Effect of poly(vinyl acetate) (PVAc) on thermal behavior and mechanical properties of poly(3-hydroxybutyrate)/poly(propylene carbonate) (PHB/PPC) blends

To assess the compatibility of blends of synthetic poly(propylene carbonate) (PPC), with a natural bacterial poly(3-hydroxybutyrate) (PHB), a simple casting procedure of blend was used. poly(3-hydroxybutyrate)/poly(propylene carbonate) blends are found to be incompatible according to DSC and DMA analysis. In order to improve the compatibility and mechanical properties of PHB/PPC blends, poly(vinyl acetate) (PVAc) was added as a compatibilizer. The effects of PVAc on the thermal behavior, morphology, and mechanical properties of 70PHB/30PPC blend were investigated. The results show that the melting point and the crystallization temperature of PHB in blends decrease with the increase of PVAc content in blends, the loss factor changes from two separate peaks of 70PHB/30PPC blend to one peak of 70PHB/30PPC/12PVAc blend. It is also found that adding PVAc into 70PHB/30PPC blend can decrease the size of dispersed phase from morphology analysis. The result of tensile properties shows that PVAc can increase the tensile strength and Young’s modulus of 70PHB/30PPC blend, and both the elongation at break and the tensile toughness increase significantly with PVAc added into 70PHB/30PPC.     

Spontaneous thinning/thickening deformation observed for plastic blend films and some factors affecting film deformation

The fully amorphous films of highly syndiotactic poly[(R,S)‐3‐hydroxybutyrate] (s‐PHB)/atactic poly(4‐vinylphenol) (PVPh) blends show reversible thinning/thickening phenomena at 37 °C in aqueous medium. On the other hand, isotactic poly[(R)‐3‐hydroxybutyrate] (i‐PHB)/PVPh blend film, in which i‐PHB blend component was partially crystalline, did not show any thinning/thickening phenomena under the same conditions. To elucidate the factors influencing these phenomena, the structure and molecular interaction in these blends were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry, and wide‐angle X‐ray diffraction. The FTIR spectra indicated that the ester carbonyl of PHB and the phenolic hydroxyl of PVPh formed hydrogen bonds in both the thinned and thickened s‐PHB/PVPh blend films. The blend composition, intermolecular hydrogen‐bonding interaction, crystallization behavior, miscibility, and the glass‐transition temperature of the blends affected the thinning/thickening phenomena. Some other polyesters such as poly(?‐caprolactone), poly (L‐lactic acid), atactic poly(D,L‐lactic acid), and poly(ethylene terephthalate) had no ability to exhibit thinning/thickening phenomena in water at 37 °C when they were blended with PVPh. This result implies that s‐PHB/PVPh is the rare example with the ability to show reversible thinning/thickening phenomena. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2736–2743, 2002     

Computer simulation studies of the miscibility of poly(3-hydroxybutyrate)-based blends

By means of the molecular dynamics simulation method, the miscibility of poly(3-hydroxybutyrate)/polyethylene (PHB/PE) blend has been investigated. Two glass transition temperatures of the PHB/PE are found by scrutinizing its volume-temperature curve, and this result is qualitatively in agreement with the experimental results. To further analyze the miscibility of poly(3-hydroxybutyrate)-based blends, the Flory-Huggins parameters of PHB/PE, poly(3-hydroxybutyrate)/poly(ethylene oxide) (PHB/PEO), poly(ethylene oxide)/polyethylene (PEO/PE) have been calculated via a Monte Carlo scheme, and the morphology of the PHB/PEO and the PHB/PE blend has been simulated using dissipative particle dynamics method. The time evolution of dividing interface for PHB/PEO/PE blend shows a dynamic phase separation process. All these results indicate that PHB and PEO tend to mix together, whereas PE aggregates to form PE-rich domains in the PHB/PE and PHB/PEO/PE blends.     

