Aging of poly(lactide)/poly(ethylene glycol) blends. Part 2. Poly(lactide) with high stereoregularity

Blending poly(ethylene glycol) (PEG) with poly(lactide) (PLA) decreases the T_g and improves the mechanical properties. The blends have lower modulus and increased fracture strain compared to PLA. However, the blends become increasingly rigid over time at ambient conditions. Previously, it was demonstrated that a PLA of lower stereoregularity was miscible with up to 30 wt% PEG. Aging was due to slow crystallization of PEG from the homogeneous amorphous blend. Crystallization of PEG depleted the amorphous phase of PEG and gradually increased the T_g until aging essentially ceased when T_g of the amorphous phase reached the aging temperature. In the present study, this aging mechanism was tested with a crystallizable PLA of higher stereoregularity. Changes in thermal transitions, solid state structure, and mechanical properties were examined over time. Blends with up to 20 wt% PEG were miscible. Blends with 30 wt% PEG could be quenched from the melt to the homogenous amorphous glass. However, this composition phase separated at ambient temperature with little or no crystallization. Changes in mechanical properties during phase separation reflected increasing rigidity of the continuous PLA-rich phase as it became richer in PLA. Construction of a phase diagram for blends of higher stereoregular PLA with PEG was attempted.     

Plasticization of semicrystalline poly(l-lactide) with poly(propylene glycol)

Plasticization of semicrystalline poly(l-lactide) (PLA) with a new plasticizer - poly(propylene glycol) (PPG) is described. PLA was plasticized with PPG with nominal M_w of 425 g/mol (PPG4) and 1000 g/mol (PPG1) and crystallized. The plasticization decreased T_g, which was reflected in a lower yield stress and improved elongation at break. The crystallization in the blends was accompanied by a phase separation facilitated by an increase of plasticizer concentration in the amorphous phase and by annealing of blends at crystallization temperature. The ultimate properties of the blends with high plasticizer contents correlated with the acceleration of spherulite growth rate that reflected accumulation of plasticizer in front of growing spherulites causing weakness of interspherulitic boundaries. In PLA/PPG1 blends the phase separation was the most intense leading to the formation of PPG1 droplets, which facilitated plastic deformation of the blends that enabled to achieve the elongation at break of about 90-100% for 10 and 12.5 wt% PPG1 content in spite of relatively high T_g of PLA rich phase of the respective blends, 46.1-47.6 °C. Poly(ethylene glycol) (PEG), long known as a plasticizer for PLA, with nominal M_w of 600 g/mol, was also used to plasticize PLA for comparison.     

Aging of poly(lactide)/poly(ethylene glycol) blends. Part 1. Poly(lactide) with low stereoregularity

Poly(lactide) (PLA) is rapidly gaining interest as a biodegradable thermoplastic for general usage in degradable disposables. To improve mechanical properties, a PLA with low stereoregularity was blended with polyethylene glycol (PEG). Blends with up to 30 wt% PEG were miscible at ambient temperature. Blending with PEG significantly decreased the T_g, decreased the modulus and increased the fracture strain of PLA. However, the PLA/PEG 70/30 blend became increasingly rigid over time at ambient conditions. The mechanism of aging primarily under ambient conditions of temperature and humidity was studied. Changes in mechanical properties, thermal transitions and solid state morphology were examined over time. Aging was caused by slow crystallization of PEG. Crystallization of PEG depleted the amorphous phase of PEG and gradually increased the T_g. As T_g approached the aging temperature, reduced molecular diffusivity slowed the crystallization rate dramatically. Aging essentially ceased when T_g of the amorphous phase reached the aging temperature. The increase in matrix T_g and the reinforcing effect of the crystals produced a change in mechanical properties from elastomer-like to thermoplastic-like.     

Morphology and nonisothermal crystallization of a polyacetal/poly(ε‐caprolactone) reactive blend prepared via a chain‐transfer reaction

A polyacetal (POM)/poly(ε‐caprolactone) (PCL) reactive blend prepared via a chain‐transfer reaction was investigated with respect to its morphology and nonisothermal crystallization, and the results were compared with those of a simple POM/PCL blend. The reactive blend had a microscopically phase‐separated morphology in which the diameter of the PCL microphase was below 100 nm, and it clearly yielded ring‐banded spherulites, whereas between the two blends, there were no significant differences in the diameters and polygonal edges of the spherulites and in the long period of the POM phases. The PCL part of the reactive blend crystallized within the confined microspace with about 10% lower crystallinity than that of the corresponding simple blend. A lower Avrami exponent and crystallization rate parameter of the PCL part were observed in the primary crystallization process of the reactive blend. In contrast, the crystallinity of the POM component and the nonisothermal crystallization kinetic parameters of the POM part showed no noticeable differences between the two blends at any given cooling rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Enhanced crystallization of poly(lactide) stereocomplex by xylan propionate

