomposite. Polym. Int. 52, 1045–1049 (2003)
98. Cai, Y., Huang, F., Xia, X., Wei, Q., Tong, X., Wei, A., Gao, W.: Comparison between
structures and properties of ABS nanocomposites derived from two different kinds of OMT.
J. Mater. Eng. Perform. 19, 171–176 (2010)
99. Ying, G.H., Fung, J.L.: Organic–inorganic composite materials from acrylonitrile–
butadiene–styrene copolymers and silica through an in situ sol–gel process. J. Appl.
Polym. Sci. 75, 275–283 (2000)
100. Yang, S., Castilleja, J.R., Barrera, E.V., Lozano, K.: Thermal analysis of an acrylonitrile–
butadiene–styrene/SWNT composite. Polym. Degrad. Stab. 83, 383–388 (2004)
101. Ma, H., Tong, L., Xu, Z., Fang, Z.: Synergistic effect of carbon nanotube and clay for
improving the flame retardancy of ABS resin. Nanotechnology 18, 375602 (2007)
190 A.C. Facio et al.
102. Liu, L., Grunlan, J.C.: Clay assisted dispersion of carbon nanotubes in conductive epoxy
composites. Adv. Funct. Mater. 17, 2343–2348 (2007)
103. Tang, C., Xiang, L., Su, J., Wang, K., Yang, C., Zhang, Q., Fu, Q.: Largely improved tensile
properties of chitosan film via unique synergistic reinforcing effect of carbon nanotube and
clay. J. Phys. Chem. B 112, 3876–3881 (2008)
104. Barick, A.K., Tripathy, D.K.: Thermal and dynamic mechanical characterization of
thermoplastic polyurethane/organoclay nanocomposites prepared by melt compounding.
Mater. Sci. Eng. A 527, 812–823 (2010)
105. Shimpi, N.G., Mishra, S.: Synthesis of nanoparticles and its effect on properties of
elastomeric nanocomposites. J. Nanopart. Res. 12, 2093–2099 (2010)
106. Chen, G., Liu, S., Chen, S., Qi, Z.: FTIR spectra, thermal properties, and dispersibility of a
polystyrene/montmorillonite nanocomposites. Macromol. Chem. Phys. 202, 1189–1193
(2001)
107. Chrissafis, K., Bikiaris, D.: Can nanoparticles really enhance thermal stability of polymers?
Part I: an overview on thermal decomposition of addition polymers. Thermochim. Acta 523,
1–24 (2011)
108. Li, H., Wang, H., Wu, Y., Zhang, X., Zheng, J.: Effect of the interfacial interaction on
thermal oxidative stability of carbon nanotubes/silicone rubber composites. Sci. Adv. Mater.
5, 453–461 (2013)
109. Wang, X., Dou, W.: Preparation of graphite oxide (GO) and the thermal stability of silicone
rubber/GO nanocomposites. Thermochim. Acta 529, 25–28 (2012)
110. Cao, X., Xu, C., Wang, Y., Liu, Y., Liu, Y., Chen, Y.: New nanocomposite materials
reinforced with cellulose nanocrystals in nitrile rubber. Polym. Testing 32, 819–826 (2013)
111. Shojaei, A., Faghihi, M.: Physico-mechanical properties and thermal stability of thermoset
nanocomposites based on styrene-butadiene rubber/phenolic resin blend. Mater. Sci. Eng., A
527, 917–926 (2010)
112. He, S.-J., Wang, Y.-Q., Xi, M.-M., Lin, J., Xue, Y., Zhang, L.-Q.: Prevention of oxide aging
acceleration by nano-dispersed clay in styrene-butadiene rubber matrix. Polym. Degrad. Stab.
98, 1773–1779 (2013)
113. Hwang, S.J., Joo, Y.L., Lee, S.J.: Properties of high-impact polystyrene/organoclay
nanocomposites synthesized via in situ polymerization. J. Appl. Polym. Sci. 110, 1441–
1450 (2008)
114. Malmberg, S.M., Parent, J.S., Pratt, D.A., Whitney, R.A.: Isomerization and elimination
reactions of brominated poly(isobutylene-co-isoprene). Macromolecules 43, 8456–8461
(2010)
115. Kong, Q., Hu, Y., Song, L., Wang, Y., Chen, Z., Fan, W.: Influence of Fe-MMT on
crosslinking and thermal degradation in silicone rubber/clay nanocomposites. Polym. Adv.
Technol. 17, 463–467 (2006)
116. Fang, S., Hu, Y., Song, L., Wu, J.: Preparation and investigation of ethylene-vinyl acetate
copolymer/silicone rubber/clay nanocomposites. J. Appl. Polym. Sci. 113, 1664–1670 (2009)
117. Liu, Q., Zhang, Y., Xu, H.: Properties of vulcanized rubber nanocomposites filled with
nanokaolin and precipitated silica. Appl. Clay Sci. 42, 232–237 (2008)
118. Prochon, M., Przepiórkowska, A.: Innovative application of biopolymer keratin as a filler of
synthetic acrylonitrile-butadiene rubber NBR. J. Chem. 2013, 1–8 (2013)
119. Ponomarenko, S.M., Privalko, E.G., Privalko, V.P., Schön, F., Gronski, W.: Structure and
thermoelasticity of synthetic rubber/silica composites. J. Macromol. Sci. Part B 43, 1231–
1242 (2004)
120. Li, Y., Han, B., Liu, L., Zhang, F., Zhang, L., Wen, S., Lu, Y., Yang, H., Shen, J.: Surface
modification of silica by two-step method and properties of solution styrene butadiene rubber
(SSBR) nanocomposites filled with modified silica. Compos. Sci. Technol. 88, 69–75 (2013)
121. Scotti, R., Conzatti, L., D’Arienzo, M., Di Credico, B., Giannini, L., Hanel, T., Stagnaro, P.,
Susanna, A., Tadiello, L., Morazzoni, F.: Shape controlled spherical (0D) and rod-like (1D)
silica nanoparticles in silica/styrene butadiene rubber nanocomposites: role of the particle
morphology on the filler reinforcing effect. Polymer 55, 1497–1506 (2014)
Thermal Degradation of Synthetic Rubber Nanocomposites 191
122. Bala, P., Samantaray, B.K., Srivastava, S.K., Nando, G.B.: Organomodified montmorillonite
as filler in natural and synthetic rubber. J. Appl. Polym. Sci. 92, 3583–3592 (2004)
123. Dal Pont, K., Gérard, J.-F., Espuche, E.: Microstructure and properties of styrene-butadiene
rubber based nanocomposites prepared from an aminosilane modified synthetic lamellar
nanofiller. J. Polym. Sci. B Polym. Phys. 51, 1051–1059 (2013)
124. Songmin, S., Lu, G., Chun-Wah, Y.M.: Improvement of carbon nanotubes dispersion by
chitosan salt and its application in silicone rubber. Compos. Sci. Technol. 86, 129–134
(2013)
125. Xiubin, Z., Haiyan, Z., Jin, L., Liping, L., Qiguang, W.: Thermal conductivity and thermal
stability enhancement of ethylene propylene diene methylene with carbon nanotube. J. Reinf.
Plast. Compos. 33, 767–774 (2014)
126. Peddini, S.K., Bosnyak, C.P., Henderson, N.M., Ellison, C.J., Paul, D.R.: Nanocomposites
from styrene-butadiene rubber (SBR) and multiwall carbon nanotubes (MWCNT) part 1:
morphology and rheology. Polymer 55, 258–270 (2014)
127. Laoui, T.: Mechanical and thermal properties of styrene butadiene rubber-functionalized
carbon nanotubes nanocomposites. Fuller. Nanotub. Carb. Nanostruct. 21, 89–101 (2013)
128. Ganter, B., Boßhammer, Irmer, U.: UV-curable silicone rubbers open up new fields. Int.
Polym. Sci. Technol. 40, 1–4 (2013)
129. Anwar Parvez, M., Al-Mehthel, M., Al-Abdul, W.H.I., Hussein, I.A.: Utilization of sulfur
and crumb rubber in asphalt modification. J. Appl. Polym. Sci. 131, 1–11 (2014)
130. Zanchet, A., Carli, L.N., Giovanela, M., Brandalise, R.N., Crespo, J.S.: Use of styrene
butadiene rubber industrial waste devulcanized by microwave in rubber composites for
automotive application. Mater. Des. 39, 437–443 (2012)
131. Costa, P.P., Silvia, C.C., Viana, J.C., Lanceros Mendez, S.S.: Extruded thermoplastic
elastomers styrene-butadiene-styrene/carbon nanotubes composites for strain sensor
applications. Compos. B Eng. 57, 242–249 (2014)
132. Chameswary, J., Sebastian, M.: Butyl rubber–Ba0.7Sr0.3TiO3 composites for flexible
microwave electronic applications. Ceram. Int. 39, 2795–2802 (2013)
133. Suksaeree, J., Pichayakorn, W., Monton, C., Sakunpak, A., Chusut, T., Saingam, W.: Rubber
polymers for transdermal drug delivery systems. Ind. Eng. Chem. Res. 53, 507–513 (2014)
Outdoor Exposure Degradation
of Ethylene-Vinyl-Acetate Encapsulant
Material for Photovoltaic Application
1 Introduction
K. Agroui (&)
Semiconductors Technology for Energetic Research Center (CRTSE),
2, Bd. Dr. Frantz Fanon, BP 140 Alger 7 Merveilles, Algiers, Algeria
e-mail: [email protected]
G. Collins
Department of Biomedical Engineering, New Jersey Institute of Technology,
Newark, NJ 07102, USA
service life in general [1]. Accelerated aging such as damp-heat, UV-irradiation and
corrosive atmosphere add to degradation and form a complex field of influencing
factors.
One important application of EVA (Ethylene Vinyl Acetate) material is the
encapsulation of solar cells in photovoltaic (PV) modules, where the material has to
fulfill several basic functions. Unfortunately, the IEC standard does not provide any
information on the changes in the internal structure of the EVA encapsulant
material as a consequence of encapsulation process or environmental exposure.
Generally, PV modules degradation is investigated by using analysis methods
such as I–V curve measurements, electroluminescence, thermo-imaging or more
sophisticated techniques [2, 3]. Investigating the mechanism causing degradation of
the components in a PV module is an approach to get information about the
degradation progress. To assess the long term performance and durability of EVA
encapsulant material, it was necessary not only to measure the deterioration of
macroscopic physical properties, but also to gain information about degradation
processes taking place at a molecular level.
Many studies have been conducted, utilizing various technical analysis to assess
the conditions of the EVA. These methods require the destructive extraction of
samples of the polymer from the module [4, 5]. Extraction of EVA samples from
field deployed PV module is very difficult and contributes to the whole destruction
of the PV module. For this reason, the durability in outdoor exposure of EVA
encapsulant under the conditions simulating those in PV module is often used to
assess the weathering of polymeric materials [6].
In several papers, the thermal behavior of EVA material is discussed in detail.