Correlative analysis between morphology and mechanical properties of poly-3-hydroxybutyrate (PHB) blended with polycarprolactone (PCL) using solid-state NMR

Blends of poly(3-hydroxybutyrate) (PHB) and poly(caprolactone) (PCL) were evaluated using multiscale instrumental analyses to reveal the effects of blend ratio and crosslinking reagent. In the multiscale instrumental analyses, molecular mobility from molecular to nano scales was examined by solid-state NMR, while the morphology at the micron scale was revealed by scanning electron microscopy (SEM). PHB-rich blends adopted a sea-island morphology and showed a larger maximum stress due to dispersed PHB filler. A PCL-rich blend also adopted a sea-island morphology but the sea domain consisted of PCL and showed a larger strain at break. An equal ratio PHB/PCL blend had a bicontinuous morphology which showed lower maximum stress and lower strain at break because of large hemispherical defects. The crosslinking reagent changes these heterogeneous morphologies of PHB/PCL blends to homogeneous at the micron scale, which improved tensile properties. Even though the molecular mobility changed with the polymer content and the crosslinking reagent, the bicontinuous and homogeneous morphologies more significantly affected the tensile properties of the PHB/PCL blends.     

Dielectric relaxation study of atactic poly(epichlorohydrin)/poly(3-hydroxybutyrate) blends

Binary blends of atactic poly(epichlorohydrin) (aPECH) and poly(3-hydroxybutyrate) (PHB) were investigated as a function of blend composition and crystallization conditions by dielectric relaxation spectroscopy. The quenched samples were found to be miscible in the whole composition range by detecting only one glass transition relaxation, for each composition, which could be closely described by the Gorden-Taylor equation. The cold-crystallized blends displayed two glass transition relaxations at all blend ratios indicating the coexisting of two amorphous populations: a pure aPECH phase dispersed mainly in the interfibrillar zones and a mixed amorphous phase held between crystal lamellae. The interlamellar trapping of aPECH was small and decreases with increasing the overall PHB content in the blend. At high crystallization temperatures the aPECH molecules was found to reside mainly in the interfibrillar regions due to its high mobility relative to the crystal growth rate of PHB. Our results suggest that because the intersegmental interaction in aPECH/PHB blends is weak, the mobility of the amorphous component at a given crystallization temperature decides diluent segregation.     

Crystallization behaviors of poly(3-hydroxybutyrate) and poly(l-lactic acid) in their immiscible and miscible blends

By adjusting the molecular weight of the poly(l-lactic acid) (PLLA) component in poly(3-hydroxybutyrate) (PHB)/PLLA blends, we investigated the crystallization behaviors of the two components in their immiscible and miscible 50:50 blends by real time infrared (IR) spectroscopy. In the immiscible PHB/PLLA blend, the stepwise crystallization of PHB and PLLA was realized at different crystallization temperatures. PLLA crystallizes first at a higher temperature (120 degrees C). Its crystallization mechanism from the immiscible PHB/PLLA melt is not affected by the presence of the PHB component, while its crystallization rate is substantially depressed. Subsequently, in the presence of crystallized PLLA, the isothermal melt-crystallization of PHB takes place at a lower temperature (90 degrees C). It is interesting to find that there are two growth stages for PHB. At the early stage of the growth period, the Avrami exponent is 5.0, which is unusually high, while in the late stage, it is 2.5, which is very close to the reported value (n approximately 2.5) for the neat PHB system. In contrast to the stepwise crystallization of PHB and PLLA in the immiscible blends, the almost simultaneous crystallization of PHB and PLLA in the miscible 50:50 blend was observed at the same crystallization temperature (110 degrees C). Detailed dynamic analysis by IR spectroscopy has disclosed that, even in such apparently simultaneous crystallization, the crystallization of PLLA actually occurs faster than that of PHB. It has been found that, both in the immiscible and miscible blends, the crystallization dynamics of PHB are heavily affected by the presence of crystallized PLLA.     

Electrospun fiber mats of poly(3‐hydroxybutyrate), poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate), and their blends

