Biodegradable poly(L‐lactic acid)/poly(butylene succinate‐co‐adipate) blends: Miscibility,morphology, and thermal behavior

Blends of two biodegradable and semicrystalline polymers, poly(L ‐lactic acid) (PLLA) and poly(butylene succinate‐co‐adipate) (PBSA), were prepared by solvent casting in different compositions. The miscibility, morphology, and thermal behavior of the blends were investigated using differential scanning calorimetry and optical microscopy. PLLA was found to be immiscible with PBSA as evidenced by two independent glass transitions and biphasic melt. Nonisothermal crystallization measurements showed that fractionated crystallization behavior occurred when PBSA was dispersed as droplets, evidenced by multiple crystallization peaks at different supercooling levels. Crystallization and morphology of the blends were also investigated through two‐step isothermal crystallization. For blends where PLLA was the major component, different content of PBSA did not make a significant difference in the crystallization mechanism and rate of PLLA. For blends where PBSA was the major component, the crystallization rate of PBSA decreased with increasing PLLA content, while the crystallization mechanism did not change. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Mechanical and thermal properties of poly(butylene succinate)/poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) biodegradable blends

Biodegradable polymer blends of poly(butylene succinate) (PBS) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) were prepared with different compositions. The mechanical properties of the blends were studied through tensile testing and dynamic mechanical thermal analysis. The dependence of the elastic modulus and strength data on the blend composition was modeled on the basis of the equivalent box model. The fitting parameters indicated complete immiscibility between PBS and PHBV and a moderate adhesion level between them. The immiscibility of the parent phases was also evidenced by scanning electron observation of the prepared blends. The thermal properties of the blends were studied through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The DSC results showed an enhancement of the crystallization behavior of PBS after it was blended with PHBV, whereas the thermal stability of PBS was reduced in the blends, as shown by the TGA thermograms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42815.     

Enhanced mechanical and thermal properties of biodegradable poly(butylene succinate‐co‐adipate)/graphene oxide nanocomposites via in situ polymerization

Poly(butylene succinate‐co‐butylene adipate) (PBSA)/graphene oxide (GO) nanocomposites were synthesized via in situ polymerization for the first time. Atomic force microscopy demonstrated the achievement of a single layer of GO, and transmission electron microscopy proved the homogeneous distribution of GO in the PBSA matrix. Fourier transform infrared spectroscopy results showed the successful grafting of PBSA chains onto GO. With the incorporation of 1 wt % GO, the tensile strength and flexural modulus of the PBSA were enhanced by 50 and 27%, respectively. The thermal properties characterized by differential scanning calorimetry and thermogravimetric analysis showed increases in the melting temperatures, crystallization temperatures, and thermal stability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4075–4080, 2013     

Miscibility and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate)/phenoxy blends

Miscibility and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST)/poly(hydroxyl ether biphenyl A) (phenoxy) blends were investigated with various techniques in this work. PBST and phenoxy are completely miscible as evidenced by the single composition‐dependent glass transition temperature over the entire blend compositions. Nonisothermal melt crystallization peak temperature is higher in neat PBST than in the blends at a given cooling rate. Isothermal melt crystallization kinetics of neat and blended PBST was studied and analyzed by the Avrami equation. The overall crystallization rate of PBST decreases with increasing crystallization temperature and the phenoxy content in the PBST/phenoxy blends; however, the crystallization mechanism of PBST does not change. Moreover, blending with phenoxy does not modify the crystal structure but reduces the crystallinity degree of PBST in the PBST/phenoxy blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of a chain extender on the rheological and mechanical properties of biodegradable poly(lactic acid)/poly[(butylene succinate)‐co‐adipate] blends

