Phase behavior and morphology in blends of poly(L‐lactic acid) and poly(butylene succinate)

Blends of poly(L ‐lactic acid) (PLA) and poly(butylene succinate) (PBS) were prepared with various compositions by a melt‐mixing method and the phase behavior, miscibility, and morphology were investigated using differential scanning calorimetry, wide‐angle X‐ray diffraction, small‐angle X‐ray scattering techniques, and polarized optical microscopy. The blend system exhibited a single glass transition over the entire composition range and its temperature decreased with an increasing weight fraction of the PBS component, but this depression was not significantly large. The DSC thermograms showed two distinct melting peaks over the entire composition range, indicating that these materials was classified as semicrystalline/semicrystalline blends. A depression of the equilibrium melting point of the PLA component was observed and the interaction parameter between PLA and PBS showed a negative value of ?0.15, which was derived using the Flory–Huggins equation. Small‐angle X‐ray scattering revealed that, in the blend system, the PBS component was expelled out of the interlamellar regions of PLA, which led to a significant decrease of a long‐period, amorphous layer thickness of PLA. For more than a 40% PBS content, significant crystallization‐induced phase separation was observed by polarized optical microscopy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 647–655, 2002     

An investigation of melt rheology and thermal stability of poly(lactic acid)/ poly(butylene succinate) nanocomposites

A systematic investigation of the rheological and thermal properties of nanocomposites prepared with poly(lactic acid) (PLA), poly(butylene succinate) (PBS), and organically modified layered silicate was carried out. PLA/PBS/Cloisite 30BX (organically modified MMT) clay nanocomposites were prepared by using simple melt extrusion process. Composition of PLA and PBS polymers were fixed at a ratio of 80 to 20 by wt % for all the nanocomposites. Rheological investigations showed that high clay (> 3 wt %) contents strongly improved the viscoelastic behavior of the nanocomposites. Percolation threshold region was attained between 3 and 5 wt % of clay loadings. With the addition of clay content for these nanocomposites, liquid‐like behavior of PLA/PBS blend gradually changed to solid‐like behavior as shown by dynamic rheology. Steady shear showed that shear viscosity for the nanocomposites decreased with increasing shear rates, exhibiting shear‐thinning non‐Newtonian behavior. At higher clay concentrations, pseudo‐plastic behavior was dominant, whereas pure blend showed almost Newtonian behavior. Thermogravimetric analysis revealed that both initial degradation temperature (at a 2% weight loss) and activation energy of thermal decomposition nanocomposite containing 3 wt % of C30BX were superior to those of other nanocomposites as well as to those of PLA/PBS blend. Nanocomposite having 1 wt % of C30BX did not achieve expected level of thermal stability due to the thermal instability of the surfactant present in the organoclay. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

DSC and TMDSC study of melting behaviour of poly(butylene succinate) and poly(ethylene succinate)

The subsequent melting behaviour of poly(butylene succinate) (PBSU) and poly(ethylene succinate) (PES) was investigated using DSC and temperature modulated DSC (TMDSC) after they finished nonisothermal crystallization from the melt. PBSU exhibited two melting endotherms in the DSC traces upon heating to the melt, which was ascribed to the melting and recrystallization mechanism. However, one melting endotherm with one shoulder and one crystallization exotherm just prior to the melting endotherm were found for PES. The crystallization exotherm was ascribed to the recrystallization of the melt of the crystallites with low thermal stability, and the shoulder was considered to be the melting endotherm of the crystallites with high thermal stability. The final melting endotherm was ascribed to the melting of the crystallites formed through the reorganization of the crystallites with high thermal stability during the DSC heating process. TMDSC experiments gave the direct evidences to support the proposed models to explain the melting behaviour of PBSU and PES crystallized nonisothermally from the melt.     

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.     

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.     