Electrospinning of poly(3‐hydroxybutyrate) (PHB), poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV), and their blends was first carried out in chloroform at 50 °C on a stationary collector. The average diameter of the as‐spun fiber from PHB and PHBV solutions decreased with increasing collection distance and increased with increasing solution concentration and applied electrical potential. In all of the spinning conditions investigated, the average diameter of the as‐spun pure fibers ranged between 1.6 and 8.8 μm. Electrospinning of PHB, PHBV, and their blends was carried out further at a fixed solution concentration of 14% w/v on a homemade rotating cylindrical collector. Well‐aligned, cross‐sectionally round fibers without beads were obtained. The average diameter of the as‐spun pure and blend fibers ranged between 2.3 and 4.0 μm. The as‐spun fiber mats appeared to be more hydrophobic than the corresponding films and much improvement in the tensile strength and the elongation at break was observed for the blend fiber mats over those of the pure fiber ones. Lastly, indirect cytotoxicity evaluation of the as‐spun pure and blend fiber mats with mouse fibroblasts (L929) indicated that these mats posed no threat to the cells. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2923–2933, 2006     

Oriented lamellar structures in uniaxially drawn films of poly(vinylidene fluoride) and poly(3‐hydroxybutyrate) blends studied by small‐angle X‐ray scattering measurements

The lamellar structures in uniaxially drawn films of miscible crystalline/crystalline polymer blends of poly(vinylidene fluoride) (PVDF) and poly(3‐hydroxybutyrate) (PHB) were investigated by static and time‐resolved measurements of small‐angle X‐ray scattering (SAXS). Intense SAXS in the low angle range of the meridian was interpreted as originating from the interlamellar inclusion structure, in which the PHB chains were included between the lamellae of PVDF. The interlamellar inclusion was induced for the uniaxially drawn films of PVDF/PHB = 30/70 blend with a draw ratio (DR) of 2.8–4.5, whereas the lamellae of the PVDF and PHB components were mutually excluded from each other forming their own lamellar stacks (interlamellar exclusion) in the blend with a higher DR (5.0–5.7). When the highly drawn film with the interlamellar exclusion structure was heat treated at 154–165 °C, the interlamellar inclusion structure was partially induced by the heat treatment. The time‐resolved SAXS measurements indicated that the interlamellar inclusion structure was developed by melting and recrystallization of PVDF during the heat treatment. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 381–392, 2009     

Nonisothermal crystallization and melting behavior of poly(β‐hydroxybutyrate)–Poly(vinyl‐acetate) blends

Nonisothermal crystallization and melting behavior of poly(β‐hydroxybutyrate) (PHB)–poly(vinyl acetate) (PVAc) blends from the melt were investigated by differential scanning calorimetry using various cooling rates. The results show that crystallization of PHB from the melt in the PHB–PVAc blends depends greatly upon cooling rates and blend compositions. For a given composition, the crystallization process begins at higher temperatures when slower scanning rates are used. At a given cooling rate, the presence of PVAc reduces the overall PHB crystallization rate. The Avrami analysis modified by Jeziorny and a new method were used to describe the nonisothermal crystallization process of PHB–PVAc blends very well. The double‐melting phenomenon is found to be caused by crystallization during heating in DSC. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 443–450, 1999     

Miscibility in blends of poly(3-hydroxybutyrate) and poly(vinylidene chloride-co-acrylonitrile)

Miscibility behavior of poly(3-hydroxybutyrate) [PHB]/poly(vinylidene chloride-co-acrylonitrile) [P(VDC-AN)] blends have been investigated by differential scanning calorimetry and optical microscopy. Each blend showed a single T_g, and a large melting point depression of PHB. All the blends containing more than 40% PHB showed linear spherulitic growth behavior and the growth rate decreased with P(VDC-AN) content. The interaction parameter χ₁₂, obtained from melting point depression analysis, gave the value of −0.267 for the PHB/P(VDC-AN) blends. All results presented in this article lead to the conclusion that PHB/P(VDC-AN) blends are completely miscible in all proportions from a thermodynamic viewpoint. The miscibility in these blends is ascribed to the specific molecular interaction involving the carbonyl groups of PHB. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2645–2652, 1997     

生物塑料--聚(β-羟基丁酸酯)的物理改性和化学改性

综述了生物塑料聚(β-羟基丁酸酯)(PHB)近年来在物理改性(共混改性)和化学改性(大分子反应改性和反应性共混改性)方面工作的进展状况。在PHB共混体系中,可解体性共混物和全生物降解性共混物是两类不同的共混体系,后者从长远意义上讲是解决环境污染问题的根本途径,而其现实意义上的用途是在生物医学领域。文章主要对PHB共混体系的相容性、热行为、结晶行为、机械性能和降解性能等方面的规律进行了总结。并指出反应性共混是较佳改善非相容PHB共混体系相容性的方法,而大单体反应改性和反应性共混则是改造PHB,提供新型功能化医用材料的有效手段。这些领域方面的研究代表了PHB改性工作新的发展方向。     

