Fibers and Polymers 2012, Vol.13, No.6, 762-768 DOI 10.

1007/s12221-012-0762-z

Thermal Characteristics of Basalt Fiber Reinforced Epoxy-Benzoxazine

Composites
Hodong Kim
Department of Fiber System Engineering, Dankook University, YongIn 448-701, Korea
(Received March 4, 2012; Revised March 15, 2012; Accepted March 31, 2012)

Abstract: This study investigates the possibility of utilizing basalt chopped fiber in order to prepare a thermally stable fiber
reinforced composite. Bi-component resin system using epoxy and benzoxazine monomer is proposed and its cure
characteristic is evaluated by FT-IR and DSC. Copolymerization of epoxy resin upon curing with benzoxazine is carried out
in the absence of a strong catalyst. Through the evaluation of Tg of the epoxy-benzoxazine copolymer resin and its composite,
it is clear that the incorporation of basalt fiber in composite has a great role and advantage. Also, this study systematically
evaluates the apparent char yield and net char yield gain of the composites using TGA thermograms. Based on the results of
DSC and TGA, it is advised that the favorable composite composition can be prepared from the range of 20 % to 50 % of
epoxy content with 10 % of basalt fiber.
Keywords: Epoxy resin, Polybenzoxazine, Basalt fiber, Composite, Thermal property

Introduction excellent heat resistance, significant capability of heat,

acoustic resistance, and outstanding vibration isolators.
Over the past few decades, there has been a growing Several articles dealing with glass and carbon fiber
interest in polymer composites as a new and unique high reinforced polymer composites mention the significance of
performance material. The combination of inorganic or basalt fiber as a possible new reinforcing material [9,10].
organic particles, powders, or fibers and polymers lead to Moreover, the demand for thermally stable epoxy composites
exceptional composites with such properties that were not is drastically growing because of the widespread applications
found in typical single phase materials. Among the in electronic industries, such as printed circuit boards and
polymeric matrices for the composites, epoxy resins are encapsulation. In general, the flame-retardancy and thermal
known to have many excellent properties, including good properties of epoxy polymers can be improved through
chemical and solvent resistances, high mechanical strengths, modification of the molecular structure or incorporation of
and high distortion temperatures. Therefore, they have been various fillers. For example, one way of achieving high
applied not only in the traditional fields such as adhesives thermal stability of epoxy composites is incorporating halogen-
and coatings, but also in advanced technological areas such containing [11] or phosphorus-containing materials [12].
as the electronics and aerospace industries. So they may be However, bromine-containing polymers release hydrogen
widely applied as materials in advanced technological areas. bromide or dioxins during combustion, even though they
It is essential to improve the flame retardancy and thermal exhibit good flame retardancy. Phosphorus-based compounds
properties of epoxy resins [1-6]. give powerful flame retardancy by covering the outer layer
In addition to the matrix resins, many reinforcing fibers of polymers with a nonflammable coating during combustion
have been studied extensively. The increasing economical but show poor hydrophobic properties which is detrimental
and environmental demands on the reinforcements of load- for electronic application. The other way is to replace the
bearing polymer structural materials encourage researchers epoxy resin to more thermally stable resins or to use their
to develop new, high-strength reinforcing materials and blends.
structures. Consequently in the few past decades, intensive Benzoxazine, a new type of thermosetting resin, can be
research has been carried out all over the world with regard polymerized by a thermally induced ring-opening reaction.
to the applicability of different organic and inorganic A phenolic-like structure can be obtained by the Mannich
reinforcing fibers in polymer matrices. Accordingly, basalt base bridge after curing. Polybenzoxazines exhibit special
fiber of mineral origin has gained increased attention as a features, such as small shrinkage upon curing, no byproduct
reinforcing material compared to traditional glass and release upon curing, low water absorption, and superior
carbon fibers [7,8]. electrical properties, so they attract much attention [13-16].
The basis of basalt fibers is basalt rock which is a However, polybenzoxazines alone display rather low crosslink
volcanic, over-ground, effusive rock saturated with 45-52 % densities due to strong hydrogen bonding restricting segmental
SiO2. As a result of this formation, basalt has several mobility and impeding network formation [17,18].
advantageous properties such as high modulus of elasticity, This shortcoming may be overcome by copolymerization
of the polybenzoxazine precursor with an epoxy resin which
*Corresponding author: [email protected] allows the network structure to achieve a higher crosslink