Poly(hydroxybutyrate)/poly(butylene succinate) blends: miscibility and nonisothermal crystallization

Four blends of poly(hydroxybutyrate) (PHB) and poly(butylene succinate) (PBSU), both biodegradable semicrystalline polyesters, were prepared with the ratio of PHB/PBSU ranging from 80/20 to 20/80 by co-dissolving the two polyesters in N,N-dimethylformamide and casting the mixture. Differential scanning calorimetry (DSC) and optical microscopy (OM) were used to probe the miscibility of PHB/PBSU blends. Experimental results indicated that PHB showed some limited miscibility with PBSU for PHB/PBSU 20/80 blend as evidenced by the small change in the glass transition temperature and the depression of the equilibrium melting point temperature of the high melting point component PHB. However, PHB showed immiscibility with PBSU for the other three blends as shown by the existence of unchanged composition independent glass transition temperature and the biphasic melt. Nonisothermal crystallization of PHB/PBSU blends was investigated by DSC using various cooling rates from 2.5 to 10 °C/min. During the nonisothermal crystallization, despite the cooling rates used two crystallization peak temperatures were found for PHB/PBSU 40/60 and 60/40 blends, corresponding to the crystallization of PHB and PBSU, respectively, whereas only one crystallization peak temperature was observed for PHB/PBSU 80/20 and 20/80 blends. However, it was found that after the nonisothermal crystallization the crystals of PHB and PBSU actually co-existed in PHB/PBSU 80/20 and 20/80 blends from the two melting endotherms observed in the subsequent DSC melting traces, corresponding to the melting of PHB and PBSU crystals, respectively. The subsequent melting behavior was also studied after the nonisothermal crystallization. In some cases, double melting behavior was found for both PHB and PBSU, which was influenced by the cooling rates used and the blend composition.     

Dielectric spectroscopy of poly(butylene succinate) films

Dielectric properties of poly(butylene succinate) crystallized under different conditions have been reported in the temperature range of 163-383 K and in the frequency range of 0.01-10⁵ Hz. Both the dipolar α and β processes have been identified at low temperatures: the α process is associated with the amorphous fraction while the β with the relaxations in both the amorphous and crystalline fractions. The space charge effect dominates the high temperature dielectric spectra. These spectra have been analyzed in the light of an equivalent circuit model. The Maxwell-Wagner-Sillars polarization, electrode polarization and free charge motion are well resolved. At 383 K, near the melting temperature (387 K), massive melting and subsequent recrystallization have been observed. The peculiar evolution of the spectra is also analyzed using the same equivalent circuit model. The relationship between the fitting parameters and the evolved microstructures is discussed.     

Biodegradable polymer blends of poly(lactic acid) and poly(ethylene glycol)

Poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) were melt-blended and extruded into films in the PLA/PEG ratios of 100/0, 90/10, 70/30, 50/50, and 30/70. It was concluded from the differential scanning calorimetry and dynamic mechanical analysis results that PLA/PEG blends range from miscible to partially miscible, depending on the concentration. Below 50% PEG content the PEG plasticized the PLA, yielding higher elongations and lower modulus values. Above 50% PEG content the blend morphology was driven by the increasing crystallinity of PEG, resulting in an increase in modulus and a corresponding decrease in elongation at break. The tensile strength was found to decrease in a linear fashion with increasing PEG content. Results obtained from enzymatic degradation show that the weight loss for all of the blends was significantly greater than that for the pure PLA. When the PEG content was 30% or lower, weight loss was found to be primarily due to enzymatic degradation of the PLA. Above 30% PEG content, the weight loss was found to be mainly due to the dissolution of PEG. During hydrolytic degradation, for PLA/PEG blends up to 30% PEG, weight loss occurs as a combination of degradation of PLA and dissolution of PEG. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1495–1505, 1997     

Electrospinning and structural characterization of ultrafine poly(butylene succinate) fibers

Biodegradable ultrafine poly(butylene succinate) (PBS) fibers were continuously electrospun for the first time from PBS solutions in chloroform (CF)/2-chloroethanol (CE) (7/3, w/w), CF/CE (6/4, w/w), dichloromethane (DM)/CE (7/3, w/w), DM/CE (6/4, w/w), and CF/3-chloro-1-propanol (9/1, w/w). These mixed solvents had an appropriate evaporation rate for the continuous electrospinning of PBS. The ultrafine PBS fibers had very high crystallinity and their average diameters were in the range of 125-315 nm. The annealed ultrafine PBS fibers exhibited a lamellar stack morphology containing crystalline and amorphous layers.     