The effect of xylan propionate (XylPr) as a novel biomass‐derived nucleating agent on the poly(lactide) sterecomplex was investigated. Addition of XylPr to an enantiomeric blend of poly(l ‐lactide) (PLLA) and poly(d ‐lactide) (PDLA) was performed in either the solution state or molten state. The solution blend of PLLA/PDLA with XylPr was prepared by mixing equal volumes of 1 wt% XylPr/PLLA and 1 wt% XylPr/PDLA solutions in chloroform and precipitating in methanol. The solution blend with XylPr showed shorter half‐time crystallization than the solution blend without XylPr in isothermal crystallization between 80 and 140 °C, although homocrystallization occurred. Enhanced stereocomplex crystallization in the solution blend with XylPr was observed at 180 °C, where no crystallization occurred in the solution blend without XylPr. Addition of XylPr to PLLA/PDLA blend in the molten state was performed at 240 °C. Thereafter, the melt blend of PLLA/PDLA with or without XylPr was either quenched in iced water or isothermally crystallized directly from the melt. Isothermal crystallization of the melt‐quenched blend with XylPr gave a similar result to the solution blend with XylPr. In contrast, the melt‐crystallized blend with XylPr formed only stereocomplex crystals after crystallization above 140 °C. Furthermore, the melt‐crystallized blend with XylPr showed a higher crystallinity index and melting temperature than the melt‐crystallized blend without XylPr. This shows that XylPr promotes stereocomplex crystallization only when the blend of PLLA/PDLA with XylPr is directly crystallized from the molten state just after blending. © 2016 Society of Chemical Industry     

聚乙二醇增塑聚乳酸的等温结晶动力学研究

采用DSC方法对聚乙二醇(PEG)增塑聚乳酸的等温结晶动力学进行了研究。结果表明,PEG的加入提高了聚乳酸的结晶速度,在相同结晶温度下,随着PEG摩尔质量的增大,结晶速率增大,结晶活化能先减小后增大。不同摩尔质量PEG增塑PLA的结晶成核机理和生长方式一样。     

Enhancing the PLA Crystallization Rate and Mechanical Properties by Melt Blending with Poly(styrene-butadiene-styrene) Copolymer

Poly(styrene-butadiene-styrene) (SBS) copolymer was used to enhance the crystallization ability and mechanical properties of poly(L-lactic acid) (PLA) through melt mixing. The thermogravimetric analysis and Fourier transform infrared results revealed the n–π interaction between PLA and SBS. Differential scanning calorimetry and X-ray diffraction analysis indicated that the crystallization ability of the PLA improved substantially. The PLA crystallized completely during the cooling process when the SBS content in the blend was above 20 wt.%. The elongation at break and the impact resistance were significantly improved compared with that of neat PLA when the SBS content was above 50 wt.%.     

The effect of poly(ethylene glycol) mixed with poly(l‐lactic acid) on the crystallization characteristics and properties of their blends

The non‐isothermal and isothermal crystallizations of extruded poly(l ‐lactic acid) (PLLA) blends with 10, 20 and 30 wt% poly(ethylene glycol) (PEG) were investigated with differential scanning calorimetry. The formation of α‐form crystals in the blend films was verified using X‐ray diffraction and an increase in crystallinity indexes using Fourier transformation infrared spectroscopy. Crystallization and melting temperatures and crystallinity of PLLA increased with decreasing cooling rate (CR) and showed higher values for the blends. Although PLLA crystallized during both cooling and heating, after incorporation of PEG and with CR = 2 °C min^?1 its crystallization was completed during cooling. Increasingly distinct with CR, a small peak appeared on the lower temperature flank of the PLLA melting curve in the blends. A three‐dimensional nucleation process with increasing contribution from nuclei growth at higher CR was verified from Avrami analysis, whereas Kissinger's method showed that the diluent effect of 10 and 20 wt% PEG in PLLA decreased the effective energy barrier. During isothermal crystallization, crystallization half‐time increased with temperature (T_ic) for the blends, decreased with PEG content and was lower than that of pure PLLA. In addition, the Avrami rate constants were significantly higher than those of pure PLLA, at the lower T_ic. Different crystal morphologies in the PLLA phase were formed, melting in a broader and slightly higher T_m range than pure PLLA. The crystallization activation energy of PLLA decreased by 56% after the addition of 10 wt% PEG, increasing though with PEG content. Finally, PEG/PLLA blends presented improved flexibility and hydrophilicity. © 2019 Society of Chemical Industry     