762
Epoxy-Benzoxazine Composites Fibers and Polymers 2012, Vol.13, No.6 763

density. Furthermore, phenolic groups which are developing to 110 oC for 20 min. with a mechanical stirrer (Scheme 1).
during the ring-opening polymerization of benzoxazine The reaction product was purified by following extraction
resins can initiate the epoxy reaction without toxic amine process. The solution of reaction product dissolved in
curing agents at elevated temperatures [19]. In addition, by diethylether was washed by cold 3 N NaOH at least 3 times,
incorporating the chopped basalt fiber with epoxy-benzoxazine followed by distilled water, and then drying over sodium
copolymers, this system leads to synergic effect on the sulfate. After evaporating the solvent in a rotary evaporator,
physical properties as well as the thermal properties over a very fine powder was obtained. The purity of the monomer
those of each homopolymers. was determined by proton nuclear magnetic resonance (1H-
Therefore, in the present work, glycidyl ether of bisphenol- NMR, Varian Gemini 200, USA) spectra.
F was copolymerized with bisphenol-A based benzoxazine
to investigate the thermal properties of the bi-component Preparation of Basalt Fiber Reinforced Composites
resins. And the chopped basalt fiber reinforced composites The appropriate amounts of benzoxazine, epoxy resin and
were prepared using these resins in order to study the basalt fiber were weighed into a glass dish and mechanically
applicability of basalt fibers as reinforcing materials which stirred at 85 oC until well mixed. The fluid resin mixture was
can enhance the physical properties. Thermal characteristics then poured into a preheated mould between two glass plates
of the resins and composites are further investigated in terms treated with a silicon based mould release agent. The resin
of curing mechanism, Tg, thermal degradation, and char filled mould was initially heated under reduced pressure at
yield. 100 oC for 1 h in order to remove any air entrapped in the
mould filling process. The material was then subjected to the
Experimental step-wise curing profile at 140 oC-1 h, 180 oC-1 h, and
220 oC-2 h in a temperature controlled oven. The curing
Materials profile was selected from the preliminary result of non-
All chemicals were used as received. Bisphenol-A (98 %, isothermal and isothermal experiment by differential scanning
Duksan), p-formaldehyde (90 %, Samchun), aniline (99 %, calorimetry (DSC). For the comparison purpose, DGEBF
Shinyo) were used for the preparation of 2,2-bis(3,4- and anhydride curing agent mixture was evacuated to
dihydro-3-phenyl-2H-1,3-benzoxazine)propane (abbreviated as remove air bubbles at room temperature for 1 h and then
BA-a). Diglycidyl ether of bisphenol-F (DGEBF, Bakelite cured at 140 oC for 2 h. In order to eliminate variability due
EPR 161) was obtained from Hexion. Tetrahydrophthalic to monomer purity or cure history, all samples were prepared
anhydride (TETA, Aldrich) were used as a curing agent for from single batches of both benzoxazine and epoxy, and
epoxy resin. Several solvents such as diethyl ether (95 %, were cured simultaneously.
Duksan), methanol (98 %, Samchun) etc. were used for
purification. 3 mm length of chopped basalt fiber was Instrumentation
prepared by cutting the basalt fiber roving which was Fourier transform infrared spectroscopy (FT-IR) was
supplied from Secotech (Korea). performed on a PERKIN ELMER spectrophotometer
(Spectrum GX FT-IR system, USA) which was equipped
Synthesis of Benzoxazine Monomer (BA-a) with a deuterated triglycine sulfide (DTGS) detector. All
Bifunctional benzoxazine monomers (2,2-bis(3,4-dihydro- spectra were recorded at a resolution of 2 cm-1 and displayed
3-phenyl-2H-1,3-benzoxazine) propane, abbreviated as BA- in the absorbance mode. Coaddition of 10 scans was
a ) based on bisphenol A and aniline was synthesized and sufficient to obtain good signal-to-noise ratio. Thin films of
purified according to the procedure of Ning and Ishida [21] monomers and resins on a potassium bromide (KBr) crystal
or Ishida [22]. The bisphenol-A, para-formaldehyde and were prepared by solvent-casting method with chloroform as
aniline in a molar ratio of 1:4:2 were mixed in a round a solvent.
bottom flask without adding any solvents and slowly heated Thermal property of the composites was analyzed by
Differential Scanning Calorimeter (DSC) (TA instrument
DSC2010 system, USA) using hermetic pan under nitrogen
gas at a flow rate 60 ml/min and a heating rate of 10 oC/min.
Overlapped exothermic peaks of the mixed resins were
curve-resolved using a mixed Lorentzian-Gaussian function
in GRAMS software. It was calculated until the least-
squares curve-fitting converged.
Thermal degradation behavior of the composites was
characterized with Thermogravimetric analysis (TGA) (TA
instrument Q series 50 system, USA) at a nitrogen flow rate
Scheme 1. Synthesis of BA-a bifunctional benzoxazine monomer. of 90 ml/min and a heating rate of 20 oC/min.
764 Fibers and Polymers 2012, Vol.13, No.6 Hodong Kim