The changes in thermal properties due to storage at room temperature and annealing
at elevated temperatures are investigated and explained by characterizing the
changes in polymer morphology [7, 8]. Nevertheless, these findings were not linked
to Thermally Stimulated Current (TSC), which defines the transitions and relax-
ations that depend on changes in the mobility of molecular scale dipolar structural
units. The high interest of TSC technique is due to the very low equivalent fre-
quency and its capability to resolve complex dielectric transitions. TSC is based on
the ability of polar molecules to be moved by an electrostatic field and also has been
frequently employed to investigate the molecular motions in polymeric materials
[9, 10]. TSC complements perfectly the thermal analysis methods like as Differ-
ential Scanning Calorimetry (DSC) to determine fundamental properties of EVA
and also has been frequently employed to investigate the molecular motions in
polymeric materials [11].
The aim of this work is to analyze the changes in the relevant thermal behavior
of the crosslinked EVA encapsulant material due to outdoor exposure in Medi-
terranean climate by TSC and DSC thermal analysis. The changes in thermal
properties should be discussed and special interest will be focused on the specific
TSC relaxation parameters like activation energy and relaxation frequency deter-
mination by using the initial rise method.
Outdoor Exposure Degradation of Ethylene-Vinyl-Acetate … 195
2 Sample Preparation
EVA encapsulant test uses EVA A9918 (33 % of vinyl acetate) standard cure from
STR (Specialized Technology Resources) manufacturer and is referred to as ori-
ginal EVA [12]. The original EVA films were inserted between two pieces of
Teflon and placed on the lower chamber of the laminator in order to produce the
correct thermal conditions during the cure. The EVA has to be crosslinked chem-
ically in order to obtain the required thermo-mechanical properties. The cure cycle
is executed using the SPIIRE-LAMINATOR (Fig. 1) at temperature of 160 °C for
15 min according to the standard module lamination conditions.
Original EVA film submitted to the cure step cycle is referred to as cured or
crosslinked EVA. The gel content can be determined by a solvent (toluene)
extraction method as a standard procedure described by STR. The gel content
measurement during the cure cycle, is 87.4 % according to STR procedure.
Natural weathering involves placing samples on inclined racks orientated at the sun
at an angle of 45° in a southerly direction as described in ASTM standard [6]. The
laminate configuration was used is: glass/cured EVA encapsulant/TPT back sheet
polymer with Aluminum frame and without the solar cell circuit as shown in Fig. 2.
This was done to simulate the similar situation of EVA material when the PV
modules operate outdoors. The outdoor measurements were performed at two
different sites. The first site is located at Renewable Energy Development Centre
(CDER) located at Algiers as Mediterranean climate and the second site is the
Applied Renewable Energy Research Unit (URAER) located at Adrar (South-west
of Algiers) as desert climate. In order to investigate the physical aging of the EVA
material, specimens were exposed for 18 months and 8 years in natural weathering
of CDER and URAER site respectively.
Special instrumentation has been provided for the measurement of the meteo-
rological parameters of CDER site, like horizontal global irradiance-humidity and
maximal-minimal ambient temperatures as illustrated in Figs. 3 and 4 respectively.
The ambient temperature and relative humidity of the exposure location site is in
the range of 18–40 °C and 20–95 % respectively.
TSC is a technique for detecting the transitions that depend on changes in the
mobility of molecular scale dipolar structural units. TSC is based on the ability of
polar molecules to be moved by an electrostatic field. Two types of current are
generated: thermally stimulated polarization current (TSPC) and thermally stimu-
lated depolarization current (TSDC). TSPC is generated when dipolar structures
orient in a static electric field with increasing in the temperature. TSDC is generated
because of the relaxation of the previously polarized molecules as reported in
Fig. 5.
In the TSC technical literature, the most frequently described experiment is
TSDC. When performing the experiment measurements by TSC technique it was
noted that the thermostimulated current is greatly influenced by the choice of the
heating rate value, due to the fact that the detected current peak is very small (in the
order of pA).
Equation (1) shows the current density J(T) at temperature T released during
thermally stimulated current measurement [11].
8 9
< W ZT =
B W
JðTÞ ¼ Aexp exp dT 0 ð1Þ
: kT q kT ;
To
where A, B are the constant of the process, W the activation energy of the process,
T and T′ the temperature, To the initial temperature, k the Boltzman’s constant and
q the heating rate. The relaxation process during a glass transition is usually the
superposition of several relaxation times. The separation of this distribution of
relaxation times can be achieved using the thermal windowing (TW) technique by
applying the excitation voltage on a narrow temperature window, the response of
Outdoor Exposure Degradation of Ethylene-Vinyl-Acetate … 199
the material can be modeled using a single relaxation time. Shifting the polarization
window across the entire temperature range of a transition generates the thermal
windowing spectra corresponding to a map of that distribution of the relaxation
times for the transition. For the determination of the characteristic parameters of the
process i.e. the activation energy and the relaxation time factor, the initial rise
method is mostly used. This method is based on the fact that the integral term in
Eq. (1) is low for T ≪ Tmax and consequently the first exponential term dominates.
In this situation the current density during a thermal stimulated measurement has an
Arrhenius expression. Therefore the activation energy can be determined by the
slope of the plot ln(J(T)) versus 1/T as shown in Eq. (2).
W
JðTÞ ¼ J0 exp ð2Þ
kT
The relaxation time τ(T) at temperature T can be extracted from the elementary
spectrum by using Eq. (3).
PðTÞ
sðTÞ ¼ ð3Þ
JðTÞ
Z1
1
PðTÞ ¼ JðT0 ÞdT0 ð4Þ
q
T
Equation (5) shows the relaxation frequency α(Tmax) at the peak temperature Tmax.
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qW
Tmax ¼ ð5Þ
kaðTmax Þ
The Debye formalism that is represented in Eqs. (1–5) strictly only applies for a
single relaxation process. That is to say, the equations can only be applied for an
isolated relaxation. The global polarization experiments that were performed pro-
duce a depolarization current that represents the entire distribution of relaxations. In
order to isolate a relaxation process and properly apply the equations, it would be
necessary to carry out thermal windowing experiments. In our study we applied the
equations to the low temperature relaxation process in order to get a first approx-
imation of the magnitude of the activation energy.
The TSC measurements provide information on the molecular scale mobility in
the internal structure of a solid material and is based on the motions of dipoles in
response to temperature and a static electric field. TSC is well suited to study the
degree of curing and the determination of the glass transition temperature. The
200 K. Agroui and G. Collins
For evaluating the dielectric properties of EVA an experimental set-up was installed
according to the NFC 26 200 et NFC 26 230 recommendations system. The main
component is the ring guard capacitor type 16451B (Hewlett-Packard). EVA
samples are contained between the upper and lower metal plate electrodes within a
confinement ring soldered to the lower plate. The upper electrode is connected to
high voltage terminal bridge type 4284A (Hewlett-Packard). The electrode are
connected to heating resistances to allow measurements to be taken at several
temperatures from −50 to 65 °C at a rate of 2 °C/min in the frequency range from
1 Hz to 100 kHz. Capacitance (C) and dissipator factor (tgδ) were measured at
0.05 % degree of precision. Dielectric constant (ε) were deduced from the
Outdoor Exposure Degradation of Ethylene-Vinyl-Acetate … 201
For evaluating the electrical properties of EVA an experimental set-up was installed
according to the IEC recommendations system. Figure 8 shows a schematic rep-
resentation of the test facility. The main component is the ring guard capacitor type
2904 (TETTEX). EVA samples are contained between the upper and lower metal
plate electrodes within a confinement ring soldered to the lower plate. The elec-
trodes are connected to heating resistances to allow measurements to be taken at
several temperatures up to 150 °C which are stabilised with a temperature regulator
type 2965 (TETTEX). The electrode pressure is kept constant and equal to
2.5 × 104 pa. The applied voltage is adjusted to a value of 500 VAC and frequency
of 50 Hz to favour optimal sensibility of measurements. Insulating resistance (R)
was measured with a Megohmeter type MOM11 WTW, capacitance (C) and dis-
sipator factor (tgδ) were measured with a precision bridge type 2891 (TETTEX).
The resistivity (ρ) and dielectric constant (ε) were deduced from the measurements.
To identify EVA formulation, degradation and even stabilizer diffusion and con-
sumption, the Fourier Transform Infrared (FTIR) spectroscopy in ATR mode is a
simple and satisfying method. The FTIR measurements were carried out with a
202 K. Agroui and G. Collins
spectrometer type Hyperion 2000 Nexus from Thermo Nicolet manufacturer. The
spectrometer is equipped with a DTGM KBr detector in transmission mode. All
FTIR spectra were recorded at 4 cm−1 resolution in the 400–4000 cm−1.
Tensile tests were carried out with a screw driven universal test machine of the type
Instron 4505 (Instron International Ltd., High Wycombe, UK) at 23 °C. The test
samples were prepared according to ASTM D638-76 IV within maximum
dimensions size of 15 × 75 mm, the standard dumbbell-shaped test samples had a
gauge length of 30 mm and a width of 12 mm [14]. The average speed value of
50 mm/min was used for plotting the stress–strain curve. From a total of at least five
samples for each test series were tested and their average plotted where the stress-at-
break (σb) and strain-at-break (εb) were deduced.
3.9 DMTA
E ¼ E0 þ jE00 ð6Þ
where: E′ is the storage modulus, E″ is the loss modulus. The loss factor tgδ
expression is given by Eq. (7).
Outdoor Exposure Degradation of Ethylene-Vinyl-Acetate … 203
E00
tgd ¼ ð7Þ
E0
Figure 9 shows the comparison of TSDC and TSPC results, after second run at
polarization temperature of 85 °C, of the EVA sample before and after aging for
6 months in outdoor exposure. TSC experiments on EVA show that a low tem-
perature peak located at −24 °C is the Tg for a polyethylene rich phase, and the high
temperature peak located at +31 °C is the Tg for a poly(vinyl acetate) rich phase.
The high temperature peak appears also to have a shoulder above 50 °C, charac-
teristic of the change in molecular crystal melting at it will be revealed by DSC
analysis. It is noted that depolarization is the relaxation of dipoles away from the
direction of the field, and polarization is the motion of the dipoles into the direction
of the field. For this reason, TSDC and TSPC experiments generate current peaks in
opposite directions; in this case, TSDC will generate positive peaks and TSPC will
generate negative peaks.
It would be expected that if the identical dipoles in the same number were
relaxing in the case of TSDC and polarizing in the case of TSPC, that the peaks
would nominally be mirror images of each other. Also, it is noted that while there is
agreement in terms of the positions of the peaks, there is substantial disagreement in
terms of their shape and magnitude. In all cases, the low temperature TSDC peak is
observably larger than the low temperature TSPC peak. Again, this is consistent
with the crystalline melting at the polarization temperature and generation of a
higher fraction of mobile amorphous material as has been discussed above.
The high temperature TSDC peak, has a smooth regular shape that would be
expected from a dipole relaxation process. In all cases, however, the high tem-
perature TSPC peak has the expected shape on the low temperature side, and
develops irregular shape on the high temperature side. These irregularities in shape
are not expected for dipole relaxations and likely reflect the non-systematic effect of
dipole motion as a consequence of crystal melting.
Figures 10 and 11 show the TSDC curves at 60 °C polarization temperature of
the EVA before and after exposure at CDER and URAER sites respectively. There
are differences in relative magnitudes of the low and high temperature relaxation
peaks. These results suggest that prolonged exposure selectively affects the poly
(vinyl acetate) rich phase, with much less impact on the polyethylene rich phase.
