Effect of The Joncryl1 ADR Compatibilizing Agent in Blends of Poly (Butylene Adipate-Co-Terephthalate) / Poly (Lactic Acid)
Effect of The Joncryl1 ADR Compatibilizing Agent in Blends of Poly (Butylene Adipate-Co-Terephthalate) / Poly (Lactic Acid)
Effect of The Joncryl1 ADR Compatibilizing Agent in Blends of Poly (Butylene Adipate-Co-Terephthalate) / Poly (Lactic Acid)
Compatibilization www.ms-journal.de
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Figure 1. Structures of (a) PBAT, (b) PLA, and (c) chain extender ADR.
2.1. Mechanical Properties in the blend, H0m is the melting enthalpy of 100% crystalline
PBAT, and the value used is 114 J g1.[13] For PLA, the melting
Tensile tests were performed in a universal testing machine enthalpy of 100% crystalline is 93 J g1.
(Instron 5900) (Instron S/A Ind. e Com. Ltda.) according to
ASTM D638. The cross-head movement speed of 50 mm min1
was used as recommended by the standard. The elastic modulus 2.3. Morphological Properties
(E), ultimate tensile strength (σmax), and elongation at break
(emax) were evaluated. The morphologies of the fractured samples were examined
through a JEOL, JCM-6000 SEM, at an acceleration voltage of
10 kV. The samples were sputtered with gold to 20 nm thickness
2.2. Thermal Properties using a Leica EM ACE 200 sputter coater.
where ΔHm is the sample melting enthalpy, ΔHcc is the PLA cold
crystallization enthalpy, WPBAT is the mass fraction of the PBAT
3. Results
3.1. Tensile Properties
Table 1. Prepared PBAT/CE/PLA compositions with their
nomenclature. Table 2 shows results for tensile strength, elongation at break
and modulus of elasticity for all studied formulations.
Sample PBAT [wt%] PLA [wt%] CE [wt%] Considering neat PBAT, the chain extender (CE) led to increase
PBAT 100 –
from 1269.3% to 1848.7% in elongation which corresponds to a
45.6% increase. The increase in elongation at break may be
PBAT/CE 99.5 – 0.5
related to the chain extender behavior after the interaction with
PBAT/PLA 80/20 80 20 – the polymer chain end.[13] However, there was a reduction in
PBAT/PLA/CE 80/20 79.5 20 0.5 tensile strength at break from 25.1 to 19.9 MPa (20% decrease).
PBAT/PLA 70/30 70 30 – Similar results are observed for neat PLA. Yan et al studied the
PBAT/PLA/CE 70/30 69.5 30 0.5 influence of ADR in poly(ethylene terephthalate) and observed
that ADR increased the elastic phenomenon, as verified. This
PLA – 100 –
high elasticity is related to the molecular structure of the
PLA/CE – 99.5 0.5
modified materials.[15]
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Table 2. Mechanical properties of neat PBAT and PLA and their blends with and without CE.
Sample Tensile strength [MPa] Elongation at break [%] Young’s modulus [MPa]
For the PBAT/PLA 80/20 blend, the addition of CE increased deformation.[15] Interestingly, the ductility of all samples can be
the elastic modulus and elongation at break. Also, the blend significantly improved by incorporation of a small amount of CE
PBAT/PLA/CE 80/20 showed a slight increase in tensile (0.5 wt%.).[14]
strength. This is because of, as the compatibility and interfacial
adhesion between the PBAT and PLA phases were improved, the
tensile and strain properties could be more efficiently 3.2. Thermal Properties
transferred from the PBAT matrix to the PLA domains after
the addition of the chain extender.[16,17] According to Li et al. the The thermal properties of the PBAT, PLA, and their blends with
ADR addition resulted in the reaction between the carboxylic and without CE are studied by using differential scanning
acid group of PBAT/PLA blends and the CE.[18] calorimeter (DSC). Table 3 shows the cold crystallization
Similar results were observed by Tang et al. which added temperature (Tcc) and enthalpy (ΔHcc), melting temperature
0.5 wt% of Joncryl ADR and observed an improve in tensile (Tm), melting enthalpy (ΔHm), and the degree of crystallinity (Xc)
strength and flexural strength from the studied blend (POM/ of the samples related to the first heating scan. The glass
TPU).[19] It is possible to note that the increase in the amount of transition temperature (Tg) values were determined in the
PLA in the blend composition results in larger modulus of second heating scan to evaluate the miscibility of the systems.