Results and Discussion increase in the tetra-substituted mode at 1477 cm-1. The
other characteristic band of benzoxazine ring can be found
Cure Characteristics of BA-a Benzoxazine and Epoxy in the region of 950-920 cm-1 which would be consumed
Resin Mixture upon curing.
A qualitative infra-red analysis was carried out in order to Figure 1(e) and (f) demonstrate that the ring opening
verify that epoxy resin was cured without the addition of a polymerization of the benzoxazine and epoxide ring
curing agent. For the purpose of comparison, the epoxy resin simultaneously occur without any external curing agents. It
was cured with an anhydride curing agent, and the infra-red can be observed that the polymerization of the benzoxazine
spectra of epoxy-anhydride system are shown in Figure 1(a) is monitored by the broadening of tetra-substituted benzene
and (b). The reaction of epoxy is monitored by the 930 cm-1 structure. Although the region for epoxide and benzoxazine
of the epoxide ring modes which disappear as the ring is
opened. It can be seen that the epoxide peaks have almost
completely disappeared in the cured epoxy resin. It is also
found that the broad band near 3540 cm-1 is intensified by
the increase of the hydroxyl group which is the resulting
structure upon curing as shown in Scheme 2(a). The ring
opening reaction of benzoxazine monomer can be investigated
by two peaks originating from the benzoxazine ring and
substituted benzene structure as shown in Figure 1(c) and
(d). As can be seen in Scheme 2(b), the benzene rings that
form the backbone of a benzoxazine monomer molecule are
tri-substituted. During polymerization, the benzoxazine
rings open and propagate, at which point the backbone
benzene rings become tetra-substituted. Therefore, the
curing of benzoxazine monomer may be monitored in the Scheme 2. Curing mechanisms of (a) epoxy-anhydride system, (b)
infra-red region by the decrease in the tri-substituted benzoxazine, and (c) epoxy-benzoxazine system.
benzene contribution at 1498 cm-1 and the corresponding

Figure 1. FT-IR spectra of the epoxy-anhydride (a) monomer, (b) Figure 2. DSC thermograms of (a) BA-a benzoxazine, (b) epoxy:
cured at 140 oC, the BA-a benzoxazine, (c) monomer, (d) cured at BA-a=2:8, (c) epoxy:BA-a=4:6, (d) epoxy:BA-a=5:5, (e)
180 oC, the epoxy-benzoxazine, (e) monomer, and (f) cured at 220 oC. epoxy: BA-a=6:4, and (f) epoxy-anhydride.
Epoxy-Benzoxazine Composites Fibers and Polymers 2012, Vol.13, No.6 765