This is due to the progress of EVA crosslinking reaction such as temperature
increase by long-term exposure. We found also, that the aged EVA after exposure
showed considerable decrease in current intensity for the high temperature polari-
zation due to secondary melting peaks as it will be revealed by DSC technique.
TSC peak parameters according to Fig. 11 are illustrated in Tables 1 and 2. The
difference of the magnitude of peak current by TSC technique is presumably
attributed to post-crosslinking and recrystallization, occurring selectively in the
high temperature phase as a result of outdoor exposure under different climatic
parameters.
For the determination of the characteristic parameters of the process i.e. the
activation energy and the relaxation time factor, the initial rise method is mostly
used. This method is based on the fact that for restricted conditions [15], the current
density during a thermal stimulated measurement can be expressed by Arrhenius
equation. From TSDC curves in Fig. 12, under polarization temperature of 0 °C, the
Outdoor Exposure Degradation of Ethylene-Vinyl-Acetate … 205
activation energy can be obtained from the plot of ln(J) versus 1000/Tm as seen in
Fig. 13. The activation energy of the unaged and aged EVA for 18 months is
calculated to be 33.5 and 33.8 kJ/mol, where the corresponding relaxation fre-
quency is 4.9 × 10−3 and 5.5 × 10−3 Hz respectively, which is in good agreement
206 K. Agroui and G. Collins
with literature results [16, 17]. It is noted that the activation energy is not affected
substantially and is identical within the range of measurement.
It is noted that the magnitude of the low temperature relaxation peak is larger for
the EVA samples after that have been held at the 60 °C polarization temperature
when compared to the 0 °C polarization temperature, due to an increase in the
number of mobile dipoles in that domain. Instead, it seems to reflect changes in the
internal structure of the material as a consequence of the two different temperature
programs.
Results concerning permittivity of EVA before and after exposure are illustrated
in Figs. 14 and 15 respectively. As shown, permittivity of EVA is a non-linear
function of temperature and it decreases with increasing frequency. The plot of
dissipator factor versus temperature at various frequency before and after exposure
as represented in Figs. 16 and 17 respectively, shows that EVA exhibits relaxation
phenomenon. It is found that the relaxation behavior changes with frequency. At
frequency of 1 Hz the glass transition temperature of the crosslinked EVA is found
to be −28.7 °C. EVA after exposure is able to maintain dielectric constant and low
dissipator factor over a wide temperature range. These low values are normally
considered satisfactory for insulating material in the photovoltaic module encap-
sulation process.
Figure 18 shows the DSC experiments, in first heating mode, of the EVA samples
before and after aging. On first heating, the unaged EVA sample show one
208 K. Agroui and G. Collins
endothermic process clearly visible with a peak at 47.5 °C and with a shoulder at
55 °C. For the aged EVA samples, the distinctive feature of these results is that
there are two different endothermic processes due to the recrystallization phe-
nomenon. There is a low temperature event with peaks at 43 and 46 °C, and a
higher temperature endothermic process clearly visible with peaks at 59 and 66 °C
for EVA samples aged during 6 and 18 months respectively. This dual endotherm
behavior in outdoor exposure is similar to that observed for EVA samples aged
under accelerated test as high-UV conditions as described in IEC 61215. These
peaks can be assigned to secondary crystallization due to the photo-degradation
[17].
For EVA aged during 6 months, the integrated enthalpy for the low and high
temperature peak is calculated to be 3.3 and 7.3 J/g respectively. This represents an
increase of the low temperature endotherm by a factor of 2. Indeed, the magnitude
of the integrated enthalpy for the low and high temperature peak decreases as the
progress of the exposure time. There are examples of this dual endotherm behavior
that have been published in the technical literature [18, 19]. The literature
Outdoor Exposure Degradation of Ethylene-Vinyl-Acetate … 209
DHm
vc ð % Þ ¼ 100 % ð8Þ
DH100
angle peak is the reflection of amorphous polymer phase. The internal structure of
the EVA exhibits a certain level of the organization, but this organization does not
seem to have the three-dimensional characteristic periodicity of the typical crystal
structure. It should be more likely to consider as a complex semi-crystalline system
caused by the coexistence of two polymers, the Poly (Ethylene) and Poly (Vinyl-
Acetate) with a block structure having different densities [24].
Figure 20 shows the heat-cool-heat data profile on the DSC instrument for
crosslinked EVA sample aged during 18 months, where the heating cycles are
expanded. The first heating shows the dual endotherm behavior previously noted.
During the rapid cooling a large exothermic peak appears at about 36 °C due to
exothermic crystallization. After cooling, the second heating is designed to remove
the possible thermal history of the sample and also it ensures good contact with the
DSC pan to enable good data acquisition to be taken. On the second heating, the
dual exotherm is no longer observed; instead, there is a very broad endotherm with
a peak at 55 °C and with a shoulder at 73 °C. It is noted that spans to higher
temperature than the unaged EVA due to the fact that the structure of the material
has changed as a result of outdoor exposure. Considering that annealing is one of
the processes that have to be considered in outdoor exposure, the development of
crystal structure with time would be a likely process to consider as important.
The basic interest in extending the thermal evaluation of EVA, was to examine
the relationship between the TSC and DSC results. The DSC experiments described
above were done using a conventional temperature program. DSC experiments
were also conducted using a temperature program that simulated the temperature
cycle used to conduct the TSDC experiments, where the EVA sample were held at
the 60 °C polarization temperature. Figure 21 shows the DSC profiles of the aged
EVA sample for 6 months before and after being held at 60 °C for 2 min and
rapidly cooled to −50 °C. It is noted that a broad, shallow low temperature
endotherm is centered at about 47 °C, and the high temperature peak is shifted to
about the temperature, 64 °C. Also, for the high temperature peak the integrated
peak is 7.1 J/g, after holding at 60 °C for 2 min, the integrated peak is 1.3 J/g. It is
Outdoor Exposure Degradation of Ethylene-Vinyl-Acetate … 211
clear that in addition to being shifted to higher temperature, the high temperature
peak is reduced in magnitude.
It appears that holding the specimen at 60 °C for 2 min melts out the entire low
temperature, poorly formed crystal population. It also partially melts out a sub-
stantial fraction of the high temperature, well formed crystal population. A higher
melting fraction of the well formed population remains and may even be annealed
to a higher melting temperature. Rapid cooling to −50 °C does not allow the
original crystallinity to reform; so that only a shallow, broad endotherm repre-
senting a small fraction of poorly formed crystals can be observed.
where:
ρ: resistivity at temperature T; ρ∞: resistivity at temperature T∞; Ea (J/mol):
Activation energy; T(°K): absolute temperature; R: Gas constant (8.314 J/mol °K).
A plot of Log ρ versus 1/T, will yield a straight line with a slope of −Ea/R as
shown in Eq. (10):
Outdoor Exposure Degradation of Ethylene-Vinyl-Acetate … 213
Ea 1
Logq ¼ þ ln q1 ð10Þ
R T
The activation energy of the crosslinked EVA before and after exposure is
calculated to be 52.8 and 162.2 kJ/mol respectively according to Fig. 25. After
exposure in desert climate, the activation energy of EVA is very high due to
environment weathering and time exposure duration.
214 K. Agroui and G. Collins
Figure 26 shows the UV-visible transmittance spectra for EVA before and after
outdoor exposure. It is seen that the transmittance of EVA after outdoor exposure is
lower than before exposure. One of the important properties of the encapsulant is
the transmittance of short-wavelength ultraviolet (UV) sunlight. Typically, the
polymer encapsulant used to laminate the superstrate to the solar cells in a module
is degraded by extended exposure to UV light. Therefore, it is desirable for the
module superstrate to prevent ultraviolet sunlight (<400 nm) from reaching the
encapsulant material. The 420 nm peak intensity corresponds to the concentration
of curing—generated, α and β-unsaturated carbonyl groups, which are responsible
for the UV-induced EVA discoloration and photodegradation [25].
Another desirable optical characteristic for the encapsulant would be rejection of
infrared (IR) sunlight of wavelengths longer than usable by the solar cells. The
rejection of the infrared sunlight would raise module performance and increase
module lifetime by reducing operating temperatures. However, a cost-effective
method for rejecting the infrared heat has not been developed.
FTIR spectrum in ATR mode of the crosslinked EVA before and after exposure
is illustrated in Fig. 27. It is noted several peaks related to different modes of
vibration of the bonds. The crosslinked EVA has two peaks due to CH bond located
at 2847 and 2921 cm−1. An important peak appears at 1736 cm−1 corresponding to
the harmonic vibration of C=O (carbonyl group). At 1372 cm−1 an intense peak
appears, corresponding to the vibration of the CH3 bond. The vibration of the ester
bond C–O–C function appears at 1247 cm−1 [26, 27]. After exposure in the natural
environment the FTIR spectra of the crosslinked EVA has a relatively broad peak
between 3402 and 3323 cm−1, which corresponds to the vibration of the hydroxyl
group (OH) due to the effect of moisture in natural exposure. Nevertheless, other
low intensity peaks appear at around 2270 and 1173 cm−1 without major significant
changes leading to the perfect overlapping of the two spectra.
Regarding tensile testing, the unaged crosslinked EVA material exhibits a high
ductile behavior with strain at break values of about 565 %, the stress at break is
found to be 13.6 MPa as described in the technical guide. The ultimate mechanical
properties of the crosslinked EVA before and after exposure are shown in Fig. 28. It
is noted that the crosslinked EVA exhibits a significant change in strain and stress at
yield point which are very sensitive to changes in molecular mass of the polymer
and therefore sensitive to chemical aging. Also, this behavior can mainly be
attributed to the recrystallization as revealed by DSC. For all investigated polymer
films, a clear influence of the weathering stress factors like UV radiation, tem-
perature and humidity on the ultimate mechanical properties of the crosslinked
EVA was observed.
The DMTA curves represented by the storage modulus (E′) and loss tangent
(tanδ) of the EVA before and after exposure are illustrated in Figs. 29 and 30
respectively. DMTA analysis revealed that the storage modulus before and after
exposure increases from 536 to 1350 MPa respectively at Tg. In the same process,
the loss tangent curve exhibits two relaxation peaks located at different tempera-
tures due to the two distinct drops in modulus compared with the TSC thermogram,
the low temperature drop is accompanied by a peak in the tanδ. This low tem-
perature mechanical loss process is taken to correspond to the low temperature
relaxation peak observed in the TSDC.
216 K. Agroui and G. Collins
Fig. 28 Evolution of stress and strain at yield point of the crosslinked EVA before and after
exposure at CDER site
After long-term operation under desert climate at URAER site, some severely
degraded PV modules were characterized [28, 29]. EVA samples taken from the
front of degraded modules, continuously exposed to light and higher temperature,
become opaque as shown in Fig. 31a. Their mechanical properties are greatly
changed, such as reduced elongation compared with EVA samples taken from the
back, not directly exposed to light and were at lower temperature than the front side
as shown in Fig. 31b. It was surmised that cells in modules having large series
resistance, or other defects that produced hot spots, could locally heat EVA leading
to severe delamination [30].