Biodegradable polymer blends based on poly(lactic acid) (PLA) and poly[(butylene succinate)‐co‐adipate] (PBSA) were prepared with a laboratory internal mixer. An epoxy‐based, multifunctional chain extender was used to enhance the melt strength of the blends. The morphology of the blends was observed with field emission scanning electron microscopy. The elongational viscosities of the blends, with and without chain extender, were measured with a Sentmanat extensional rheometer universal testing platform. The blends with chain extender exhibited strong strain‐hardening behavior, whereas the blends without chain extender exhibited only weak strain‐hardening behavior. Measurements of the linear viscoelastic properties of the melts suggested that the chain extender promoted the development of chain branching. The results show that PBSA contributed to significant improvements in the ductility of the PLA/PBSA blends, whereas the chain extender did not have a significant effect on the elastic modulus and strain at break of the blends. The combined blending of PLA with PBSA and the incorporation of the chain extender imparted both ductility and melt strength to the system. Thus, such an approach yields a system with enhanced performance and processability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Miscibility and crystallization behavior of biodegradable poly(ε‐caprolactone)/tannic acid blends

Miscibility, isothermal melt crystallization kinetics, spherulitic morphology and growth rates, and crystal structure of completely biodegradable poly(ε‐caprolactone) (PCL)/tannic acid (TA) blends were studied by differential scanning calorimetry, polarized optical microscopy, and wide angle X‐ray diffraction in detail in this work. PCL and TA are miscible as evidenced by the single composition dependent glass transition temperature over the whole compositions range and the depression of equilibrium melting point of PCL in the PCL/TA blends. Isothermal melt crystallization kinetics of neat PCL and an 80/20 PCL/TA blend was investigated and analyzed by the Avrami equation. The overall crystallization rates of PCL decrease with increasing crystallization temperature for both neat PCL and the PCL/TA blend; moreover, the overall crystallization rate of PCL is slower in the PCL/TA blend than in neat PCL at a given crystallization temperature. However, the crystallization mechanism of PCL does not change despite crystallization temperature and the addition of TA. The spherulitic growth rates of PCL also decrease with increasing crystallization temperature for both neat PCL and the PCL/TA blend; moreover, blending with TA reduces the spherulitic growth rate of PCL in the PCL/TA blend. It is also found that the crystal structure of PCL is not modified in the PCL/TA blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical properties of poly(ε‐caprolactone) and poly(lactic acid) blends

The aim of this work was to better understand the performance of binary blends of biodegradable aliphatic polyesters to overcome some limitations of the pure polymers (e.g., brittleness, low stiffness, and low toughness). Binary blends of poly(ε‐caprolactone) (PCL) and poly(lactic acid) (PLA) were prepared by melt blending (in a twin‐screw extruder) followed by injection molding. The compositions ranged from pure biodegradable polymers to 25 wt % increments. Morphological characterization was performed with scanning electron microscopy and differential scanning calorimetry. The initial modulus, stress and strain at yield, strain at break, and impact toughness of the biodegradable polymer blends were investigated. The properties were described by models assuming different interfacial behaviors (e.g., good adhesion and no adhesion between the dissimilar materials). The results indicated that PCL behaved as a polymeric plasticizer to PLA and improved the flexibility and ductility of the blends, giving the blends higher impact toughness. The strain at break was effectively improved by the addition of PCL to PLA, and this was followed by a decrease in the stress at break. The two biodegradable polymers were proved to be immiscible but nevertheless showed some degree of adhesion between the two phases. This was also quantified by the mechanical property prediction models, which, in conjunction with material property characterization, allowed unambiguous detection of the interfacial behavior of the polymer blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Miscibility,crystallization, and mechanical properties of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)/ poly(butylene succinate) blends

Naturally amorphous biopolyester poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P3/4HB) containing 21 mol % of 4HB was blended with semi‐crystal poly(butylene succinate) (PBS) with an aim to improve the properties of aliphatic polyesters. The effect of PBS contents on miscibility, thermal properties, crystallization kinetics, and mechanical property of the blends was evaluated by DSC, TGA, FTIR, wide‐angle X‐ray diffractometer (WAXD), Scanning Electron Microscope (SEM), and universal material testing machine. The thermal stability of P3/4HB was enhanced by blending with PBS. When PBS content is less than 30 wt %, the two polymers show better miscibility and their crystallization trend was enhanced by each other. The optimum mechanical properties were observed at the 5–10 wt % PBS blends. However, when the PBS content is more than 30 wt %, phase inversion happened. And the two polymers give lower miscibility and poor mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Characterization of microstructure and mechanical properties of biodegradable polymer blends of poly(L‐lactic acid) and poly(butylene succinate‐co‐ε‐caprolactone) with lysine triisocyanate