Crystallization of triethyl-citrate-plasticized poly(lactic acid) induced by chitin nanocrystals

The aim of this study was to gain a better understanding of the crystallization behavior of triethyl-citrate-plasticized poly(lactic acid) (PLA–TEC) in the presence of chitin nanocrystals (ChNCs). The isothermal crystallization behavior of PLA–TEC was studied by polarized optical microscopy, scanning electron microscopy, differential scanning calorimetry, and X-ray diffraction (XRD). Interestingly, the addition of just 1 wt % ChNCs in PLA–TEC increased the crystallization rate in the temperature range of 135–125 °C. The microscopy studies confirmed the presence of at least three distinct types of spherulites: negative, neutral, and ring banded. The ChNCs also increased the degree of crystallinity up to 32%, even at a fast cooling rate of 25 °C min⁻¹. The XRD studies further revealed the nucleation effect induced by the addition of ChNCs and thus explained the faster crystallization rate. To conclude, the addition of a small amount (1 wt %) of ChNC to plasticized PLA significantly affected its nucleation, crystal size, and crystallization speed; therefore, the proposed route can be considered suitable for improving the crystallization behavior of PLA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47936.     

Miscibility, thermal characterization and crystallization of poly(l-lactide) and poly(tetramethylene adipate-co-terephthalate) blend membranes

Binary blend membranes of biodegradable poly(l-lactide) (PLLA) with poly(tetramethylene adipate-co-terephthalate) (PTAT) copolymer were prepared by solution casting via air evaporation. The miscibility of PLLA/PTAT blends was studied by dynamic mechanical analysis (DMA) and thermal mechanical analysis (TMA) in a tensile mode. Differential scanning calorimetry (DSC) measurement was carried out. The surface microstructure and tensile properties of the blend membranes were examined using atomic force microscopy (AFM) and tensile tester. It was concluded that PLLA/PTAT blends should be partially miscible for all ranges of compositions. Higher roughness and porosity were observed for the blend containing 50% PTAT, suggesting more phase separation occurred. The DSC analysis showed that the fusion enthalpy and crystallinity (X_c) of the PLLA-rich phase decreased with increasing PTAT content. Solidification process strongly suggested that the crystallization rate was accelerated by blending with 25% PTAT content, which served as the nucleation agent. Furthermore, the crystallization rate coefficient (CRC) depended on the blending miscibility and cooling rate in the non-isothermal crystallization process. Besides, PTAT addition could be proved to enhance the thermal stability and elongation of resulting blend membranes, even superior to those properties of poly(lactic acid-co-glycolic acid) (PLGA).     

Spherulite nucleation in blends of isotactic polypropylene with isotactic poly(butene-1)

The phase morphology and the influence of composition on the primary nucleation of isotactic polypropylene in isotactic polypropylene/isotactic poly(butene-1) (iPP/iPB) blends were investigated by electron and light microscopy and small-angle light scattering. It was found that iPP and iPB are miscible but the thermal treatment induces partial phase separation of components and the formation of iPP-rich and iPB-rich phases. The complete phase separation needs high temperatures and/or a long time of melt annealing. In samples crystallized isothermally at low undercooling the heterogeneous primary nucleation in blends is depressed as compared to plain iPP. In blends the less active heterogeneities lose their activity because of an increase of the energy barrier for critical size nucleus formation due to phase separation of blend components during crystallization. For the same reason the rate of homogeneous nucleation in blends decreases, as observed in samples crystallized at very high undercooling. At very high undercooling iPP and iPB are able to crystallize with similar rates, which results in the formation of a fraction of iPB spherulites in addition to iPP spherulites. Consequently the number of spherulites in the blend is larger than that in plain iPP, in spite of the decrease in the homogeneous nucleation rate of iPP in the blend. © 1994 John Wiley & Sons, Inc.     

Isothermal crystallization kinetics and spherulite morphologies of poly(lactic acid)/ethylene acrylate copolymer blends

Isothermal crystallization kinetics and spherulite morphologies of partially immiscible blends of poly(lactic acid) (PLA) and ethylene acrylate copolymer (EAC) were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy. The DSC data obtained was analyzed using the Avrami equation. Crystallization kinetics of PLA from the melt was strongly influenced by the blend composition and the crystallization temperature. At a given crystallization temperature, the overall crystallization rate value was greater in the blends than in PLA suggesting that the presence of EAC enhanced crystallization of PLA. Polarized optical micrographs showed that the crystallization of PLA initially took place at the PLA/EAC interface. At high EAC content (>1 wt %), EAC domains acted as hindrance to crystallization reducing the overall crystallization rate of PLA in the blends. Based on the DSC analysis, the crystallization rate was maximum when PLA blend with 1 wt % EAC was isothermally crystallized at 103 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45487.     