Outdoor Exposure Degradation of Ethylene-Vinyl-Acetate … 217
Fig. 30 Loss factor of the crosslinked EVA before and after exposure at CDER site
Fig. 31 PV module degradation at URAER site. a PV module front surface: EVA discoloration
(yellowing). b PV module rear surface: EVA no discoloration
218 K. Agroui and G. Collins
5 Conclusion
References
1. Schlothauer, J., Jungwirtha, S., Kohl, M., Roder, B.: Degradation of the encapsulant polymer
in outdoor weathered photovoltaic modules: spatially resolved inspection of EVA ageing by
fluorescence and correlation to electroluminescence. Sol. Energy Mater. Sol. Cells 102, 75–85
(2012)
2. Wohlgemuth, J.H., Cunningham, D.W., Monus, P., Miller, J., Nguyen, A.: Long term
reliability of photovoltaic modules. In: Proceedings of the 4th World Conference on PV
Energy Conversion (2006)
3. Herrmann, W., Bogdanski, N., Reil, F., Köhl, M., Weiss, K.-A., Assmus, M., Heck, M.: PV
module degradation caused by thermo-mechanical stress: real impacts of outdoor weathering
versus accelerated testing in the laboratory. In: Proceedings of the SPIE 7773 (2010). http://dx.
doi.org/10.1117/12. 859809
4. Dhere, N.G., Gadre, K.S.: Comparison of mechanical properties of EVA encapsulant in new
and field-deployed PV modules. In: Proceedings of the 2nd World Photovoltaic Solar Energy
Conference and Exhibition, Vienna, 6–10 July 1998
5. Dechthummarong, C., Wiengmoon, B., Chenvidhya, D., Jivacate, C., Kirtikara, K.: Physical
deterioration of encapsulation and electrical insulation properties of PV modules after long-
term operation in Thailand. Sol. Energy Mater. Sol. Cells 94(9), 1437–1440 (2010)
6. Standard practice for outdoor weathering of plastics. ASTM D1435–05, 1985
7. Stark, W., Jaunich, M.: Investigation of ethylenevinyl acetate copolymer (EVA) by thermal
analysis DSC and DMA. Polym. Test 30(2), 236–242 (2011)
8. Oreski, G., Wallner, G.M.: Damp heat induced physical aging of PV encapsulation materials.
In: 12th IEEE Intersociety Conference on Thermal and Thermo-Mechanical Phenomena in
Electronic Systems (Itherm 2010), Las Vegas, 2–5 June 2010, pp. 1–6
9. Collins, G., Yoo, S.U., Recber, A., Jaffe, M.: Thermal analysis of complex relaxation
processes in poly (desaminotyrosyl-tyrosine arylates). Polymer 48(4), 975–988 (2007)
10. Saffell, J.R., Matthiesen, A., McIntyre, R., Ibar, J.P.: Comparing thermal stimulated current
(TSC) with other thermal analytical methods to characterize the amorphous phase of polymers.
Thermochim. Acta 192, 243–264 (1991)
11. Agroui, K., Collins, G., Farenc, J.: Measurement of glass transition temperature of crosslinked
EVA encapsulant by thermal analysis for photovoltaic application. Renew. Energy 43, 218–
223 (2012)
Outdoor Exposure Degradation of Ethylene-Vinyl-Acetate … 219
12. Czanderna, A.W., Pern, F.J.: Encapsulation of PV modules using ethylene vinyl acetate
copolymer as a pottant: a critical review. Sol. Energy Mater. Sol. Cells 43, 101–181 (1996)
13. Agroui, K., Segui, Y., Farenc, J., Benrekaa, N.: Characterisation of EVA encapsulant by glass
transition temperature method for photovoltaic application. In: 1st International Conference on
Energy (IEC 2000), University of El-Ain (UAE) 7–9 May 2000
14. Agroui, K.: Experimental aging study of EVA in outdoor exposure, internal report UDTS/2011
15. Agroui, K., Collins, G.: Thermal relaxations and transitions in EVA encapsulant material
during photovoltaic module encapsulation process, in materials and processes for energy:
communicating current research and technological developments. In: Méndez-Vilas, A. (ed.)
Formatex Research Center, ISBN: 978-84-939843-7-3, pp. 150–157 (2013) http://www.
formatex.info/energymaterialsbook/book/150-157.pdf
16. Agroui, K., Collins, G.: Characterization of EVA by thermally stimulated current technique.
Sol. Energy Mater. Sol. Cells 80(2), 33–45 (2003)
17. Bregulla, M., Köhl, M., Lampe, B., Oreski, G., Philipp, D., Wallner, G., Andersnd Weiß, K.:
Degradation mechanisms of ethylene vinyl acetate copolymer: new studies including ultra fast
cure foils. In: Proceedings of the 22nd European Photovoltaic Solar Energy Conference,
Milan, 3–7 Sept 2007, pp. 2704–2707
18. Bistac, S., Kunemannand, P., Schultz, J.: Crystalline modifications of ethylene-vinyl acetate
copolymers induced by a tensile drawing: effect of the molecular weight. Polymer 39(20),
4875–4881 (1998)
19. Tsocheva, D., Tsanovand, T., Terlemezyan, L.: Structure of composite films containing
polyaniline studied by DSC. J. Therm. Anal. Calorim. 66(2), 415–422 (2001)
20. Reyes-Labarta, J.A., Olaya, M.M., Marcilla, A.: DSC and TGA study of the transitions
involved in the thermal treatment of binary mixtures of PE and EVA copolymer with a
crosslinking agent. Polymer 47, 8194–8202 (2006)
21. McEvoy, R.L., Krause, S., Wut, P.: Surface characterization of ethylene vinyl acetate (EVA)
and ethylene-acrylic acid (EAA) co-polymers using XPS and AFM. Polymer 39(21), 5223–
5239 (1998)
22. Brogly, M., Nardin, M., Schultz, J.: Effect of vinyl acetate content on crystallinity and second-
order transitions in ethylene—vinyl acetate copolymers. J. Appl. Polym. Sci. 64(10), 1903–
1912 (1998)
23. Sung, Y.T., Kum, C.K., Lee, H.S., Kim, J.S., Yoon, H.G., Kim, W.N.: Effects of crystallinity
and crosslinking on the thermal and rheological properties of ethylene vinyl acetate
copolymer. Polymer 46(25), 11844–11848 (2005)
24. Agroui, K., Belghachi, A., Collins, G., Farenc, J.: Quality control of EVA during photovoltaic
module encapsulation process. Desalination 209, 1–9 (2007)
25. Pern, F.J.: Ethylene-vinyl acetate (EVA) encapsulants for PV modules: degradation and
discoloration mechanisms and formulation modifications for improved photostability. Sol.
Energy Mater. Sol. Cells 252, 195–216 (1997)
26. Allen, N.S., et al.: Aspects of the thermal oxidation of ethylene vinyl acetate copolymer.
Polym. Degrad. Stab. 68(3), 363–371 (2000)
27. Giurgincaa, M., Popab, L., Zaharescuc, T.: Thermo-oxidative degradation and radio-
processing of ethylene vinyl acetate elastomers. Polym. Degrad. Stab. 82(3), 463–466 (2003)
28. Agroui, K., Hadj Mahammed, I., Hadj Arab, A., Belghachi, A.: Characterization photovoltaic
modules based on thin films solar cells in environmental operating conditions of Algerian
Sahara. Proc. SPIE 7048, 70480Q.1–70480Q.8 (2008)
29. Sadok, M., Mehdaoui, A.: Outdoor testing of photovoltaic arrays in the Saharan region.
Renew. Energy 33(12), 2516–2524 (2008)
30. Wiengmoon, B., Sangpongsanont, Y., Jivacate, C., Chenvidhya, D., Kirtikara, K.:
Determination of PV module deterioration based on physical properties investigation of
EVA. In: Proceedings of the 21st European Photovoltaic Solar Energy Conference, pp. 2514–
2516 (2006)
Thermal Degradation
of Bio-nanocomposites
Abstract Bio-nanocomposites have attracted a great deal of attention over the last
number of years due to the excellent characteristics the material has to offer. With
ever increasing demands of environmental controls, more sustainable materials like
bio-nanocomposites are required to substitute the various petropolymers utilised
nowadays. These bio-based polymers provide exceptional performance and have
smart properties that have proven useful to the food packaging industry and a wide
range of other applications. This chapter reviews the recent developments of bio-
nanocomposites where the related biodegradable polymers include Polylactic acid
(PLA), polycaprolactone (PCL), polyhydroxyvalerate (PHV), polyhydroxyalkano-
ates (PHAs), polyhydroxybutyrate (PHB), poly(3-hydroxybutyrate-co-3-hydroxy-
valerate) (PHBV) and poly(d,l-lactide) (PDLLA). A concise history outlining the
development of bio-nanocomposites materials is explored, while the importance of
environmental conditions and in particular the rate of biodegradability is high-
lighted. Furthermore, this chapter addresses the steps of thermal degradation and the
systematic approaches used to overcome these concerns. It discusses the behaviour
of various nanoparticles on the thermal stability of biopolymers and other topics
related to research challenges, future trends and applications.
1 Introduction
Each year approximately 140 million tons of petroleum based synthetic polymers
are developed worldwide, where large quantities of various polymers are introduced
into the ecosystem as industrial waste products [1]. Due to the environmental
concerns of synthetic polymers in terms of environmental pollution, depletion of
fossil resources and greenhouse gas emissions, alternative polymers derived from
renewable resources are necessary to replace these microbial resistant materials [2,
3], especially for use in short term packaging and disposable applications. These
renewable biological resource polymers are usually called biopolymers, which are
excellent vehicles for adding a wide range of additives such as antimicrobials,
antioxidants, antifungal agents, colour and other nutrients [3, 4]. Under suitable
conditions of temperature, moisture and oxygen availability, biodegradation can
initiate fragmentation or disintegration of the materials with no toxic or environ-
mentally harmful residues [5]. Biopolymers can be broken up into various cate-
gories which are based on the type of manufacturing process and the source of raw
materials. These categories include natural biopolymers, synthetic biodegradable
polymers and biopolymers developed by microbial fermentation [6].
Biopolymers such as aliphatic polyesters are now produced on a semi-com-
mercial scale by numerous companies that make biodegradable plastics [7]. Ali-
phatic polyesters have repeating units that are bonded via ester linkages and these
natural esters can be degraded by enzymes (esterases) that are ubiquitous in nature
[8]. Polylactic acid (PLA), polyglycolate (PGA), poly(3-hydroxybutyrate), polyc-
aprolactone (PCL), polyhydroxyvalerate (PHV) and their copolymers poly(butylene
succinate) (PBSu), poly(ethylene succinate) (PESu), poly(propylene adipate)
(PPAd), etc., are the most commonly used aliphatic polyesters for such applications
as packaging materials, mulch films, tissue engineering, implants, drug delivery etc.
[9]. However, aliphatic polyesters exhibit relatively poor thermal stability,
mechanical strength, solvent resistance, gas permeability, hydrophobic character
and slower resorption/degradation kinetics as compared to other polymers which
have strongly limited their applications [10, 11]. Pandey et al. [12] and Rhim et al.
[6] mentioned that the problems related to biopolymers are threefold: performance,
processing and cost. These issues are similar to some degree, where the problems
related to performance and processing are common to all biodegradable polymers
irrespective of their origin.
