Rheological and mechanical behavior of non-spherical poly(lactic acid) particles embedded poly(butylene adipate-co-terephthalate) blend

In this study, the poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate)(PBAT) blend is investigated to improve rheological and mechanical performances of PBAT based on rheological, mechanical, and thermal behavior analyses. The multi-step mixing method is developed to fabricate the blend with non-spherical morphology. In the multi-step mixing method, blends with a wide composition range (25/75–75/25) are mixed with additional PBAT at a mixing temperature between the melting temperatures of PBAT and PLA to produce the PBAT blend embedded with non-spherical PLA particles (10 wt%). The embedding of non-spherical PLA particles in PBAT increases the resistance against deformation, resulting in strain hardening behavior and an increase in the yield strength as well as the tear resistance of the PBAT. The presence of stiff PLA particles enhances the crystallization behavior of PBAT, meaning that polymer chains may interpenetrate. The findings of this study suggest that the multi-step mixing method is beneficial for embedding non-spherical PLA particles into a PBAT matrix, which in turn facilitates the maintenance of good interfacial adhesion to increase the melt strength, yield strength, and tear resistance.     

Synergistic reinforcing of poly(lactic acid) by poly(butylene adipate-co-terephthalate) and alumina nanoparticles

Biodegradable poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blends and PLA/PBAT/Al₂O₃ nanocomposites were fabricated via solution blending. The influence of PBAT and Al₂O₃ content on the thermal stability, flexural properties, impact strength, and morphology of both the PLA/PBAT blends and the PLA/PBAT/Al₂O₃ nanocomposites were investigated. The impact strength of the PLA/PBAT/Al₂O₃ nanocomposites containing 5 wt% PBAT increased from 4.3 to 5.2 kJ/m² when the Al₂O₃ content increased from 0 to 1 wt%. This represents a 62% increase compared to the impact strength of pristine PLA and a 20% increase compared to the impact strength of PLA/PBAT blends containing 5 wt% PBAT. Scanning electron microscopy imaging revealed that the Al₂O₃ nanoparticles in the PLA/PBAT/Al₂O₃ nanocomposites function as a compatibilizer to improve the interfacial interaction between the PBAT and the PLA matrix.     

A study of poly vinyl chloride / poly(butylene adipate-co-terephthalate) blends

Polymer blends were prepared by melt blending technique using poly vinyl chloride (PVC) and poly(butylene adipate-co-terephthalate) (PBAT). Different ratios of the blends were studied to investigate their mechanical, thermal and morphological properties. The FTIR spectrum indicated a slight increase of frequencies at C = O peak from 1714 to 1718 cm^-1 indicating a chemical interaction between C = O of PBAT and α-hydrogen of PVC. The tensile properties of PVC/PBAT blends highest at weight ratio of 50/50. The dynamic mechanical analysis (DMA) result proves that PVC and PBAT formed a miscible system with one glass transition temperature (T_g). The incorporation of PBAT results in a gradual decrease of the viscosity (loss modulus) and an increase of elasticity (storage modulus). The thermal properties of blend show the decomposition temperature of PVC in the blend decrease with the addition of PBAT. Scanning electron micrograph shows good interfacial adhesion on the tensile fractured surface of PVC/PBAT blend, which played important roles in enhancing the mechanical properties (strength and modulus).     

Compatible and crystallization properties of poly(lactic acid)/poly(butylene adipate‐co‐terephthalate) blends

Differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD) and dynamic mechanical analysis (DMA) properties of poly(lactic acid)/ poly(butylene adipate‐co‐terephthalate) (PLA/PBAT) specimens suggest that only small amounts of poor PLA and/or PBAT crystals are present in their corresponding melt crystallized specimens. In fact, the percentage crystallinity, peak melting temperature and onset re‐crystallization temperature values of PLA/PBAT specimens reduce gradually as their PBAT contents increase. However, the glass transition temperatures of PLA molecules found by DSC and DMA analysis reduce to the minimum value as the PBAT contents of PLA_xPBAT_y specimens reach 2.5 wt %. Further morphological and DMA analysis of PLA/PBAT specimens reveal that PBAT molecules are miscible with PLA molecules at PBAT contents equal to or less than 2.5 wt %, since no distinguished phase‐separated PBAT droplets and tan δ transitions were found on fracture surfaces and tan δ curves of PLA/PBAT specimens, respectively. In contrast to PLA, the PBAT specimen exhibits highly deformable properties. After blending proper amounts of PBAT in PLA, the inherent brittle deformation behavior of PLA was successfully improved. Possible reasons accounting for these interesting crystallization, compatible and tensile properties of PLA/PBAT specimens are proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterization of extruded films based on poly (butylene succinate) blends to utilize a partially degraded poly (butylene adipate-co-terephthalate)