Effects of molten poly(3-hydroxybutyrate) on crystalline morphology in stereocomplex of poly(L-lactic acid) with poly(D-lactic acid)

Effects of poly(3-hydroxybutyrate) (PHB) on crystalline morphology of stereocomplexing capacity of poly(L- and D-lactic acid) (PLLA and PDLA) were studied by differential scanning calorimetry (DSC), polarizing-light optical microscopy (POM), atomic-force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). When crystallized at high T_c (130 °C or above), morphology transition of stereocomplexed PLA (sc-PLA) occurs from original well-rounded Maltese-cross spherulites to dendritic form in blends of high PHB contents (50 wt.% or higher), where PHB acts as an amorphous species. Microscopy characterizations show that morphology of sc-PLA in PHB/sc-PLA blends crystallized at T_c = 170 °C no longer retain original complexed Maltese-cross well-rounded spherulites; instead, the spherulites are disintegrated and restructured into two types of dendrites: (1) edge-on feather-like dendrites (early growth) and (2) flat-on wedge-like crystal plates (later growth) by growing along different directions and exhibiting different optical brightness. The concentration and/or distribution of amorphous PHB at the crystal growth front, corresponding to variation of the slopes of spherulitic growth rates, is a factor resulting in alteration and restructuring of the sc-PLA spherulites in the blends. Despite of spherulite disintegration, WAXD result shows that these two PHB-induced dendrites still retain the original unit cells of complexes, and thus these two new dendrites are sc-PLA.     

Effect of poly(propylene carbonate) on the crystallization and melting behavior of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)

The crystallization and melting behavior of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate) (PHBV) and a 30/70 (w/w) PHBV/poly(propylene carbonate) (PPC) blend was investigated with differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR). The transesterification reaction between PHBV and PPC was detected in the melt‐blending process. The interaction between the two macromolecules was confirmed by means of FTIR analysis. During the crystallization process from the melt, the crystallization temperature of the PHBV/PPC blend decreased about 8°C, the melting temperature was depressed by 4°C, and the degree of crystallinity of PHBV in the blend decreased about 9.4%; this was calculated through a comparison of the DSC heating traces for the blend and pure PHBV. These results indicated that imperfect crystals of PHBV formed, crystallization was inhibited, and the crystallization ability of PHBV was weakened in the blend. The equilibrium melting temperatures of PHBV and the 30/70 PHBV/PPC blend isothermally crystallized were 187.1 and 179°C, respectively. The isothermal crystallization kinetics were also studied. The fold surface free energy of the developing crystals of PHBV isothermally crystallized from the melt decreased; however, a depression in the relative degree of crystallization, a reduction of the linear growth rate of the spherulites, and decreases in the equilibrium melting temperature and crystallization capability of PHBV were detected with the addition of PPC. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2514–2521, 2004     

Small-angle X-ray scattering studies on melting and recrystallization behaviors of poly(oxyethylene) crystallites in poly(d,l-lactide)/poly(oxyethylene) blends

Direct determination of the discrete distribution for crystalline lamellar thickness has been performed for poly(d,l-lactic acid)/poly(oxyethylene) (PDLLA/PEG) blends by conducting small-angle X-ray scattering (SAXS) measurements using synchrotron radiation. The PDLLA used was an random (racemic) copolymer of bio-based poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) with the lactide monomer ratio of l:d = 50:50. It is known that PLA is miscible with PEG in the amorphous state. In the current paper, we report comprehensive results on structural analyses of PDLLA/PEG blends in the course of heating and cooling process using SAXS to elucidate the change in the thickness distribution of the lamellae. As a consequence, it was found that the distribution of the lamellar thickness moves toward the larger value (in other words, lamellar thickening) as temperature approaches the melting point. Typically, the thickness distribution was dispersed in the range of 10–20 nm at room temperature and it changed toward 40 nm in the vicinity of the melting temperature. To the best of our knowledge, this is the first report of direct determination of the discrete distribution for the crystalline lamellar thickness and their in-situ changes in the course of the lamellar thickening process. As a result, the lamellar thickening was found to occur at much lower temperature for the blend samples with 10% and 20% of PDLLA contents as compared to the PEG 100% sample. This phenomenon can be ascribed to the melting point depression owing to the miscibility between PEG and PDLLA. Thereby, thinner lamellae were melted and thicker ones appeared at much lower temperature for the blends than for the PEG 100% sample. As for the average repeating distance (long period) of the lamellar stacks, an abrupt increase similar to the critical divergence was observed (from 25 nm to 50 nm) in the heating process. Not only for the melting behavior but also in the course of recrystallization, change in the lamellar-thickness distribution was uncovered, which shows strong hysteresis depending on what temperature the sample was cooled down from.     