In order to make biopolymers more attractive for commercial end-use applica-
tions, it is necessary to enhance the thermomechanical properties through the util-
isation of nanocomposite technology. In the last decade, polymer nanocomposites
have become a global research interest, due to the superior advances in polymer
characteristics by the addition of nano-scale materials (preferably in the range 10–
100 nm) into the polymer matrix [13]. Due to the nanoscopic dimensions and
extreme aspect ratios of the nanofillers, this results in six interrelated characteristics,
which defines the type of nanocomposite. These are (1) low-percolation threshold
(~0.1–2 vol%), (2) particle to particle correlation (orientation and position) arising
Thermal Degradation of Bio-nanocomposites 223
at low volume fractions (Фc < 0.001), (3) high density of particles per particle
volume (106–108 particles/μm3), (4) extensive interfacial area per volume of particles
(10–50 nm at Ф ~ 1–8 vol%), and (6) comparable size scales among the rigid
nanoparticles inclusion, distance between particles, and the relaxation volume of
polymer chains [13, 14]. One of the key advantages of nanofillers is the miscibility
with the polymer matrix due to the low size, which provides unique synergism
between the combined materials. Nanofillers can be classified into three different
categories depending on the dimensions of the dispersed particles [15]:
(a) Nanolayers: these are a one dimensional layered material with typical
dimensions of 1 nm thick and an aspect ratio following their two remaining
dimensions of at least 25. They will usually stack on top of each other to form
tactoids and these tactoids can contain up to hundreds of layers of platelets. In
this category, layered silicate include sematic clays, layered double hydroxides
and grapheme sheets.
(b) Nanotubes: these are two dimensional with a diameter below 100 nm and an
aspect ratio of at least 100. This category includes nanocellulose subtracts
carbon nanotubes silica and titanium nanotubes.
(c) Nanoparticles: these have three dimensions below 100 nm and are sometimes
called isodimensional nanoparticles. The most popular nanofillers in this
category include, silica particles, polyhedral oligomeric silesquioxane and
metal oxides.
These nanocomposites can be further classified into the following areas:
(1) clayed based nanocomposites, (2) nanocellulose based nanocomposites, (3)
carbonaceous based nanocomposites, (4) metal/metallic hydroxide based nano-
composites and silicon based nanocomposites. Table 1 displays each of the
Table 1 Biopolymers and inorganic or antimicrobial materials typically used for the preparation
of bio-nanocomposites [6]
Biodegradable polymers Antimicrobial materials
Starch or thermoplastic starch (TPS) Clay (e.g. Montmorillonite (MMT))
Chemically modified cellulose (e.g., cellulose Organically modified nanoclay (quaternary
acetate (CA) and cellulose acetate butyrate ammonium modified MMT, Ag-zeolite)
(CAB))
Polylactic acid (PLA) Metal ions (e.g. silver, copper, gold,
platinum)
Polycaprolactone (PCL) Metal oxide (e.g. TiO2, ZnO, MgO)
Polyhydroxyalkanoate (PHA) Natural biopolymers (e.g. chitosan)
Polyhydroxybutyrate (PHB) Natural antimicrobial agents (e.g. nisin,
thymol, carvacrol, isothiocyanate,
antibiotics)
Poly(butylene succinate) (PBS) Enzymes (peroxidase, lysozyme)
Synthetic antimicrobial agents (quaternary
ammonium salts, EDTA, propionic acid,
benzoic acid, sorbic acid)
Copyright 2013. Reproduced by permission of Elsevier Science Ltd.
224 K.A. Murray et al.
biopolymers and inorganic or antimicrobial materials typically used for the prep-
aration of bio-nanocomposites.
Clay based nanocomposites have received remarkable interest since they were
first introduced [16]. Based on the pioneered worked performed by the Toyota’s
research team [17], widespread research has been carried out by various industrial
and academic groups [6, 18, 19]. Among the various nanocomposites available,
clay based nanocomposites would be regarded as the most popular for the
improvement of various biopolymer characteristics, such as the mechanical and
thermal properties. Montmorillonite is a semantic clay which has weak bonding
between its layers; where each layer consists of two sheets of silica tetrahedral with
an edge shared octahedral sheet of alumina as demonstrated (layer thickness of
around 1 nm) Fig. 1 [20]. As a result of this isomorphic substitution of alumina
between the layers, each unit cell has a negative charge between 0.5 and 1.3. These
layers are held together by a layer of charge compensating ions such as Li+, Na+, K+
or Ca2+ which are allocated within the galleries of the silicate layers [21].
Layered silicates have positive ions present on the surface which makes them
hydrophilic and therefore incompatible with many polymers as they are generally
hydrophobic [22]. To make bio-nanocomposites, it is necessary to modify the
layered silicates by replacing the interlayer cations with cations bearing long alkyl
chains, such as alkylphosphonium or alkylammonium [23]. Alkyl ammonium
cations are employed to lower the surface energy and enhance the wetting char-
acteristics with the polymer [24]. By incorporating polymers or monomers into the
interlayer, this can lead to the formation of a bio-nanocomposite. Different struc-
tures can exist for polymer/clay bio-nanocomposites and they are as follows (see
Fig. 2):
(a) Phase separated (Microcomposite): When a polymer is not able to intercalate
with the layered silicate. Their properties remain in the same range as tradi-
tional microcomposites.
(b) Intercalated: When polymer chains penetrate in between the layered silicate
which in turn increases the gallery height.
Fig. 1 Representation for the crystal structure of montmorillonite [14]. Copyright 2011.
Reproduced by permission of Elsevier Science Ltd.
Thermal Degradation of Bio-nanocomposites 225
weight and the control of degradation (see Fig. 3). Based on the results from TGA
(Fig. 4), the addition of clay into the PLA matrix decreased the thermal stability,
whereas the incorporation of a chain extender resulted in an increase in the onset
temperature for thermal degradation. Joncryl was the most efficient chain extender
which strongly influence the rheological properties and the control of degradation
over a wide range of processing temperatures [44].
Thermal degradation of PCL in an inert atmosphere can transpire through the
rupture of polyester chains via ester pyrolysis reaction with the release of CO2, H2O
and a carboxylic acid [45]. According to Chrissafis et al. [46], organomodified
MMT and nanosilica accelerated the decomposition of PCL, however; unmodified
MMT and multi-walled carbon nanotubes inhibited the thermal degradation of PCL.
Based on the results from the calculated activation energies through using the
Ozawa, Flynn and Wall (OFW) and Friedman methods, it was determined that
virgin PCL degraded by two different mechanisms. The first one corresponded to a
small mass loss, whereas the second was related to the main decomposition
mechanism, where a substantial mass loss took place. In addition, the nanocom-
posites did not affect the decomposition mechanism but only the activation
energies.
From the TGA data obtained for virgin PCL and different loadings of dodecyl
sulphate modified CoAl-LDH (OCoAl-LDH) in an nitrogen atmosphere, it was
identified that degradation of nanocomposites occurs at lower temperatures in
contrast to the virgin PCL. Furthermore, the thermal degradation temperature
decreases gradually with the increase of OCoAl-LDH concentration [47]. Chen
et al. [22] reported that PCL/multi-walled carbon nanotube (MWCNT) composites
prepared by ultrasonically mixing the PCL and as-fabricated MWCNT in a tetra-
hydrofuran solution lead to better thermal stability. The activation energy of the
composites was smaller than virgin PCL which can be attributed to the MWCNT
loading. MWCNT loading causes a decrease in the degradation rate and an increase
in the residual weight for PCL/MWCNT nanocomposites. An enhancement in the
Thermal Degradation of Bio-nanocomposites 229
thermal stability is due to the CNTs having exceptional thermal conductivity but
also due to the formation and stabilisation of MWCNTs bonded macroradicals.
It appears that no consistent conclusions are available concerning the thermal
stability of nanocomposites in contrast to the parent polymer. However, Carrasco
et al. [48], stated that the thermostability is determined by the nature and content of
nanoclay, but in particular the method used to produce the nanocomposite as a less
depolymerising process would provide better stability.
Fig. 5 Molecular weight distribution of initial and degraded samples [53]. Copyright 2014.
Reproduced by permission of Elsevier Science Ltd.
Thermal Degradation of Bio-nanocomposites 231
were carried out at 46 and 24 °C in a soil composting medium. Both materials were
assessed by examining loss of mass, tensile strength and polymer roughness. Tem-
peratures were shown to increase the rate of the biodegradation process with both
samples completely degraded after 104 days at 46 °C, while only 51 % of PHB and
56 % of PHBV were degraded after 321 days of composting at 24 °C [56]. Studies
have also demonstrated that PHAs degrade in aquatic environments within 254 days,
at temperatures below 6 °C [57].
4.2 Hydrolysis
Hydrolysis is a chemical reaction during which molecules of water are split into
hydrogen cations and hydroxide anions. In the case of polyester based polymers,
the molecular weight decrease is principally instigated by the hydrolysis of the ester
linkage which randomly occurs throughout the polymer. The basic mechanism of
hydrolysis for PLA is shown in Fig. 6. The amount of hydrolysis or degradation is
controlled by the temperature, amount of water, acid or base catalyst and mor-
phology of the polymer [58].
As mentioned above, temperature is a critical parameter in controlling the
hydrolysis reaction. Degradation studies have been carried out at temperatures to
simulate in vivo conditions (T = 37 °C), soil or compost conditions, (T = 25-
60 °C) and polymer processing conditions (T = 200 °C) in which the biopolymers
are hydrolysed to give low molecular weight water-soluble oligomers [59]. The
hydrolytic degradation of bio-nanocomposites has been reported to take place mainly
in the bulk of the material rather than on the surface [60] and has been assumed to be
an autocatalytic hydrolysis of biopolymers which occurs homogeneously along
sample cross-sections.
Figure 7 shows the TGA degradation profiles for polylactic closite bio-nano-
composites in which the samples were exposed for 8 weeks at both 37 and 58 °C.
In summary, the results showed an overall increase in thermal degradation of the
bio-nanocomposites with an increase in temperature. In comparing the effect of
nanocomposites on the degradation profile, hydrolysis degradation was a lot more
prevalent at the high temperature [59].
Fig. 6 Hydrolysis of
polylactic acid
232 K.A. Murray et al.
4.3 Chain-Scission
4.4 Transesterification
The transesterification mechanism occurs when the carbonyl carbon of the starting
ester (RCOOR1) undergoes nucleophilic attack by the incoming alkoxide (R2O-) to
give a tetrahedral intermediate, which either reverts to the starting material, or
proceeds to the transesterified product (RCOOR2). This is not an attractable
occurrence as it increases the polydispersity and reduces the molecular weight,
which affects the mechanical properties of the material.
There are two different types of transesterfication: intramolecular and intermo-
lecular. Intramolecular transesterfication for PLA bio-nanocomposites is found to
dominate at high temperatures (>200 °C) and results in the formation and degra-
dation of cyclic polylactide oligomers. In comparison, intermolecular transesterfi-
cation affects the sequence of different polymeric segments [44]. As a result of such
Thermal Degradation of Bio-nanocomposites 233
reactions, the molecular weight and the mechanical properties decrease. Consid-
ering that the rate of thermal degradation increases often after clay loading, con-
trolling the thermal degradation of PLA nanocomposites is a major challenge.
Carrasco et al. [50] conducted a wide ranging study into the thermal stability of
polylactic acid. The researchers studied the effects of different processing and thermal
conditioning steps and of multiple polymer processing steps on thermal stability. The
unprocessed PLA was more thermally stable than the processed and thermally
conditioned PLA. The raw material decomposed over a narrow range (331–375 °C).