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     

Enzymatic degradation kinetics of poly(butylene succinate) nanocomposites

In this work, poly(butylene succinates) (PBS)/organically modified layered silicates (OMLS) composites were prepared by solution blending. The degradability of PBS, PBS/layered silicates and PBS/OMLS nanocomposites have been investigated using enzymatic degradation method. Effects of layered silicates and OMLS contents on the degradation behavior of PBS were explored. The results reveal that the degradability of the composites was both enhanced by the addition of layered silicates or OMLS as compared to the pristine PBS sample. The calculated data based on the autocatalytic model show that the degradation kinetics of PBS/layered silicates composites is the chain scission process with the following autocatalytic reactions, which is very similar to that of pure PBS matrix. On the other hand, the surface-catalyzed reaction model may be more suitable to describe the degradation behavior of the PBS/OMLS nanocomposite. Moreover, the results show that rate-controlling step of the degradation reaction for PBS/OMLS nanocomposite is more probable to be the desorption step.     

Poly(butylene succinate)/poly(vinyl phenol) blends. Part 1. Miscibility and crystallization

Miscibility has been investigated in blends of poly(butylene succinate) (PBSU) and poly(vinyl phenol) (PVPh) by differential scanning calorimetry in this work. PBSU is miscible with PVPh 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 PBSU using the Nishi–Wang equation, is composition dependent, and its value is always negative. This indicates that PBSU/PVPh blends are thermodynamically miscible in the melt. Preliminary morphology study of PBSU/PVPh blends was also studied by optical microscopy (OM). OM experiments show the spherulites of PBSU become larger with the PVPh content, indicative of a decrease in the nucleation density, and the coarseness of PBSU spherulites increases too with increasing the PVPh content in the blends.     

Synthesis and properties of poly(butylene succinate) with N-hexenyl side branches

N-hexenyl side branches were introduced into poly(butylene succinate) (PBS) by polymerization of succinic acid (SA) with 1,4-butanediol (BD) in the presence of 7-octene-1,2-diol (OD). Thermal properties and biodegradability of the aliphatic polyesters were investigated before and after epoxidation of the pendant double bonds. The glass-transition temperature (T_g) decreased with the branching density to give a minimum at 0.03 mol of branching units per mole of structural units. Thereafter, T_g increased due to the in situ crosslinking of the unsaturated groups during the differential scanning calorimetry (DSC) measurements. N-Hexenyl side branches decreased melting temperature (T_m) more significantly than ethyl side branches, but the effect was on par with that by n-octyl branches. Epoxidation of the double bonds decreased T_m and melting enthalpy (ΔH_m), but increased T_g of the aliphatic polyester. Biodegradability was enhanced to some extent by the presence of n-hexenyl side branches. However, the epoxidation of the unsaturated groups did not notably affect the biodegradability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2219–2226, 2001     

Melting behaviour of poly(butylene succinate) in miscible blends with poly(ethylene oxide)

The melting behavior of poly(butylene succinate) (PBSU) in miscible blends with poly(ethylene oxide) (PEO), which is a newly found polymer blends of two crystalline polymers by our group, has been investigated by conventional differential scanning calorimetry (DSC). It was found that PBSU showed double melting behavior after isothermal crystallization from the melt under certain crystallization conditions, which was explained by the model of melting, recrystallization and remelting. The influence of the blend composition, crystallization temperature and scanning rate on the melting behavior of PBSU has been studied extensively. With increasing any of the PEO composition, crystallization temperature and scanning rate, the recrystallization of PBSU was inhibited. Furthermore, temperature modulated differential scanning calorimetry (TMDSC) was also employed in this work to investigate the melting behavior of PBSU in PBSU/PEO blends due to its advantage in the separation of exotherms (including crystallization and recrystallization) from reversible meltings (including the melting of the crystals originally existed prior to the DSC scan and the melting of the crystals formed through the recrystallization during the DSC scan). The TMDSC experiments gave a direct evidence of this melting, recrystallization and remelting model to explain the multiple melting behavior of PBSU in PBSU/PEO blends.     

Kinetics of nucleation and crystallization in poly(butylene succinate) nanocomposites

Differential fast scanning calorimetry (DFSC) was employed on poly(butylene succinate) nanocomposites containing silver nanoparticles and multi-walled carbon nanotubes (MWCNT), in order to identify the temperature range of heterogeneous nucleation caused by both nanofillers. The fast scanning rates also allow investigating self-nucleation by recrystallization experiments approaching the crystallization temperature from low temperatures. The recrystallization behavior of PBSu and its nanocomposites is distinct from all other polymers studied so far as only the previously crystallized part of the material is able to recrystallize, independently on the available large number of nuclei. Since full melting of small crystals at low temperatures is observed this highlights the importance of ordered structures remaining in the polymer melt. On cooling from the melt the neat polymer did not crystallize at rates higher than 70 K/s, while the nanocomposites needed rates of 500 K/s and 300 K/s for silver and MWCNT, respectively. Below 280 K the crystallization kinetics of the matrix was almost the same with the nanocomposite samples. The nucleation mechanism changes at 280 K from heterogeneous to homogeneous. The study further confirms that below the glass transition nucleation and crystallization appears only after approaching the enthalpy value of the extrapolated supercooled liquid by enthalpy relaxation.     