Figure 3. Variation of the relative cure exotherm area of the

epoxy-benzoxazine copolymers as a function of epoxy content.
Figure 4. Variation of Tg of the epoxy-benzoxazine copolymers as
a function of epoxy content.
rings is overlapped, the complete consumption clearly
implies the reaction of the epoxide ring. It should be noted polybenzoxazines have been known to display relatively low
that a large amount of hydroxyl group is formed in cured chemical crosslink densities compared to the conventional
epoxy-benzoxazine copolymer due to the extensive amount resins with similar properties. This somewhat mismatching
of crosslinking reaction (Scheme 2(c)). result has been explained by the fact that the hydrogen
This ring opening reaction of the epoxide ring, initiated bonding prevalent in the benzoxazines [17,18] gives sufficiently
solely by the curing of benzoxazine, is also confirmed by the strong physical crosslinking to constrain segmental mobility
fact that the exotherm areas of the DSC thermograms are and contribute to the rigidity that has been observed in the
observed for the epoxy-benzoxazine copolymers. Although glassy state. For this reason, polybenzoxazine may possess
the epoxy resin with anhydride, which is executed for the further potential which can be tightened by additional
purpose of comparison, shows a significant exothermic peak chemical crosslinking using epoxy reaction. Although the
(Figure 2(f)), an inevitable amount of exothermic peak for addition of epoxy resin such as DGEBF provides more
epoxy resin is observed in the region of 115-170 oC as chemical crosslinking to the benzoxazine, a relatively flexible
shown in Figure 2(b)-(e). It is interesting that the shape of structure of DGEBF may lower the Tg of copolymer than that
the exothermic peak for benzoxazine is sharper than that of of polybenzoxazine homopolymer. Therefore, the optimized
the pure BA-a benzoxazine, and becomes narrower with an composition of copolymer becomes essential. As expected
increase of epoxy content. This may be related to the fact and shown in Figure 4, Tgs of copolymers are systematically
that developing phenol groups are rapidly consumed by the decreased with the increase of epoxy resin content.
large amount of epoxy ring, which suppress the complex The Tg decrement of copolymers due to the epoxy
side reaction of the benzoxazine monomer [18]. However, as component can be improved by the incorporation of basalt
seen in Figure 3, the relative cure exotherm area of the fiber. As shown in Figure 5, The Tgs of the chopped basalt
epoxy to that of benzoxazine is clearly increased by the fiber reinforced epoxy-benzoxazine composites are increased
increase of epoxy resin. up to the level of polybenzoxazine homopolymer with the
increase of fiber content. This means that the optimization of
Glass Transition Temperature (Tg) of the Copolymer Tg without noticeable difference can be achieved by the
Resins and the Composites design of composite composition. Great attention has been
Prior to studying the Tg of the composites, the Tg of the drawn from the fact that the compositions of 3 to 10 % of
copolymer resin without basalt fiber is investigated and basalt fiber with epoxy:BA-a=2:8 copolymer show the
shown in Figure 4. Despite the high modulus and Tg, the comparable Tg of 170 oC.
766 Fibers and Polymers 2012, Vol.13, No.6 Hodong Kim

Figure 7. Theoretical prediction of TGA thermogram based on the

thermograms of each component and the net gain by composite
Figure 5. Variation of Tg of the basalt fiber reinforced epoxy- preparation.
benzoxazine composites as a function of fiber content.