Fully-biodegradable poly(3-hydroxybutyrate)/poly(vinyl alcohol) blend films with compositional gradient

Fully-biodegradable bacterial poly(3-hydroxybutyrate) (PHB)/chemosynthetic poly(vinyl alcohol) (PVA) blend films with compositional gradient from one surface to the other surface of the films were prepared by a dissolution-diffusion technique. Three kinds of PVA samples, high- and low-molecular weight atactic PVA and highly syndiotactic PVA (s-PVA), were used in order to investigate the effects of molecular weight and tactic structure on the generation of compositional gradient. The solution of PHB in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), which is also a good solvent for PVA, was cast on the PVA film and then the solvent HFIP was evaporated. By selecting the optimum volume of solvent and the evaporation rate, the PHB/PVA blend film with compositional gradient was obtained. The formation of compositional gradient was confirmed by FT-IR microscopy and ATR-FT-IR analysis. The 50%/50% PHB/s-PVA blend film with a nearly ideal compositional gradient, that is, the composition of PHB (or PVA) in the film changing gradually from 100% at one surface to 0% at the other surface of the film was obtained by casting PHB/HFIP solution on to the s-PVA film. Positional dependence of the absorbance of C==O and OH stretching bands along the film thickness direction for the PHB/S-PVA cast films.     

聚(3-羟基丁酸酯)/聚氧化乙烯共混物非晶区相容性的固体核磁共振研究

用固体高分辨核磁共振碳谱方法研究了不同组成比的聚 (3 羟基丁酸酯 ) 聚氧化乙烯共混物的结晶度、非晶区的相容性和分子运动能力 .结果表明聚 (3 羟基丁酸酯 )的结晶度几乎不随组成比变化 ,而聚氧化乙烯的结晶度则随其在共混物中含量的降低而显著降低 .聚氧化乙烯的加入使得聚 (3 羟基丁酸酯 )非晶区的分子运动能力有所增强 .共混物的非晶区表现出一定的相容性 ,相容程度与共混物的组成比有关     

Thermal behavior and intermolecular interactions in blends of poly(3‐hydroxybutyrate) and maleated poly(3‐hydroxybutyrate) with chitosan

The thermal behavior and intermolecular interactions of blends of poly(3‐hydroxybutyrate) (PHB) and maleated PHB with chitosan were studied with differential scanning calorimetry, Fourier transform infrared (FTIR), wide‐angle X‐ray diffraction (WAXD), and X‐ray photoelectron spectroscopy (XPS). The differences in the two blend systems with respect to their thermal behavior and intermolecular interactions were investigated. The melting temperatures, melting enthalpies, and crystallinities of the two blend systems gradually decreased as the chitosan content in the blends increased. Compared with that of the PHB component with the same composition, the crystallization of the maleated PHB component was more intensively suppressed by the chitosan component in the blends because of the rigid chitosan molecular chains and the intermolecular hydrogen bonds between the components. FTIR, WAXD, and XPS showed that the intermolecular hydrogen bonds in the blends were caused by the carbonyls of PHB or maleated PHB and chitosan aminos, and their existence depended on the compositions of the blends. The introduction of maleic anhydride groups onto PHB chains promoted intermolecular interactions between the maleated PHB and chitosan components. In addition, the intermolecular interactions disturbed the original crystal structures of the PHB, maleated PHB, and chitosan components; this was further proven by WAXD results. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 35–47, 2005     

Calorimetric and SEM studies of PHB–PET polymeric blends

PHB [poly (3-hydroxybutyrate)], post-consumer soft-drink bottles poly (ethylene terephthalate) PET (herein named PET-R) and PHBPET-R (blends of PHB and PET-R in several compositions) samples were evaluated by differential scanning calorimetry (DSC) and scanning electronic microscopy (SEM) in order to verify their thermal properties and porosity according to amounts of PET-R added the blends. The DSC curve showed that the solvents used to solve the polymer mixture cause changes in the thermal behavior of PET-R films and in PHBPET-R blends. SEM studies of the PHBPET-R blends show that with a gradual mass increase of PET-R, there are gradual increases in the porosity of the films.     