Effect of lysine triisocyanate (LTI) as an additive on the microstructure and the mechanical properties of biodegradable polymer blends of poly(L ‐lactic acid) (PLLA) and poly(butylene succinate‐co‐ε‐caprolactone) (PBSC) were investigated by using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), field‐emission scanning electron microscope (FE‐SEM), and bending and mode I fracture testing techniques. It was found that the addition of LTI dramatically improves the phase‐separation morphology of the PLLA/PBSC blends. FTIR analysis suggested that the NCO groups of LTI were acted as compatibilizer by attributing secondary process between the two polymers PLLA and PBSC, resulting lower peak intensity of ACI samples, understood as secondary process is polar interaction and hydrophobic process. DSC and FE‐SEM results also supported such improvement of immiscibility between PLLA and PBSC. Macroscopic mechanical properties such as the bending fracture energy and the mode I fracture properties are also effectively improved by the LTI addition. Void formation is suppressed due to such morphological change in PLLA/PBSC/LTI blends, and, as a result, energy dissipation in the notch‐tip region of the blends becomes higher than in that of PLLA/PBSC where localized stress concentration due to voids tends to accelerate fracture initiation and, therefore, lowers the fracture energy. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Thermal degradation of ternary blends of poly(ε‐caprolactone)/poly(vinyl acetate)/poly(vinyl chloride)

The thermal degradation of ternary blends of poly(ε‐caprolactone) (PCL), poly(vinyl acetate) (PVAC), and poly(vinyl chloride) (PVC) was studied using a thermogravimetry analyzer under dynamic heating in flowing nitrogen atmosphere. PCL degraded in a single stage, whereas the PVAC and PVC degraded in two stages during which acid is released in the first stage followed by backbone breakage in the second stage. The addition of PVC to either PCL or PVAC affected the thermal stability of the blend, whereas the addition of PVAC to PCL did not alter the thermal stability of the blend. In ternary blends, the addition of PVC affected the degradation of PVAC but did not influence the degradation of PCL in the range investigated. The increased addition of PCL to the binary blends of PVC/PVAC decreased the extent of thermal instability of PVAC because of the addition of PVC. The addition of even 10% PVAC to the PCL/PVC blend removed the thermal instability of PCL resulting from the addition of PVC and can be attributed to the ease of chlorine or hydrogen chloride capture of PVAC over PCL. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1378–1383, 2004     

Toward environment‐friendly composites of poly(ε‐caprolactone) reinforced with stereocomplex‐type poly(l‐lactide)/poly(d‐lactide)

In this work, stereocomplex‐poly(l ‐ and d ‐lactide) (sc‐PLA) was incorporated into poly(ε‐caprolactone) (PCL) to fabricate a novel biodegradable polymer composite. PCL/sc‐PLA composites were prepared by solution casting at sc‐PLA loadings of 5–30 wt %. Differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD) demonstrated the formation of the stereocomplex in the blends. DSC and WAXD curves also indicated that the addition of sc‐PLA did not alter the crystal structure of PCL. Rheology and mechanical properties of neat PCL and the PCL/sc‐PLA composites were investigated in detail. Rheological measurements indicated that the composites exhibited evident solid‐like response in the low frequency region as the sc‐PLA loadings reached up to 20 wt %. Moreover, the long‐range motion of PCL chains was highly restrained. Dynamic mechanical analysis showed that the storage modulus (E′) of PCL in the composites was improved and the glass transition temperature values were hardly changed after the addition of sc‐PLA. Tensile tests showed that the Young's modulus, and yield strength of the composites were enhanced by the addition of sc‐PLA while the tensile strength and elongation at break were reduced. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40208.     