Stretching induced phase separation in poly(vinylidene fluoride)/poly(butylene succinate) blends studied by in-situ X-ray scattering

The structure evolution of poly(vinylidene fluoride)/poly(butylene succinate) (PVDF/PBS) blends during stretching above the melting point of PBS is investigated by synchrotron-based simultaneous wide angle and small angle X-ray scattering (WAXS/SAXS). Before stretching, PVDF crystallizes into the α-form, whereas the chains of molten PBS locate at the inter-lamellar amorphous phase of PVDF. Crystal transition from α to β of PVDF is observed in all samples during stretching. The morphological transformation from a lamellar structure into a fibrillar structure occurs at low and intermediate strains. With further deformation, a “stretching induced phase separation” phenomenon is observed. The final microstructure of PVDF/PBS blends contains PVDF microfibrils with PBS chains preferentially distributed in the inter-fibrillar region. The PBS molecular weight influences the onset and end strain for the transition. A new “two-step model” is proposed to describe the deformation process.     

聚丁二酸丁二醇酯的扩链改性及共混研究

采用扩链剂2,4-甲苯二异氰酸酯（TDI）、2,2′-双（2-恶唑啉）（BOZ）以及新型扩链剂ADR-4370对聚丁二酸丁二醇酯（PBS）进行扩链,对比研究3种扩链剂对PBS性能的影响。采用聚乳酸（PLA）与PBS共混,选择最佳配比以及合适的共混工艺。结果表明,新型扩链剂ADR-4370可以良好的改善PBS的加工性能和机械性能,m（PBS）/m（PLA）最佳配比为70：30,在共混同时进行扩链比扩链后再共混可以更好的提高PBS/PLA的性能。     

Miscibilities and rheological properties of poly(butylene succinate)–Poly(butylene terephthalate) blends

An aliphatic/aromatic polyester blend has been dealt with in this study. As an aliphatic polyester, poly(butylene succinate) (PBS) was used, which is thought to possess biodegradability, but it is relatively expensive. It has been blended with poly(butylene terephthalate) (PBT) in order to obtain a biodegradable blend with better mechanical properties and lower cost. The miscibilities of PBS–PBT blends were examined not only from the changes of T_g but also from log G′–log G" plots. Dynamic mechanical thermal analyzer (DMTA) was an appropriate, sensitive method to obtain the glass transitions properly. Thermal stabilities of PBS and PBT were also verified at the temperature of 240°C. A transesterification reaction between two polyesters at 240°C was hardly detectable so that it did not affect the miscibilities and properties of the blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 945–951, 1999     

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.     

Morphology and hydrogen‐bond restricted crystallization of poly(butylene succinate)/cellulose diacetate blends

Poly(butylene succinate)/cellulose diacetate (PBS/CDA) blends were prepared by the solution blending method from poly(butylene succinate) (PBS) and cellulose diacetate (CDA). The influence of hydrogen bond on the structure, morphology, crystallization, as well as the physical properties of PBS/CDA blends was significantly investigated. The fourier transform infrared spectroscopy (FTIR) results indicated that the carbonyl groups of PBS shifted to higher wavenumbers and disappeared at the content of 60% CDA, due to the formation of hydrogen bond between PBS and CDA. The wide‐angle X‐ray diffractometer (WAXD) and differential scanning calorimeter (DSC) analysis suggest that the crystallization of PBS was significantly restricted by the incorporation of CDA, which is also attributed to the hydrogen bonding. The scanning electron miscroscope (SEM) and polarized optical microscopy (POM) results revealed that PBS and CDA were miscible without appearance of obvious phase separation. The hydrogen bonding interaction led to the change of decomposing mechanism of blends as determined by thermogravimetric analysis (TGA), as well as the increase of the elongation at break due to the reduced crystallinity of PBS. The existence of CDA led to the decrease of water contact angle, showing of the improved hydrophilicity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012