elasticity, because when a weakly conducting polymer with high PLA showed a double endothermic peak (melting temperature)
tensile strength is added as the dispersed phase, it is expected at 149 and 157.6 C. This double peak is common in polyesters,
that there should be an increase in the elastic modulus, and the literature justifies its presence by a melt/recrystalliza-
satisfying the additivity rule.[13] tion/re-melt mechanism.[16,20]
For the PBAT/PLA 70/30 blend, the addition of the CE caused For the PBAT/PLA blends, there was an overlap between the
a small reduction in the modulus of elasticity, which may be PBAT melting region and the PLA cold-crystallization region.
justified by a structural change occurring in the mixture,[13] Consequently, it was difficult to determine the cold crystalliza-
where the PLA phase appeared as ellipsoids, as deformed tion temperature (Tcc) and enthalpy (ΔHcc), besides PBAT
droplets with low aspect ratio and possibly acting as stress melting temperature for PBAT/PLA/CE 80/20 blend. It was
concentrators in the PBAT matrix. These results were observed reported that this behavior occurs because of the crystals melted
by Arruda et al. in their study.[12] In addition, it possibly occurs in at different temperatures had the similar structure but different
consequence of numerous cavities and/or cracks formed during lamellar thickness, which results in double endothermic
Table 3. DSC data of PBAT, PLA, and PBAT/PLA blends with and without CE.
Sample Tga [ C] Tgb [ C] Tcc [ C] ΔHcc [J g1] Tma [ C] Tmb [ C] ΔHm [J g1] Xc [%]
Tga is the glass temperature of PBAT, Tgb is the glass temperature of PLA, Tma is the melting temperature of PBAT, Tmb is the melting temperature of PLA.
It was not possible to determine the Tcc and ΔHcc in this blend.
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Figure 2. Scheme and micrographs of the fractured neat PBAT, neat PLA, and their blends with and without CE.
peak.[16,20] In all blends, the variation on the Tmb probably is due 3.3. Morphological Analysis
to the increase in the organization of the polymers chains due to
the high crystallinity of PLA. The morphologies of neat PBAT and PLA and their blends with
All the blends showed two distinct glass transition temperature, and without CE are shown in Figure 2. The morphology of
and no change occurred in this transition, indicating that the immiscible polymers blends is the result of the interaction
formed blends are thermodynamically immiscible.[13] Further- between process variables as well as temperature, deformation
more, the presence of the chain extender did not lead to changes in types, and shear rate and blend components properties (phases
this transition temperature (Tg), but it decreased the ΔHcc, and percentage, interfacial tension, viscosity ratio, and the elasticity)
slightly increased the melting temperature for the blends. The PLA and the final morphology is the combination of all factors.[13]
phases in the blends reduced the degree of crystallinity from 13.7% The addition of the CE did not cause any visible morphological
in the neat PBAT to 8.1% and 3.7%, respectively, in the blends with changes to neat PBAT, which is an indication that the CE acted
20% and 30% PLA. This occurred because PLA has lower chain just as a chain extender. The same behavior is observed for PLA
flexibility and a higher viscosity, and that restricts the PBAT and PLA/CE. However, when analyzing the morphology of the
molecular reorganization and the chains mobility in the blend, blends without the CE, a characteristic of immiscible blends with
which decreases the degree of crystallinity.[13] low adhesion is observed. In the PBAT/PLA 80/20 without chain
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Figure 3. Contact angle for the neat PBAT and their blends with and without CE.