Crystallization and melting behavior of biodegradable poly(ethylene succinate‐co‐6 mol % butylene succinate)

The crystallization, melting behavior, and spherulitic growth kinetics of biodegradable poly(ethylene succinate‐co‐6 mol % butylene succinate) [P(ES‐co‐6 mol % BS)] were investigated and compared with those of the homopolymer poly(ethylene succinate) (PES) in this work. The crystal structure of P(ES‐co‐6 mol % BS) was the same as that of neat PES, but the crystallinity decreased slightly because of the incorporation of the butylene succinate content. The glass‐transition temperature decreased slightly for P(ES‐co‐6 mol % BS) compared to that for neat PES. The melting point of P(ES‐co‐6 mol % BS) decreased apparently; moreover, the equilibrium melting point was also reduced. Two melting endotherms were found for P(ES‐co‐6 mol % BS) after isothermal crystallization; this was ascribed to the melting, recrystallization, and remelting mechanism. The spherulitic growth rate of P(ES‐co‐6 mol % BS) was slower than that of neat PES at a given crystallization temperature. Both neat PES and P(ES‐co‐6 mol % BS) exhibited a crystallization regime II to III transition; moreover, the crystallization regime transition temperature of P(ES‐co‐6 mol % BS) shifted to a low temperature compared with that of neat PES. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Influence of LiClO4 on the thermal,mechanical, and morphological properties of P(DMS‐co‐EO)/ P(EPI‐co‐EO) blends

The UV‐vis absorption, thermal analysis, ionic conductivity, mechanical properties, and morphology of a blend of poly(dimethylsiloxane‐co‐ethylene oxide) [P(DMS‐co‐EO)] and poly(epichlorohydrin‐co‐ethylene oxide) [P(EPI‐co‐EO)] (P(DMS‐co‐EO)/P(EPI‐co‐EO) ratio of 15/85 wt %) with different concentrations of LiClO₄ were studied. The maximum ionic conductivity (σ = 1.2 × 10^?4 S cm^?1) for the blend was obtained in the presence of 6% wt LiClO₄. The crystalline phase of the blend disappeared with increasing salt concentration, whereas the glass transition temperature (T_g) progressively increased. UV‐vis absorption spectra for the blends with LiClO₄ showed a transparent polymer electrolyte in the visible region. The addition of lithium salt decreased the tensile strength and elongation at break and increased Young's modulus of the blends. Scanning electron microscopy showed separation of the phases between P(DMS‐co‐EO) and P(EPI‐co‐EO), and the presence of LiClO₄ made the blends more susceptible to cracking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1230–1235, 2004     

The role of polycarbonate molecular weight in the poly(L‐lactide) blends compatibilized with poly(butylene succinate‐co‐L‐lactate)

Poly(butylene succinate‐co‐L ‐lactate) (PBSL)–compatibilized poly(L ‐lactide) (PLLA) polymer blends with two commercial grades of polycarbonate (PC) were investigated. The capillary tests showed that the steady shear viscosity of high molecular weight PC (PC‐L) was 10 times higher than that of low molecular weight PC (PC‐AD) throughout the shear rate range under investigation. Morphologic examination revealed that the shape of the dispersed PC‐L phase in the as‐extruded blends was largely spherical, but the PC‐AD phase was more like a rod and elongated further during injection molding. Notched Izod impact strength (IS) of the unmodified PLLA/PC‐L blend was higher than that of PC‐AD blend. The IS of modified ternary blends increased with PBSL content because of enhanced phase interaction indicated from thermal and morphologic analysis. The PBSL modification also enhanced IS more significantly in PLLA/PC‐L than in PLLA/PC‐AD blends. On the contrary, the heat deflection temperature (HDT) of PLLA/PC‐L binary system was much lower than that of PLLA/PC‐AD. HDT of PBSL‐modified PLLA/PC‐AD blends dropped with increasing PBSL content, which is a ductile polymer. Thermal and dynamic mechanical analysis of the ternary blends showed that individual components were immiscible with distinct T_gs for PC and PLLA and distinct T_ms for PBSL and PLLA. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Barrier and mechanical properties of biodegradable poly(ε‐caprolactone)/cellophane multilayer film