All the processed and annealed samples began to decompose sooner (325 °C) and
would be fully decomposed 5 mins sooner than the raw PLA. The difference in
thermal stability was shown to be related to the presence of lower molecular weight
PLA chains in the processed samples formed due to thermal decomposition at ele-
vated temperatures in melt processing. A follow on study by Carrasco et al. [48]
investigated organo-modified montmorillonite reinforced PLA nanocomposites (0.5
and 2.5 % loading) where the 0.5 % was exfoliated and the 2.5 % was intercalated
and exfoliated. The nanoclay had only limited reinforcement effect on the PLA (no
change in Young’s modulus), however; it did promote plastic deformation. Processed
nanocomposite samples decomposed sooner than the processed PLA, however; the
nanocomposite samples took longer to fully decompose. The authors attributed the
protective effects of nanoclay to the tortuous path created by the exfoliated clay
hindering diffusion of volatile degradation products. The 2.5 % loaded sample was
much less thermally stable due to the destabilising effect of ammonium cation present
in the nanoclay. Indeed, there has only been limited success with nanoclay and PLA
in the literature, due mainly to the difficulty in achieving exfoliation of the clay
through melt processing. Nieddu et al. [63] investigated the effect of different
nanoclays on the properties of PLA, achieving an intercalated structure for all but one
of the nanoclays (Nanofil). The PLA nanocomposites had higher moduli compared to
the neat PLA with maximum increase (47 %) achieved for a 10 % Somasif® MEE
loading. These reinforced PLA samples showed increased thermal stability; the
reinforced samples had both a 20 °C higher onset decomposition temperature and an
18 °C higher total decomposition temperature.
Starch containing organo-modified sepiolite provided for a considerable increase
(164 %) in Young’s modulus for a 6 % loaded sample [64]. This large reinforce-
ment effect had no bearing on thermal stability; instead increasing organo-modified
nanoclay loading actually reduced the total decomposition temperature by 9 °C at
up to 6 % loading. Reduction in thermal stability had a linear relationship to
increasing the cationic starch content that had been used to modify the sepiolite.
Unmodified sepiolite provided for the opposite trend and increasing nanoparticle
loading produced a 3 and 8 °C increase in the total decomposition temperature for
234 K.A. Murray et al.
the 3 and 6 % sepiolite loading, respectively. The authors speculated that the
increase in thermal stability was due to the interplay of two actions—the retardation
of volatile degradation compounds by extensive molecular interactions, via phys-
isorption and/or chemisorption, occurring at the polymer/sepolite interface and the
sepiolite forming a protective inorganic layer at the surface of the starch. The
unmodified sepiolite did reinforce the starch but to a much less of an extent than the
cationic starch modified sepiolite, with Young’s modulus only increasing 77 % for
the 6 % loading. Another study investigated the montmorillonite (MMT) based
starch nanocomposites. The authors reported that MMT had a reinforcement effect
which increased with increasing loading, with 198 % increase in Young’s modulus
observed for the 5 % loading. Concurrently, MMT also enhanced the thermal
stability of starch. The onset decomposition temperature of starch was 223 °C and
the addition of 5 % MMT increased this temperature by 19 °C (242 °C), indicating
an improvement in the stability. However, this increase in thermal stability is
probably, as stated previously, a factor of both the tortuous path created by the
exfoliated nanoclay and the thermal barrier presented by the nanoclay layers.
Bruzaud and Bourmaud [65] investigated a poly(3-hydroxybutyrate-co-3-hy-
droxyvalerate) (PHBV) polymer reinforced with an organo-modified montmoril-
lonite. The nanoclay provided a 65, 107 and 165 % increase in Young’s modulus
for 1, 2.5 and 5 % loading, respectively. Thermal stability increased with increasing
nanoclay loading, a 30 °C improvement was obtained with a 5 % loading of
nanoclay in the 50 % decomposition temperature. The nanoclay acts as a heat
barrier retarding the diffusion of oxygen and volatile degradation products. Cellu-
lose nanowhiskers reinforced PHBV showed the opposite trend with reinforcement
[66]. Young’s modulus increased with an increase in loading, where the 5 %
loading increased the stiffness by 77 %. The thermal stability of the neat PHBV was
higher compared to the sample loaded with 5 % cellulose nanofiber. Addition of the
nanoparticle reduced the total decomposition temperature by 5 °C. In essence this
reduction in thermal stability is due to the cellulose based nanoparticles acting as a
thermal conductor as opposed to the nanoclay which acted as a thermal barrier.
Taken as a review of the work in the literature, it must be concluded that thermal
stability is less dependent on reinforcement, but is in fact much more dependent on
properties of the actual nanoparticle during decomposition.
In the previous section, it was outlined how the thermal stability of bio-nanocom-
posites is more related to the type and to the modification of the nanoparticle dis-
persed within the biopolymer, than to do with any reinforcement effect attributable to
the nanoparticle. Different nanoparticles have different effects on the thermal stability
of biopolymers. Nanoclay can greatly enhance the thermal stability of a number of
different biopolymers—PLA [48, 63], PCL [67], starch [68, 69] and PHBV [65]. As
Thermal Degradation of Bio-nanocomposites 235
stated above this stabilisation effect is related to the nanolayers acting as a thermal
barrier slowing the diffusion of volatile compounds through the polymer matrix.
For cellulose based nanoparticles there is a mixed effect on the thermal stability
of biopolymers. A study by de Paula et al. [70] investigated the effects of incor-
porating cellulose nanowhiskers in poly (d,l-lactide). These nanoparticles signifi-
cantly increased the thermal stability of biopolymers, where the onset
decomposition temperature increased by 12 and 26 °C for 1 and 5 % loadings,
respectively. Cellulose nanowhiskers were shown to have negligible effect on the
thermal stability of PLA [71]. Wang et al. [72] investigated the cellulose nano-
whisker nanocomposites based on a novel poly (propylene carbonate) (PPC) syn-
thesised by copolymerisation of propylene oxide and carbon dioxide. The addition
of cellulose nanowhiskers significantly increased thermal stability of the biode-
gradable polymer. From up to 5 % loading of the nanoparticle, the onset decom-
position temperature of the PPC increased by 20 °C. After this point additional
cellulose nanowhiskers had less of a stabilisation effect on the PPC and 10 %
loading had no effect on the onset decomposition temperature. Identical trends were
observed for the total decomposition temperature.
Carbon nanotubes (CNTs) do not greatly affect the thermal stability of bio-
polymers. Single wall CNTs did change the thermal decomposition temperatures of
PCL [73]. In the same study, silver nanoparticles significantly destabilised PCL
reducing both the onset and total decomposition temperatures by 50 °C. The
thermal stability hybrid film containing both CNTs and silver nanoparticles was
similar to the binary film containing only silver nanoparticles, reflecting that the
CNTs did not act to stabilise the system. A study incorporating multi-wall CNTs in
polylactic acid also reported negative effects on thermal stability [74]. In air, the
onset decomposition temperature of the bio-nanocomposite material significantly
decreased with increased loading, while under nitrogen the decrease in the onset
decomposition temperature only occurred for in excess of 2 % loading. The de-
stabilisation mechanism was speculated to be different under the two conditions. In
the presence of oxygen CNTs have a catalysing effect for decomposition, while
under nitrogen and in excess of 2 % the CNTs for a percolating network acts as a
conducting pathway for assisting decomposition reactions.
Fig. 8 Crystallinity degree of PLA bio-nanocomposites before and after thermal degradation [53].
Copyright 2014. Reproduced by permission of Elsevier Science Ltd.
Fig. 9 Thermogravimetric
analysis of silica, modified
and unmodified
montmorillonite [46].
Copyright 2007. Reproduced
by permission of Elsevier
Science Ltd.
In the literature some authors suggest that clays significantly improves the PLA
thermal stability under thermo-oxidative conditions, i.e. nitrogen environment [36].
However, a portion of the literature suggests the thermal stability under nitrogen
increased linearly as the quantity of clay reduced from 2 to 8 wt% [53]. Pluta et al.
[36] studied the thermal properties of PLA bio-nanocomposites and microcom-
posites by TGA under helium and oxygen environments. Samples were prepared by
melt blending and quench processing. Under both environments, nano and micro
composites did not alter the polymer thermal degradation. However, when com-
paring virgin PLA, microcomposites and nanocomposites, the thermal stability for
the nanocomposite considerably improved under thermo-oxidative conditions.
238 K.A. Murray et al.
9 Future Trends
The future of bio-nanocomposites will be very much tied up in the application areas
to which these materials are best suited. By far the greatest utility of these materials
is within packaging. Packaging plays an essential role in society by meeting the
needs of consumers for convenience and portability, as well as protecting and
preserving products throughout the supply chain. Conventional plastics have been
ideal to achieve these aims due to having limited interaction with food; not sup-
porting microorganisms; being light-weight and strong enough to survive the dis-
tribution chain; and being easily formed into a wide range of structures, shapes and
designs which are effective, convenient and aesthetically pleasing. The global
packaging material and machinery industry generates $500 billion yearly,
accounting for between 1 and 2 % of gross domestic product in industrialised
240 K.A. Murray et al.
nations, according to the World Packaging Organisation [89]. There are 100,000
packaging manufacturing companies in operation, representing 5 million jobs.
However, due to environmental regulations and also consumer demands there is an
increasing need for more recyclable and/or biodegradable packaging. Although
conventional plastic packaging is now expediently streamed for recycling and well
able to tolerate extensive recycling, it is non-biodegradable and is almost exclu-
sively sourced from non-renewable fossil fuels. Biopolymers would be the perfect
replacement for conventional plastics as they are derived from sustainable resour-
ces. Over the last decade, improvements in the performance of biodegradable
packaging make them a match of conventional plastic packaging in some niche
areas. However, more technological development is required to extend the utility of
biopolymers in packaging applications. Nanotechnology is one of the key methods
to provide increased product functions as the addition of nanoparticles can provide
packaging with improved performance and smarter properties. Nanoclay technol-
ogy has been deployed in biopolymer based packaging to improve the mechanical
performance and the barrier properties to oxygen, water vapour and carbon dioxide.
Active and smart packaging solutions are rapidly being developed for conven-
tional plastic packaging based on nanotechnology. Most active packaging tech-
nologies are aimed at extending the shelf-life of food. The shelf-life of food is
determined by such environmental factors as relative humidity, pH, temperature,
UV light and gas composition. These factors can alter taste, quality and safety of the
food through chemical modification, biochemical change or microbiological
spoilage. Nanotechnology can be incorporated into plastic packaging to overcome
these shortcomings and improve food safety. The majority of active packaging
techniques are concerned with substances that absorb oxygen, ethylene, moisture,
carbon dioxide, flavours/odours and those which release carbon dioxide, antimi-
crobial agents, antioxidants and flavours. Therefore, the future of bio-nanocom-
posites will be shaped by two complimentary needs—the requirement to match the
properties of conventional plastic packaging and the demand for smarter packaging.
The effect of incorporating novel nanoparticles on the thermal stability of bio-
polymers will need to be extensively studied.
10 Conclusion
Even though bio-nanocomposites have strong future prospects, they present low
levels of production and high costs limit them from a wide range of applications.