Miscibility and crystallization in crystalline/crystalline blends of poly(butylene succinate)/poly(ethylene oxide)

Miscibility and crystallization behavior have been investigated in blends of poly(butylene succinate) (PBSU) and poly(ethylene oxide) (PEO), both semicrystalline polymers, by differential scanning calorimetry and optical microscopy. Experimental results indicate that PBSU is miscible with PEO as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer-polymer interaction parameter, obtained from the melting depression of the high-T_m component PBSU using the Flory-Huggins equation, is composition dependent, and its value is always negative. This indicates that PBSU/PEO blends are thermodynamically miscible in the melt. The morphological study of the isothermal crystallization at 95 °C (where only PBSU crystallized) showed the similar crystallization behavior as in amorphous/crystalline blends. Much more attention has been paid to the crystallization and morphology of the low-T_m component PEO, which was studied through both one-step and two-step crystallization. It was found that the crystallization of PEO was affected clearly by the presence of the crystals of PBSU formed through different crystallization processes. The two components crystallized sequentially not simultaneously when the blends were quenched from the melt directly to 50 °C (one-step crystallization), and the PEO spherulites crystallized within the matrix of the crystals of the preexisted PBSU phase. Crystallization at 95 °C followed by quenching to 50 °C (two-step crystallization) also showed the similar crystallization behavior as in one-step crystallization. However, the radial growth rate of the PEO spherulites was reduced significantly in two-step crystallization than in one-step crystallization.     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and poly(DL-lactide)-co-poly(ethylene glycol)

The melting and crystallization behavior and phase morphology of poly(3-hydroxybutyrate) (PHB) and poly(DL-lactide)-co-poly(ethylene glycol) (PELA) blends were studied by DSC, SEM, and polarizing optical microscopy. The melting temperatures of PHB in the blends showed a slight shift, and the melting enthalpy of the blends decreased linearly with the increase of PELA content. The glass transition temperatures of PHB/PELA (60/40), (40/60), and (20/80) blends were found at about 30°C, close to that of the pure PELA component, during DSC heating runs for the original samples and samples after cooling from the melt at a rate of 20°C/min. After a DSC cooling run at a rate of 100°C/min, the blends showed glass transitions in the range of 10–30°C. Uniform distribution of two phases in the blends was observed by SEM. The crystallization of PHB in the blends from both the melt and the glassy state was affected by the PELA component. When crystallized from the melt during the DSC nonisothermal crystallization run at a rate of 20°C/min, the temperatures of crystallization decreased with the increase of PELA content. Compared with pure PHB, the cold crystallization peaks of PHB in the blends shifted to higher temperatures. Well-defined spherulites of PHB were found in both pure PHB and the blends with PHB content of 80 or 60%. The growth of spherulites of PHB in the blends was affected significantly by 60% PELA content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1849–1856, 1997     

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     

Unique isothermal crystallization phenomenon in the ternary blends of biopolymers polylactide and poly[(butylene succinate)-co-adipate] and nano-clay

Melt and cold isothermal crystallization studies were carried out on polylactide (PLA)/poly[butylene succinate)-co-adipate] (PBSA) neat blend and blend-clay composites. The neat blend and blend-clay composites were prepared by melt-blending in a batch mixer. The weight ratio of PLA to PBSA was fixed at 70:30, while the content of the organoclay was varied from 0 to 9 wt%. The spherulitic growth rates and morphologies of PLA and PBSA in the samples were examined through polarized optical microscopy, while the rate of crystallization and the extent of crystallinity were studied through differential scanning calorimetry. The kinetics of melt and cold crystallization of PLA were adequately described by the Avrami model. There was a strong dependence of the rate of crystallization and extent of crystallinity of PLA on the extent of clay loading and flow induced morphology. For composites with 2 and 6 wt% clay loading, uniquely slower crystallization occurred. A qualitative relationship between phase morphology and crystallization, as affected by clay loading, is therefore described.