Polymer blends can improve material processability and can be used to extrude partially degraded materials, such as expired poly (butylene adipate-co-terephthalate) (PBAT), which cannot be normally extruded. Therefore, in this study, the extrudability of PBAT that has passed its expiration date was restored by blending it with poly (butylene succinate) (PBS). Various polymer blends were extruded and characterized to achieve high-efficiency extrusion. The carbonyl indices in partially degraded PBAT and the corresponding control sample detailed the effects of 98 months of aging on molecular properties. The semicrystalline structure consisted of a mixed ordered arrangement of PBS and PBAT chains dispersed in an amorphous matrix. The microscopic images of the surfaces of the polymer films revealed defects and roughness, followed by an increase in the PBAT concentration in blends. Changes in mechanical properties and water vapor permeability correlated with the PBAT concentration in the blends. To avoid polymer loss, we reported a simple method for using PBAT that has passed its expiration date and cannot be extruded. The results revealed that the polymer films could be used in the packaging industry, especially in food and agricultural sectors.     

Structure development and properties of high-speed melt spun poly(butylene terephthalate)/poly(butylene adipate-co-terephthalate) bicomponent fibers

Ultra-high-speed bicomponent spinning of poly(butylene terephthalate) (PBT) as sheath and biodegradable poly(butylene adipate-co-terephthalate) (PBAT) as core was accomplished with the take-up velocity up to 10 km/min. The structure development of the individual component and the properties of PBT/PBAT fibers were investigated through the measurements on differential scanning calorimetry, wide-angle X-ray diffraction, birefringence and tensile test. Due to the mutual interaction between two polymer-melts along the spinline, the processability of both components in PBT/PBAT bicomponent spinning was improved compared with those of corresponding single component spinnings. Furthermore, in PBT/PBAT fibers, the structure development of PBT component was found to be greatly enhanced, which led to the improvement in its thermal and mechanical properties; whereas the structure development of PBAT component was significantly suppressed, in which nearly non-oriented structure was observed in both crystalline and amorphous phases.     

Reactable versus soluble DOPO derivatives in poly(lactic acid)/poly(butylene adipate-co-terephthalate) composites: Flame retardance,mechanical properties and morphology

Flame retardant poly(lactic acid)/poly(butylene adipate-co- terephthalate) (PLA/PBAT) composites containing 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide (DOPO) derivatives (phosphorus-containing diol compound of DOPO-HQ, and bis DOPO phosphonates of DIDOPO) were systematically and comparatively investigated. Results showed that the different structures of the two derivatives with reactable or soluble characteristics display different effects. DIDOPO endows a higher limiting oxygen index and a better UL-94 rating for PLA/PBAT composites compared with DOPO-HQ. Compared with that of PLA/PBAT, the peak heat release rate of PLA/PBAT/DIDOPO-12.5 is 8.4% lower and that of PLA/PBAT/DOPO-HQ-12.5 is 30.6% lower. The flame retardant mechanism of the main gaseous and minor condensed phases is evident for the flame retardant PLA/PBAT composites. In comparison, DIDOPO displays a greater flame inhibition effect, and DOPO-HQ shows better barrier and protective functions in PLA/PBAT composites. Besides, the elongation at break of the composites with DOPO-HQ is slightly superior to that of PLA/PBAT/DIDOPO. After the introduction of flame retardant, the blends show dispersed particles with size reduction relative to those of PLA/PBAT. This work provides a guidance to design PLA composites with simultaneously improved flame retardancy and toughness.     

Fabrication of reinforced and toughened poly(lactic acid)/poly(butylene adipate-co-terephthalate) composites through solid die drawing process

In this study, poly(butylene adipate-co-terephthalate) (PBAT) was introduced to poly(lactic acid) (PLA) matrix to improve its inherent poor toughness. Besides, the orientation structure was also introduced via die drawing process to compensate for strength loss. The results indicate that die drawing process contributes to improve the mechanical properties of PLA. The tensile strength, modulus, and elongation at break of die-drawn pure PLA increased by 76.6, 36.1, and 1,375.0%, respectively, compared with those of isotropic PLA. Moreover, the tensile strength can be further improved by the addition of PBAT. The die drawing process can remarkably improve crystallinity, and the orientation factor is high when the PBAT content is less than 30 wt%. By combining the PBAT with highly oriented structure imported by die drawing process, it is possible to prepare simultaneously reinforced and toughened materials, which provides a new insight into the modification of PLA.     