extender, voids are observed in the matrix, where “beads” of PLA samples, the addition of CE can promote biodegradation and/or
were pulled out from the polymer matrix. The spheres dispersed hydrolysis, being indicative of increased biodegradability.[25] In
in the continuous phase are a characteristic of reinforcement the case of the blends, there is an opposite behavior, and it is
morphology for rubber tenacification.[12] possible to observe that higher PLA content in the mixture with
After the addition of the CE, the voids presented smaller PBAT/CE resulted in greater WCA (higher degree of
diameter (according to Figure 2), and the sample was more hydrophobicity).
homogeneous. The CE can act as a compatibilizer and lead to
the reduction of interfacial tension that stabilizes the dispersed
phase in smaller sizes, leading to the refinement of the 4. Conclusions
dispersed phase.[13] This behavior can be seen in the PBAT/
Both the neat PBAT and the studied blends showed, after the
PLA/CE 80/20, corroborating the results of the mechanical
CE addition, an increase in the elongation at break, while the
tensile tests.
elastic modulus slight increased in the neat PBAT and PBAT/
In the case of the PBAT/PLA/CE 70/30 blend, the addition of
PLA 80/20 and decreased into the PBAT/PLA 70/30 blend.
the CE presented a dispersed phase in the form of oriented
This decrease probably occurs due to the change in the form of
ellipsoids, which possibly acted as stress concentrator, which
the PLA particles dispersed in the PBAT matrix, from spherical
justifies the decrease of the mechanical properties, as shown
to ellipsoid phase, that may have acted as a stress concentrator.
previously.
The addition of CE caused an increase in tensile strength,
which is an indicator of the compatibilizer behavior of the
chain extender, as expected. All the samples showed a slight
3.4. Water Contact Angle (WAC)
variation in the melting temperature after the blending,
resulted in the changes in the organization chains. However,
The water contact angle value is used as an indicator of surface
the thermal behavior of the neat PBAT, PLA, and their blends
hydrophilicity or hydrophobicity of polymers, and for PBAT was
did not present significant changes. By the morphological
in the range of 69–73 , depending on the preparation method.[21]
analysis, it can be concluded that the chain extender, in the
Also, according to Smith and Verbeek, the variation in the
content added in this work, was not enough to increase the
contact angle can be justified by the dispersion between the
adhesion between the phases, but significantly altered the
minor phase and major phase.[22] Figure 3 shows the behavior of
dispersion of the PLA phase. After the addition of the CE, neat
the water droplet for the PBAT surfaces and their blends.
PBAT and PLA showed a higher hydrophilicity degree.
Generally, a surface is considered hydrophobic when the
However, in the blends, there is a contrary behavior, with a
WCA is greater than 65 . It is possible to observe that both
higher degree of hydrophobicity. The addition of the chain
PBAT and PLA have a hydrophobic character, and their behavior
extender can either improve the adhesion between the phases
is close to the hydrophilic-hydrophobic transition limit, so, the
or act as a stress concentrator, depending on the proportion of
degree of hydrophobicity is not so high.[21] With the addition of
PLA present in the blend. However, in both PLA concen-
PLA in the PBAT matrix there was a decrease in contact angle,
trations, CE acts in the dispersion of PLA particles.
as long as when PLA content is increased, the WCA increases
too. The results indicate that the hydrophilicity of the PBAT
samples can be tuned by blending with PLA.[23] These results
are due to the variation on the chains length and force field of Acknowledgements
the contacting solid.[24] After CE addition, there was an The authors thank CNPq (n 830094/2008-3, 306401/2013-4, 47180/
inversion in the behavior of neat PBAT and neat PLA, wich 2014-2), REVALORES Strategic Unit, and Multiuser Central Facilities
in both cases, the hydrophilic character growth. For these (UFABC) for the support.
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