Based on the discussions throughout this chapter, there have been different and
sometimes contradictory results concerning the effects of nanoparticles on the
biopolymer thermal degradation and stability. The largest discrepancy was found
for clay nanoparticles like montmorillonite, which are generally used for property
improvement of biopolymers. Depending on the chemical structure of the bio-
polymer and the interaction of it with the various nanoparticles, this can decide the
effect it has on the thermal stability and the different stages of thermal degradation.
Thermal Degradation of Bio-nanocomposites 241
This is due to the difficulty of the clay plates dispersing in the polymer matrix where
the untreated clays form microcomposites instead of nanocomposites. Improve-
ments in the thermal stability can be as a result of (1) the absorption of gas formed
in the clay plates (2) the improvement in barrier properties (3) the large surface
volume (4) low permeability and a reduction in the rate of evolution of the formed
volatile products and (5) the development of high performance carbonaceous sili-
cate char on the surface of the nanoparticles, therefore insulating the underline
material while reducing the escape of volatiles formed during decomposition [14].
When a low concentration of clay nanoparticles is added to the polymer matrix they
are well dispersed and the barrier effect is predominant. However, if the concen-
tration is increased, degradation rapidly rises and becomes impressible, hence,
leading to a decrease in the thermal stability of the nanocomposite [14]. Carbon
nanotubes also demonstrated an increase in the thermal stability of polymers due to
their excellent thermal conductivity and the development and stabilisation of multi-
walled carbon nanotube-bonded macroradicals. Overall, this chapter has shown that
the addition of nanoparticles can provide thermal stabilisation of polymers during
decomposition, except for montmorillonite clays. Successful thermal stability
enhancement generally takes place where a low concentration (4–5 wt%) of
nanoparticles is used. Above this threshold, the thermal stability can deteriorate
significantly due the formation of aggregates which forms macrocomposites instead
of nanocomposites. At the moment the level of improvement for biopolymers is not
enough to compete with petroleum based polymers. Further enhancements of bio-
nanocomposites is required, for example, developing optimum formulations for
individual biopolymers and processing techniques to promote the desirability to
meet a diverse range of end use applications and also to reduce the cost of bio-
nanocomposites.
References
1. Shah, A.A., Hasan, F., Hameed, A., Ahmed, S.: Biological degradation of plastics: a
comprehensive review. Biotechnol. Adv. 26, 246–265 (2008)
2. Jenck, J.F., Agterberg, F., Droescher, M.J.: Products and processes for a sustainable chemical
industry: a review of achievements and prospects. Green Chem. 6, 544–556 (2004)
3. Kümmerer, K.: Sustainable from the very beginning: rational design of molecules by life cycle
engineering as an important approach for green pharmacy and green chemistry. Green Chem.
9, 899–907 (2007)
4. Clarinval, A.M., Halleux, J.: Classification of biodegradable polymers, pp. 3–31. CRC Press,
Boca Raton (2005)
5. Chandra, R., Rustgi, R.: Biodegradable polymers. Prog. Polym. Sci. 23, 1273–1335 (1998)
6. Rhim, J.W., Park, H.M., Ha, C.S.: Bio-nanocomposites for food packaging applications. Prog.
Polym. Sci. 38, 1629–1652 (2013)
7. Bikiaris, D.N.: Nanocomposites of aliphatic polyesters: an overview of the effect of different
nanofillers on enzymatic hydrolysis and biodegradation of polyesters. Polym. Degrad. Stab.
98, 1908–1928 (2013)
8. Shimao, M.: Biodegradation of plastics. Curr. Opin. Biotechnol. 12, 242–247 (2001)
242 K.A. Murray et al.
9. Gandini, A.: Polymers from renewable resources: a challenge for the future of macromolecular
materials. Macromolecules 41, 9491–9504 (2008)
10. Koh, H.C., Park, J.S., Jeong, M.A., Hwang, H.Y., Hong, Y.T., Ha, S.Y., et al.: Preparation and
gas permeation properties of biodegradable polymer/layered silicate nanocomposite
membranes. Desalination 233, 201–209 (2008)
11. Trznadel, M.: Biodegradable polymer materials. Int Polym Sci Technol. 22, 58–65 (1995)
12. Pandey, J.K., Raghunatha R.K., Pratheep K.A., Singh, R.P.: An overview on the degradability
of polymer nanocomposites. Polym Degrad Stab. 88, pp. 234-50 (2005)
13. Kumar, A.P., Depan, D., Singh Tomer, N., Singh, R.P.: Nanoscale particles for polymer
degradation and stabilization-trends and future perspectives. Prog in Polym Sci (Oxford)
34, 479–515 (2009)
14. Chrissafis, K., Bikiaris, D.: Can nanoparticles really enhance thermal stability of polymers?
Part I: an overview on thermal decomposition of addition polymers. Thermochim. Acta
523, 1–24 (2011)
15. Herron, N., Thorn, D.L.: Nanoparticles: uses and relationships to molecular cluster
compounds. Adv. Mater. 10, 1173–1184 (1998)
16. Carter, L.W., Hendricks, J.G., Bolley, D.S.: Elastomer reinforced with a modified clay.
Google patents (1950)
17. Deguchi, R., Nishio, T., Okada, A.: Polyamide composite material and method for preparing
the same. Google patents (1992)
18. Wang, Y., Chen, F.-B., Li, Y.-C., Wu, K.-C.: Melt processing of polypropylene/clay
nanocomposites modified with maleated polypropylene compatibilizers. Compos. B Eng.
35, 111–124 (2004)
19. Hasegawa, N., Kawasumi, M., Kato, M., Usuki, A., Okada, A.: Preparation and mechanical
properties of polypropylene-clay hybrids using a maleic anhydride-modified polypropylene
oligomer. J. Appl. Polym. Sci. 67, 87–92 (1998)
20. Liang, Z.M., Yin, J.: Poly(etherimide)/montmorillonite nanocomposites prepared by melt
intercalation. J. Appl. Polym. Sci. 90, 1857–1863 (2003)
21. Raquez, J.M., Habibi, Y., Murariu, M., Dubois, P.: Polylactide (PLA)-based nanocomposites.
Prog. Polym. Sci. 38, 1504–1542 (2013)
22. Bafna, A., Beaucage, G., Mirabella, F., Mehta, S.: 3D hierarchical orientation in polymer–clay
nanocomposite films. Polymer 44, 1103–1115 (2003)
23. Alexandre, M., Dubois, P.: Polymer-layered silicate nanocomposites: preparation, properties
and uses of a new class of materials. Mater Sci Eng. R Reports 28, 1–63 (2000)
24. Giannelis, E.P., Krishnamoorti, R., Manias, E.: Polymer-silicate nanocomposites: model
systems for confined polymers and polymer brushes. Adv. Polym. Sci. 138, 108-147 (1999)
25. Dennis, H.R., Hunter, D.L., Chang, D., Kim, S., White, J.L., Cho, J.W., et al.: Effect of melt
processing conditions on the extent of exfoliation in organoclay-based nanocomposites.
Polym. 42, 9513–9522 (2001)
26. Sinha Ray, S., Bousmina, M.: Biodegradable polymers and their layered silicate
nanocomposites: in greening the 21st century materials world. Prog. Mater Sci. 50,
962–1079 (2005)
27. Sinha Ray, S., Okamoto, M.: Polymer/layered silicate nanocomposites: a review from
preparation to processing. Prog. Polym. Sci. 28, 1539–1641 (2003)
28. Chen, J.-S., Poliks, M.D., Ober, C.K., Zhang, Y., Wiesner, U., Giannelis, E.: Study of the
interlayer expansion mechanism and thermal–mechanical properties of surface-initiated epoxy
nanocomposites. Polymer 43, 4895–4904 (2002)
29. Prime, R.B., Bair, H.E., Vyazovkin, S., Gallagher, P.K., Riga, A.: Thermogravimetric analysis
(TGA). In: Menczel, D.J., Prime, B.R. (eds.) Thermal Analysis of Polymers, p. 241. Wiley,
Hoboken (2009)
30. Earnest, C.M., Compositional Analysis by Thermogravimetry: ASTM International (1988)
31. Kumar, P.: Development of Bio-nanocomposite Films with Enhance Mechanical and Barrier
Properties using Extrusion Processing. North Carolina State University, Raleigh (2009)
Thermal Degradation of Bio-nanocomposites 243
32. Bikiaris, D.: Can nanoparticles really enhance thermal stability of polymers? Part II: An
overview on thermal decomposition of polycondensation polymers. Thermochim. Acta
523, 25–45 (2011)
33. Yang, K.K., Wang, X.L., YZ, W.: Progress in nanocomposite of biodegradable polymer. J Ind
Eng Chem. 13, 485–500 (2007)
34. Mohanty, A.K., Wibowo, A., Misra, M., Drzal, L.T.: Development of renewable resource–
based cellulose acetate bioplastic: effect of process engineering on the performance of
cellulosic plastics. Polym. Eng. Sci. 43, 1151–1161 (2003)
35. Bandyopadhyay, S., Chen, R., Giannelis, E.P.: Biodegradable organic-inorganic hybrids based
on poly(L-lactide). Polym. Mater. Sci. Eng. 81, 159–160 (1999)
36. Pluta, M., Galeski, A., Alexandre, M., Paul, M.A., Dubois, P.: Polylactide/montmorillonite
nanocomposites and microcomposites prepared by melt blending: structure and some physical
properties. J. Appl. Polym. Sci. 86, 1497–1506 (2002)
37. Chen, C.X., Yoon, J.S.: Morphology and thermal properties of poly(L-lactide)/poly(butylene
succinate-co-butylene adipate) compounded with twice functionalized clay. J. Polym. Sci. Part
B: Polym. Phys. 43, 478–487 (2005)
38. Marras, S.I., Zuburtikudis, I., Panayiotou, C.: Nanostructure vs. microstructure: morphological
and thermomechanical characterization of poly(l-lactic acid)/layered silicate hybrids. Eur.
Polymer J. 43, 2191–2206 (2007)
39. Chang, J.H., An, Y.U., Cho, D., Giannelis, E.P.: Poly(lactic acid) nanocomposites:
comparison of their properties with montmorillonite and synthetic mica (II). Polymer
44, 3715–3720 (2003)
40. Chang, J.H., An, Y.U., Sur, G.S.: Poly(lactic acid) nanocomposites with various organoclays.
I. Thermomechanical properties, morphology and gas permeability. J. Polym. Sci., Part B:
Polym. Phys. 41, 94–103 (2003)
41. Paul, M.A., Alexandre, M., Degée, P., Calberg, C., Jérôme, R., Dubois, P.: Exfoliated
polylactide/clay nanocomposites by in-situ coordination-insertion polymerization. Macromol.
Rapid Commun. 24, 561–566 (2003)
42. Paul, M.A., Alexandre, M., Degée, P., Henrist, C., Rulmont, A., Dubois, P.: New
nanocomposite materials based on plasticized poly(L-lactide) and organo-modified
montmorillonites: thermal and morphological study. Polymer 44, 443–450 (2003)
43. Zhou, Q., Xanthos, M.: Nanosize and microsize clay effects on the kinetics of the thermal
degradation of polylactides. Polym. Degrad. Stab. 94, 327–338 (2009)
44. Najafi, N., Heuzey, M.C., Carreau, P.J., Wood-Adams, P.M.: Control of thermal degradation
of polylactide (PLA)-clay nanocomposites using chain extenders. Polym. Degrad. Stab.