Improved mechanical properties,barrier properties and degradation behavior of poly(butylenes adipate-co-terephthalate)/poly(propylene carbonate) films

Poly(butylene adipate-co-terephthalate) (PBAT) was blended with poly(propylene carbonate) (PPC) by a twin screw extruder and then the blends were made onto films via the blown film technique. PPC dispersed uniformly in the PBAT matrix, and the glass transition temperature (T _g ) of PBAT were decreased with the increasing content of PPC. Wide angle X-ray diffraction confirmed that the crystallite dimension of PBAT was decreased after blending PBAT with the amorphous PPC. The results of mechanical tests indicated that the PBAT/PPC films showed high tensile strength and tear strength. In addition, the PBAT/PPC films showed high carbon dioxide permeability and moderate oxygen and nitrogen permeability. After embedding in soil, the weight loss and mechanical properties analysis demonstrated that the films were remarkably biodegraded. These findings contributed to application of the biodegradable materials, such as design and manufacture polymer packaging.     

Mechanical properties and morphological changes of poly(lactic acid)/polycarbonate/poly(butylene adipate‐co‐terephthalate) blend through reactive processing

The mechanical properties and morphological changes of poly(lactic acid) (PLA), polycarbonate (PC), and poly(butylene adipate‐co‐terephthalate) (PBAT) polymer blends were investigated. Several types of blend samples were prepared by reactive processing (RP) with a twin‐screw extruder using dicumyl peroxide (DCP) as a radical initiator. Dynamic mechanical analyses (DMA) of binary polymer blends of PC/PBAT indicated that each component was miscible over a wide range of PC/PBAT mixing ratios. DMA of PLA/PBAT/PC ternary blends revealed that PBAT is miscible with PC even in the case of ternary blend system and the miscibility of PLA and PBAT can also be modified through RP. As a result, the tensile strain and impact strength of the ternary blends was increased considerably through RP, especially for PLA/PBAT/PC = 42/18/40 (wt/wt/wt) with DCP (0.3 phr). Scanning electron microscopy (SEM) analysis of the PLA/PBAT/PC blends revealed many small spherical island phases with a domain size of approximately 0.05–1 μm for RP, whereas it was approximately 10 μm without RP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Molecular interactions in poly(methacrylic acid)/poly(N‐isopropyl acrylamide) interpenetrating polymer networks

The molecular interactions between the component networks in poly(methacrylic acid)/poly(N‐isopropyl acrylamide) (PMAA/PNIPAAm) interpenetrating polymer networks (IPNs) were investigated using attenuated total reflectance (ATR)‐Fourier transform IR (FTIR) spectroscopy. Hydrogen‐bond formation was noted between the carboxyl groups of PMAA and the amide groups of PNIPAAm. The ATR‐FTIR results showed shifts in the carboxylic and amide groups, indicating the existence of hydrogen bonding between these two individual networks within the IPNs. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1077–1082, 2001     

Crystallization behavior of fully biodegradable poly(lactic acid)/poly(butylene adipate‐co‐terephthalate) blends

Both poly(lactic acid) (PLA) and poly(butylene adipate‐co‐terephthalate) (PBAT) are fully biodegradable polyesters. The disadvantages of poor mechanical properties of PLA limit its wide application. Fully biodegradable polymer blends were prepared by blending PLA with PBAT. Crystallization behavior of neat and blended PLA was investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and wide angle X‐ray diffraction (WAXD). Experiment results indicated that in comparison with neat PLA, the degree of crystallinity of PLA in various blends all markedly was increased, and the crystallization mechanism almost did not change. The equilibrium melting point of PLA initially decreased with the increase of PBAT content and then increased when PBAT content in the blends was 60 wt % compared to neat PLA. In the case of the isothermal crystallization of neat PLA and its blends at the temperature range of 123–142°C, neat PLA and its blends exhibited bell shape curves for the growth rates, and the maximum crystallization rate of neat PLA and its blends all depended on crystallization temperature and their component. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of poly(butylene adipate‐co‐terephthalate) and ultrafined wollastonite on the physical properties and crystallization of recycled poly(ethylene terephthalate)