thermal weight loss of epoxy-benzoxazine copolymer resins

and their derivatives. Although there is no big difference in
the initial weight loss below 400 oC even if epoxy content is
increased, the weight loss of copolymers with high epoxy
content drastically decreases over 400 oC compared to the
BA-a benzoxazine homopolymer. It is well known that BA-a
polybenzoxazine has 3 distinctive thermal degradation steps
which are clearly found from the derivative curve of weight
loss thermogram: a loss of the amine functional group
centered at 350 oC, chain scission of Mannich bridge
centered at 400 oC, and loss of benzene structure over 500 oC
[23-25]. However, it is shown that the thermal degradation
behaviors for the loss of the amine group and benzene
structure are noticeably diminished despite the overall poor
degradation behavior. This may be caused by the increase of
additional crosslinking due to the epoxy resin.
This negative aspect of the thermal stability of the copolymer
system can be effectively improved by the incorporation of
basalt fiber. As shown in Figure 7 which is TGA thermograms
for the composite of epoxy:BA-a=5:5 with 10 % of basalt
chopped fiber, the addition of basalt fiber drastically increases
Figure 6. TGA thermograms of epoxy-benzoxazine copolymers
the char yield from 28.4 % of bulk resin to 46.1 % of the
with different compositions.
composite. However, it is difficult to interpret whether this
favorable improvement is just from the simple addition of
Thermal Degradation Behavior of the Copolymer Resins non-degradable inorganic basalt fiber or not. In order to
and the Composites exclude the influence of simple addition and to observe the
The other important thermal property is thermal degradation possible interactions between the components, the difference
behavior and char yield because they are closely related to (WLnet) between the experimental and theoretical curves is
the practical application environment. Figure 6 is the obtained as follows:
Epoxy-Benzoxazine Composites Fibers and Polymers 2012, Vol.13, No.6 767

Figure 8. TGA and WLnet thermograms of the basalt fiber Figure 9. Variation of the char yield and char yield gain of the
reinforced epoxy-benzoxazine (Epoxy:BA-a=4:6) composites. basalt fiber reinforced epoxy-benzoxazine copolymers as a
function of epoxy content.

WLtheo = rWLresin + (1 − r) WLbf (1)

result of char yield gain and Tg depression of the composites,
WLnet = WLexp − WLtheo (2)
it is advised to prepare the composite of 20 % to 50 % of
WLresin : Weight loss in TGA thermograms of a used resin epoxy content with more than 10 % of basalt fiber in order to
WLbf: Weight loss in TGA thermograms of a pure basalt fiber obtain the optimum thermal properties. Further evaluation of
r: Resin fraction of a composite the physical properties is needed and is in progress.
WLtheo : Theoretical weight loss of a composite
WLexp : Experimental weight loss in TGA thermograms of Conclusion
a composite
WLnet : Net gain of weight loss of a composite. The basalt chopped fiber reinforced epoxy-benzoxazine
composites were prepared in order to investigate the thermal
If WLnet >0, we can assume the presence of positive characteristics of epoxy-benzoxazine copolymer and its
interactions between the resin and the basalt fiber that allow composite. Upon curing of benzoxazine resin, epoxy resin
a relatively good thermal stability of the composite. In was successfully cured and copolymerized with benzoxazine
contrast, if WLnet <0, negative interactions between the without any strong catalyst. While the Tg of epoxy-
components are observed which indicates a lower thermal benzoxazine copolymer is lowered with the increase of
stability. The result is impressive. The WLnet for the composite epoxy content as expected, the Tg of the corresponding
of epoxy:BA-a=5:5 with 10 % of basalt chopped fiber basalt fiber reinforced composite is comparable to that of the
shows more than 10 % which implies the synergic interaction BA-a polybenzoxazine. Also, this study systematically
between the resin and the basalt fiber. evaluates the apparent char yield and net char yield gain due
The effectiveness of this analysis is well shown in Figure 8 to the incorporation of basalt fiber. From the results of DSC
for the composite of epoxy:BA-a=4:6 with different fiber and TGA, it was found that the optimum thermal properties
content. Although the apparent char yields are increasing of the composite can be prepared from 20 % to 50 % of
with the increase of fiber content, it is clearly seen that the epoxy content with more than 10 % of basalt fiber.
WLnet is not so noticeable for the composites with low fiber
content. However, the composite with 10 % basalt fiber shows Acknowledgements
significant net gain of weight loss. The apparent char yield
and its net gain for all samples are summarized in Figure 9. This work was supported by 2009 Dankook university
It seems that all composites have a higher char yield than project for funding RICT. I also would like to thank to the
that of resin in the range of 30 % to 46 %. Considering the assistance of Hwayeon Moon.
768 Fibers and Polymers 2012, Vol.13, No.6 Hodong Kim

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