In this study, cellophane (PT) multilayer films were prepared by coating with different thickness of poly(ε‐caprolactone) (PCL) and chitosan (CH), and its effects on barrier and mechanical properties were evaluated. It was shown that the PCL/PT/PCL and PCL/CH/PT/CH/PCL multilayer films exhibit much better water vapor barrier than PT, and these films still keep the high oxygen barrier. And the barrier properties of multilayer film were improved with the increase of the thickness of coating materials. The Young's modulus and tensile strength of PT multilayer film were slightly decreased, and their elongations at break were increased by coating. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1805–1811, 2013     

Crystallization behavior and mechanical properties of poly(ε‐caprolactone)/cyclodextrin biodegradable composites

The poly(ε‐caprolactone) (PCL)/α‐cyclodextrin (α‐CD) inclusion complex (PCLIC) was successfully prepared, and its effect on the thermal behavior and mechanical properties of PCL was thoroughly studied. It is shown that the addition of PCLIC greatly increased the crystallization rate and thermal stability of the PCL. The Young's modulus and yield strength of PCL/PCLIC composite are about 2 and 1.3 times of the pure PCL, and the elongation at break of the PCL/PCLIC composites kept above 350%, when the PCLIC composition is 15 wt %. It is shown that PCLIC is a good enforcing biofiller for the PCL. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Disclosing the crystallization behavior and morphology of poly(ϵ‐caprolactone) within poly(ϵ‐caprolactone)/poly(l‐lactide) blends

In this work, the effect of poly(l ‐lactide) (PLLA) components on the crystallization behavior and morphology of poly(?‐caprolactone) (PCL) within PCL/PLLA blends was investigated by polarized optical microscopy, DSC, SEM and AFM. Morphological results reveal that PCL forms banded spherulites in PCL/PLLA blends because the interaction between the two polymer components facilitates twisting of the PCL lamellae. Additionally, the average band spacing of PCL spherulites monotonically decreases with increasing PLLA content. With regard to the crystallization behaviors of PCL, the crystallization ability of PCL is depressed with increase of the PLLA content. However, it is interesting to observe that the growth rate of PCL spherulites is almost independent of the PLLA content while the overall isothermal crystallization rate of PCL within PCL/PLLA blends decreases first and then increases at a given crystallization temperature, indicating that the addition of PLLA components shows a weak effect on the growth rate of the PCL but mainly on the generation of nuclei. © 2018 Society of Chemical Industry     

Synthesis and characterization of poly(L‐lactide‐co‐ϵ‐caprolactone)‐b‐poly(L‐lactide) biodegradable diblock copolyesters: Effect of the block lengths on their thermal properties

Poly(L ‐lactide‐co‐ε‐caprolactone)‐b‐poly(L ‐lactide) [P(LL‐co‐CL)‐b‐PLL] diblock copolyesters were synthesized in a two‐step process with 1‐dodecanol (DDC) and stannous octoate as the initiating system. In the first‐step reaction, a 50:50 mol % amorphous poly(L ‐lactide‐co‐ε‐caprolactone) [P(LL‐co‐CL)] copolyester was synthesized via the bulk copolymerization of L ‐lactide and ε‐caprolactone, which was followed by the polymerization of the PLL crystalline block at the end chain in the second‐step reaction. The yielded copolyesters were characterized with dilute‐solution viscometry, gel permeation chromatography, ¹H‐ and ¹³C‐NMR, and differential scanning calorimetry methods. The molecular weights of the P(LL‐co‐CL) copolyesters from the first‐step reaction were controlled by the DDC concentrations, whereas in the second‐step reaction, the molecular weights of the P(LL‐co‐CL)‐b‐PLL diblock copolyesters depended on the starting P(LL‐co‐CL) copolyester molecular weights and L ‐lactide/prepolymer molar ratios. The starting P(LL‐co‐CL) copolyester molecular weights and PLL block lengths seemed to be the main factors affecting specific thermal properties, including the melting temperature (T_m), heat of melting (ΔH_m), crystallizing temperature (T_c), and heat of crystallizing (ΔH_c), of the final P(LL‐co‐CL)‐b‐PLL diblock copolyester products. T_m, ΔH_m, T_c, and ΔH_c increased when the PLL block lengths increased. However, these thermal properties of the diblock copolyesters also decreased when the P(LL‐co‐CL) block lengths increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007