Recycled poly(ethylene terephthalate) (rPET), obtained mainly from postconsumer bottles, was melt‐mixed with either poly(butylene adipate‐co‐terephthalate) (PBAT) or PBAT plus ultrafine wollastonite (～5 μm) at different weight ratios on a twin‐screw extruder and then injection‐molded. Among the five rPET/PBAT blends (10–50 wt% PBAT) evaluated, the 80/20 wt% rPET/PBAT blend exhibited the highest tensile strength and degree of crystallinity, a slight increase in the tensile strain, and a remarkable increase in the melt flow index, but a lower tensile modulus and thermal stability with respect to the neat rPET. This blend was subsequently filled with four loading levels of wollastonite (10–40 wt%), where the tensile properties (modulus, strain at break, and strength) and thermal stability of the blend were all improved by the addition of wollastonite in a dose‐dependent manner. Based on differential scanning calorimetry analysis, the crystallinity of rPET in the rPET/PBAT/wollastonite composites decreased in the presence of wollastonite, accompanied with a noticeable increase in the glass transition, cold crystallization, and crystallization temperatures, but only a slight change in the melting temperature was noted compared with those of the neat 80/20 wt% blend. Moreover, the addition of wollastonite at 30 wt% or higher showed a strong reduction in the melt dripping of the composites during combustion. J. VINYL ADDIT. TECHNOL., 23:106–116, 2017. © 2015 Society of Plastics Engineers     

Drug releasing characteristics of thermo- and pH-sensitive interpenetrating polymer networks based on poly (N-isopropylacrylamide)

Interpenetrating polymer networks (IPNs) of poly(N-isopropylacrylamide)/polyurethane (PNIPAAm/PU) and poly(N-isopropylacrylamide)/poly(acrylic acid) (PNIPAAm/PAA) were synthesized to investigate the swelling and drug releasing behavior. The presence of urethane network in PNIPAAm/PU IPNs improved the mechanical strength, but reduced the swelling and drug releasing rates because of its hydrophobic characteristics. The swelling transition temperatures of PNIPAAm gels were little affected by the incorporation of PU networks in IPN structures. The drug releasing process was analyzed with a simple exponential expression of time dependent fractional drug release. The swelling and drug releasing behavior of PNIPAAm/PAa IPNs was significantly affected by the variation of PAA compositions. The drug release process changed from anomalous to dual type via zero-order mode with increasing PAA concentration due to the competitive swelling rates between PNIPAAm and PAA during release process. The releasing rate decreased in the buffer solution of pH 7.4, but increased in that of pH 5.0 with increasing PAA concentration at both 28 and 37°C because the swelling power of PAA in pH 5.0 was much less than that in pH 7.4. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2647–2655, 1997     

Influence of phthalic anhydride and bioxazoline on the mechanical and morphological properties of biodegradable poly(lactic acid)/poly[(butylene adipate)‐co‐terephthalate] blends

Poly(lactic acid) (PLA)/poly[(butylene adipate)‐co‐terephthalate] (PBAT) blends were fabricated by melt blending, with 2,2′‐(1,3‐phenylene)bis(2‐oxazoline) (BOZ) and phthalic anhydride (PA) used as compatibilizers. It was found that a small amount of BOZ or PA greatly increased the elongation at break of the PLA/PBAT blends without sacrificing their high tensile strength. Scanning electron microscopy results revealed that the PBAT particles became finer and were uniformly dispersed in the matrix when the compatibilizers were incorporated, which indicated that the interfacial bonding and compatibilization between PLA and PBAT were improved in the presence of the compatibilizers. Compared with PLA/PBAT blends, the molecular weight of PLA/PBAT/PA/BOZ blends was increased due to chain‐extending reactions. Differential scanning calorimetry results suggested PBAT decreased the crystallization rate and crystallinity of PLA in the blends. Moreover, the glass transition temperature of PBAT was further decreased when the compatibilizers were used. © 2013 Society of Chemical Industry     

Effect of chain extrender on the compatibility,mechanical and gas barrier properties of poly(butylene adipate-co-terephthalate)/poly(propylene carbonate) bio-composites

Bio-composites consisting of poly(butylene adipate-co-terephthalate) (PBAT), poly(propylene carbonate) (PPC) and epoxy chain extender ADR 4468 were fabricated via melt blending using a torque rheometer. The relationship of the torque, melt viscosity, and molecular weight of the bio-composites was established via polymeric liquid theory to estimate the real-time chain extension reaction rate under different ADR contents. At the meantime, rheological behavior, thermal and mechanical properties, morphologies, gas barrier properties of the PBAT/PPC/ADR bio-composites were systematically characterized. The corresponding results revealed that the water vapor transmission rate (WVTR) reduced by 50% under 30 phr (parts per hundreds of resin) PPC content. The addition of ADR is beneficial to improve the mechanical properties, thermal stability and phase dispersion of PBAT/PPC without affecting the water barrier property. With 3 phr ADR, the tensile stress and elongation at break were increased from 19.5 MPa and 1184% to 26.9 MPa and 1443%, respectively. In addition, the data of the torque rheometer revealed that the chain extension reaction rate and the melt viscosity was increased with the increasing ADR content, but the reaction rate was reduced with the excessive viscosity.     