97, 554–565 (2012)
45. Sivalingam, G., Madras, G.: Thermal degradation of binary physical mixtures and copolymers
of poly(ε-caprolactone), poly(D, L-lactide), poly(glycolide). Polym. Degrad. Stab. 84,
393–398 (2004)
46. Chrissafis, K., Antoniadis, G., Paraskevopoulos, K.M., Vassiliou, A., Bikiaris, D.N.:
Comparative study of the effect of different nanoparticles on the mechanical properties and
thermal degradation mechanism of in situ prepared poly(ε-caprolactone) nanocomposites.
Compos. Sci. Technol. 67, 2165–2174 (2007)
47. Peng, H., Han, Y., Liu, T., Tjiu, W.C., He, C.: Morphology and thermal degradation behavior
of highly exfoliated CoAl-layered double hydroxide/polycaprolactone nanocomposites
prepared by simple solution intercalation. Thermochim. Acta 502, 1–7 (2010)
48. Carrasco, F., Gámez-Pérez, J., Santana, O.O., Maspoch, M.L.: Processing of poly(lactic acid)/
organomontmorillonite nanocomposites: microstructure, thermal stability and kinetics of the
thermal decomposition. Chem. Eng. J. 178, 451–460 (2011)
49. Reich, L.: Elements of Polymer Degradation. McGraw-Hill, New York (1971)
50. Carrasco, F., Pagès, P., Gámez-Pérez, J., Santana, O.O., Maspoch, M.L.: Processing of poly
(lactic acid): characterization of chemical structure, thermal stability and mechanical
properties. Polym. Degrad. Stab. 95, 116–125 (2010)
244 K.A. Murray et al.
51. Moreira, F.K.V., Pedro, D.C.A., Glenn, G.M., Marconcini, J.M., Mattoso, L.H.C.: Brucite
nanoplates reinforced starch bionanocomposites. Carbohydr. Polym. 92, 1743–1751 (2013)
52. Espino-Pérez, E., Bras, J., Ducruet, V., Guinault, A., Dufresne, A., Domenek, S.: Influence of
chemical surface modification of cellulose nanowhiskers on thermal, mechanical, and barrier
properties of poly(lactide) based bionanocomposites. Eur. Polymer J. 49, 3144–3154 (2013)
53. Araújo, A., Botelho, G., Oliveira, M., Machado, A.V.: Influence of clay organic modifier on
the thermal-stability of PLA based nanocomposites. Appl. Clay Sci. 88–89, 144–150 (2014)
54. Hakkarainen, M. Aliphatic Polyesters: abiotic and biotic degradation and degradation
products. In: Albertsson, A.-C (ed.) Degradable Aliphatic Polyester, pp. 113–138. Springer,
Heidelberg (2002)
55. Rosa, D.S., Lotto, N.T., Lopes, D.R., Guedes, C.G.F.: The use of roughness for evaluating the
biodegradation of poly-β-(hydroxybutyrate) and poly-β-(hydroxybutyrate-co-β-valerate).
Polym. Testing 23, 3–8 (2004)
56. Lotto, N.T., Calil, M.R., Guedes, C.G.F., Rosa, D.S.: The effect of temperature on the
biodegradation test. Mater. Sci. Eng. C 24, 659–662 (2004)
57. Reddy, C.G.: R. Rashmi, Kalia, VC. Polyhydroxyalkanoates: an overview. Bioresour.
Technol. 87, 137–146 (2003)
58. de Jong, S.J., Arias, E.R., Rijkers, D.T.S., van Nostrum, C.F., Kettenes-van den Bosch, J.J.,
Hennink, W.E.: New insights into the hydrolytic degradation of poly(lactic acid): participation
of the alcohol terminus. Polymer 42, 2795–2802 (2001)
59. Fukushima, K., Tabuani, D., Dottori, M., Armentano, I., Kenny, J.M., Camino, G.: Effect of
temperature and nanoparticle type on hydrolytic degradation of poly(lactic acid)
nanocomposites. Polym. Degrad. Stab. 96, 2120–2129 (2011)
60. Zhou, Q., Xanthos, M.: Nanoclay and crystallinity effects on the hydrolytic degradation of
polylactides. Polym. Degrad. Stab. 93, 1450–1459 (2008)
61. Signori, F., Coltelli, M.-B., Bronco, S.: Thermal degradation of poly(lactic acid) (PLA) and
poly(butylene adipate-co-terephthalate) (PBAT) and their blends upon melt processing.
Polym. Degrad. Stab. 94, 74–82 (2009)
62. Gleadall, A., Pan, J., Kruft, M.-A., Kellomäki, M.: Degradation mechanisms of bioresorbable
polyesters. Part 1. Effects of random scission, end scission and autocatalysis. Acta Biomater.
10, 2223–2232 (2014)
63. Nieddu, E., Mazzucco, L., Gentile, P., Benko, T., Balbo, V., Mandrile, R., et al.: Preparation
and biodegradation of clay composites of PLA. React. Funct. Polym. 69, 371–379 (2009)
64. Chivrac, F., Pollet, E., Schmutz, M., Avérous, L.: Starch nano-biocomposites based on needle-
like sepiolite clays. Carbohydr. Polym. 80, 145–153 (2010)
65. Bruzaud, S., Bourmaud, A.: Thermal degradation and (nano)mechanical behavior of layered
silicate reinforced poly(3-hydroxybutyrate-co-3-hydroxyvalerate) nanocomposites. Polym.
Testing 26, 652–659 (2007)
66. Ten, E., Turtle, J., Bahr, D., Jiang, L., Wolcott, M.: Thermal and mechanical properties of poly
(3-hydroxybutyrate-co-3-hydroxyvalerate)/cellulose nanowhiskers composites. Polymer 51,
2652–2660 (2010)
67. Pantoustier, N., Alexandre, M., Degée, P., Calberg, C., Jérôme, R., Henrist, C., et al.: Poly(η-
caprolactone) layered silicate nanocomposites: effect of clay surface modifiers on the melt
intercalation process. e-Polymers 77 (2001)
68. Cyras, V.P., Manfredi, L.B., Ton-That, M.-T., Vázquez, A.: Physical and mechanical
properties of thermoplastic starch/montmorillonite nanocomposite films. Carbohydr. Polym.
73, 55–63 (2008)
69. Schlemmer, D., Angélica, R.S., Sales, M.J.A.: Morphological and thermomechanical
characterization of thermoplastic starch/montmorillonite nanocomposites. Compos. Struct.
92, 2066–2070 (2010)
70. Luiz de Paula E, Mano V, Pereira FV. : Influence of cellulose nanowhiskers on the hydrolytic
degradation behavior of poly (d,l-lactide). Polym Degrad Stab. 96, 1631-1638 (2011)
Thermal Degradation of Bio-nanocomposites 245
71. Hossain, K.Z., Ahmed, I., Parsons, A., Scotchford, C., Walker, G., Thielemans, W., et al.:
Physico-chemical and mechanical properties of nanocomposites prepared using cellulose
nanowhiskers and poly(lactic acid). J. Mater. Sci. 47, 2675–2686 (2012)
72. Wang, D., Yu, J., Zhang, J., He, J., Zhang, J.: Transparent bionanocomposites with improved
properties from poly (propylene carbonate) (PPC) and cellulose nanowhiskers (CNWs).
Compos. Sci. Technol. 85, 83–89 (2013)
73. Fortunati, E., D’Angelo, F., Martino, S., Orlacchio, A., Kenny, J.M., Armentano, I.: Carbon
nanotubes and silver nanoparticles for multifunctional conductive biopolymer composites.
Carbon 49, 2370–2379 (2011)
74. Hapuarachchi, T.D., Peijs, T.: Multiwalled carbon nanotubes and sepiolite nanoclays as flame
retardants for polylactide and its natural fibre reinforced composites. Compos. A Appl. Sci.
Manuf. 41, 954–963 (2010)
75. Sadegh-Hassani, F., Mohammadi Nafchi, A.: Preparation and characterization of
bionanocomposites films based on potato starch/halloysite nanoclay. Int. J. Biol. Macromol.
67, pp. 458-462 (2014)
76. Ojijo, V., Ray, S.S.: Nano-biocomposites based on synthetic aliphatic polyesters and nanoclay.
Prog. Mater. Sci. 62, 1–57 (2014)
77. Nerantzaki, M., Papageorgiou, G.Z., Bikiaris D.N.: Effect of nanofiller’s type on the thermal
properties and enzymatic degradation of poly(ε-caprolactone). Polym. Degrad. Stab. 108,
257–268 (2014)
78. Liu, X., Zou, Y., Li, W., Cao, G., Chen, W.: Kinetics of thermo-oxidative and thermal
degradation of poly(d, l-lactide) (PDLLA) at processing temperature. Polym. Degrad. Stab. 91,
3259–3265 (2006)
79. Hule, R.A., Pochan, D.J.: Polymer nanocomposites for biomedical applications. MRS Bull.
32, 354–358 (2007)
80. Bharadwaj, R.K.: Modeling the barrier properties of polymer-layered silicate nanocomposites.
Macromolecules 34, 9189–9192 (2001)
81. Sorrentino, A., Gorrasi, G., Vittoria, V.: Potential perspectives of bio-nanocomposites for food
packaging applications. Trends Food Sci. Technol. 18, 84–95 (2007)
82. Emamifar, A., Kadivar, M., Shahedi, M., Soleimanian-Zad, S.: Evaluation of nanocomposite
packaging containing Ag and ZnO on shelf life of fresh orange juice. Innovative Food Sci.
Emerg. Technol. 11, 742–748 (2010)
83. Chaudhry, Q., Scotter, M., Blackburn, J., Ross, B., Boxall, A., Castle, L., et al.: Applications
and implications of nanotechnologies for the food sector. Food Addit. Contam. Part A Chem.
Anal. Control Exposure Risk Asses. 25, 241–258 (2008)
84. Tiwari, A.: Frontiers in bio-nanocomposites. Advanced. Mater. Lett. 2, 377 (2011)
85. Madhavan Nampoothiri, K., Nair, N.R., John, R.P.: An overview of the recent developments
in polylactide (PLA) research. Bioresour. Technol. 101, 8493–8501 (2010)
86. Li, H.Y., Chang, C.M., Hsu, K.Y., Liu, Y.L.: Poly(lactide)-functionalized and Fe 3O 4
nanoparticle-decorated multiwalled carbon nanotubes for preparation of electrically-
conductive and magnetic poly(lactide) films and electrospun nanofibers. J. Mater. Chem.
22, 4855–4860 (2012)
87. Murariu, M., Bonnaud, L., Yoann, P., Fontaine, G., Bourbigot, S., Dubois, P.: New trends in
polylactide (PLA)-based materials: ``Green” PLA-Calcium sulfate (nano) composites tailored
with flame retardant properties. Polym. Degrad. Stab. 95, 374–381 (2010)
88. Cabedo, L., Feijoo, J.L., Villanueva, M.P., Lagarén, J.M., Giménez, E.: Optimization of
biodegradable nanocomposites based on aPLA/PCL blends for food packaging applications.
Macromol. Symp. 233, 191–197 (2006)
89. ReportLinker. Packaging Industry: Market Research Reports, Statistics and Analysis.
ReportLinker (2014)