Biodegradable blends of poly(butylene adipate-co-terephthalate) and polyglycolic acid with enhanced mechanical,rheological and barrier performances

Blends of poly(butylene adipate-co-terephthalate)/polyglycolic acid (PBAT/PGA) were prepared by melt blending, in which PGA was used as reinforcing component. Impacts of PGA content on tensile property, microstructure, crystallization property, melt viscosity, barrier performance of the blends were researched. Compared with very soft behavior of PBAT, the tensile yield strength and modulus of PBAT/PGA (65/35) sample increased from 7.67, 62.6 MPa of neat PBAT to 12.05, 158.9 MPa, respectively. However, owing to poor PBAT/PGA interface compatibility, its elongation at break decreased significantly from 1082.1% to 88.7%. An epoxy chain extender (ADR) was used as reactive modifier to improve its interface compatibility and rheological property. The related physical properties of PBAT/PGA/ADR (65/35/x) samples with various ADR contents were evaluated in detail. It was found that ADR exerted relatively complex influences on the properties. Overall, compared with neat PBAT and PBAT/PGA (65/35) sample, the PBAT/PGA/ADR (65/35/x) samples exhibited better stiffness-ductility balance and higher processing stability.     

Facile fabrication of highly flexible poly(lactic acid) film using alternate multilayers of poly[(butylene adipate)‐co‐terephthalate]

Poly(lactic acid) (PLA) and poly[(butylene adipate)‐co‐terephthalate] (PBAT) are both commonly used biodegradable polymers. In this study, co‐extrusion of PLA and PBAT was used to create alternately multilayered films in order to obtain high‐flexibility PLA film. The incorporation of PBAT provides enhanced flexibility to PLA and the effect is more distinct in the PLA/PBAT multilayer film as the number of layers increases. Through differential scanning calorimetric and wide‐angle X‐ray scattering analyses, the crystallinity of PLA is shown to decrease more in the multilayer film than in the blended film. Transparency is also enhanced in the multilayer film. The fabrication of alternate multilayered film by co‐extrusion of PLA and PBAT shows a new method of preparing a flexible, transparent and fully biodegradable film, which is impossible through a blending process. © 2014 Society of Chemical Industry     

Study on poly(butylene adipate‐co‐terephthalate)/starch composites with polymeric methylenediphenyl diisocyanate

To lower the cost of poly(butylene adipate‐co‐terephthalate) or PBAT, starch was used as a filler in this study. To increase tensile strength of PBAT/starch composites, polymeric methylenediphenyl diisocyanate (pMDI) was used as a compatibilizer. PBAT was melt‐mixed with starch in a kneader, and then the mixtures were compression‐molded. The effects of starch and pMDI content on the tensile strength and elongation at break of PBAT/starch composites were examined. The morphology and biodegradability of the composites in soil were also studied. The tensile strength of PBAT and PBAT/starch composites increases with increasing content of pMDI. The increase of weight average molecular weight of PBAT and improved interaction between PBAT and starch were observed with increasing content of pMDI. The weight average molecular weights of buried PBAT and the composites in soil significantly decrease. Especially, the reduction of the weight average molecular weight of PBAT/starch (70/30) composite is the most significant. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41884.     

Biodegradation of poly(butylene adipate‐co‐butylene terephthalate)/layered‐silicate nanocomposites

The biodegradability of poly(butylene adipate‐co‐butylene terephthalate) (PBAT) and PBAT/starch composites with layered silicates prepared by melt intercalation was evaluated with aerobic biodegradability tests in soil and in an aqueous medium containing activated sludge. Nonmodified montmorillonite (MMT) and octadecylamine‐modified montmorillonite (ODA‐M), known to give a microcomposite and an intercalated nanocomposite for PBAT, respectively, were used as layered silicates. After they were buried in the soil for 8 months, the PBAT/MMT microcomposite exhibited a higher weight loss than the control PBAT, whereas the PBAT/ODA‐M nanocomposite showed a lower weight loss instead. Also, the biodegradability test in the aqueous medium, by determining the biochemical oxygen demand, showed that the addition of MMT and/or starch to PBAT promoted biodegradation, whereas the addition of ODA‐M did not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007