Miscibility,Crystallization, and Rheological Behavior of Solution Casting Poly(3-hydroxybutyrate)/poly(ethylene succinate) Blends Probed by Differential Scanning Calorimetry,Rheology, and Optical Microscope Techniques

The miscibility and crystallization of solution casting biodegradable poly(3-hydroxybuty-rate)/poly(ethylene succinate) (PHB/PES) blends was investigated by differential scanning calorimetry, rheology, and optical microscopy. The blends showed two glass transition temperatures and a depression of melting temperature of PHB with compositions in phase diagram, which indicated that the blend was partially miscible. The morphology observation supported this result. It was found that the PHB and PES can crystallize simultaneously or upon stepwise depending on the crystallization temperatures and compositions. The spherulite growth rate of PHB increased with increasing of PES content. The influence of compositions on the spherulitic growth rate for the partially miscible polymer blends was discussed.     

Rheo-optical FT-IR spectroscopy of poly(3-hydroxybutyrate)/poly(lactic acid) blend films

The orientation of poly(3-hydroxybutyrate) (PHB) and poly(lactic acid) (PLA) segments in PHB/PLA blend films cast from chloroform solutions with compositions PHB < PLA was studied during uniaxial elongation up to 250% strain at 50 °C by in-situ rheo-optical FT-IR spectroscopy. From the orientation functions of the ν(CO) bands of the blend components, it was derived that the PLA chains orient in the direction of elongation while the PHB chains orient perpendicular to the drawing direction. PHB homopolymer and PHB/PLA blend films with PHB > PLA compositions could only be oriented by cold drawing in ice water after quenching from the melt. The IR-dichroic effects of films drawn under these conditions indicate for both blend components a chain alignment parallel to the drawing direction.     

Evaluation of homogeneity of binary blends of poly(3-hydroxybutyrate) and poly(L-lactic acid) studied by near infrared chemical imaging (NIRCI).

The homogeneity of blends of poly((R)-3-hydroxybutyrate) (PHB) and poly(L-lactic acid) (PLLA) was evaluated by the near infrared chemical imaging (NIRCI) technique. NIRCI can nondestructively investigate a sample over a wide field of view within a few minutes to acquire a large number of spatially resolved NIR spectral data. NIRCI may be combined with multivariate analysis not only for qualitative analysis but also for statistically based quantitative analysis. The score images derived from the partial least squares regression (PLSR) analysis directly show that PHB/PLLA blends are highly homogeneous. The standard deviations (STD) of the histograms, indicating the distribution of the score values, show small values for the blends. These results qualitatively and quantitatively show the high level of homogeneity of PHB/PLLA blends. The predictions of the spatially averaged concentrations of the blend components obtained from PLSR results show values similar to the actual contents for the blends. The small errors of the predictions are also explained by STD values.     

Effect of aging on fractional crystallization of poly(ethylene oxide) component in poly(ethylene oxide)/poly(3‐hydroxybutyrate) blends

The effect of aging on the fractional crystallization of the poly(ethylene oxide) (PEO) component in the PEO/poly(3‐hydroxybutyrate) (PHB) blend has been investigated. The partial miscibility of the PEO/PHB blends with high PEO molecular weight (M_v = 2.0 × 10⁵ g/mol) was confirmed by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis. The fractional crystallization behavior of the PEO component in the PEO/PHB blends with low PEO content (not more than 30 wt% of PEO), before and after aging under vacuum at 25 °C for 6 months, were compared by DSC, fourier transform infrared microscopic spectroscopy, small angle X‐ray diffraction, and scanning electron microscopy. It was confirmed that nearly all the PEO components remain trapped within interlamellar regions of PHB for the PEO/PHB blends before aging. Under this condition, the crystallization of PEO is basically induced by much less active heterogeneities or homogeneous nucleation at high supercoolings. While, after the same PEO/PHB samples were stored at 25 °C in vacuum for 6 months, a part of the PEO component was expelled from the interlamellar region of PHB. Under this condition, the expelled PEO forms many separate domains with bigger size and crystallizes at low supercoolings by active heterogeneous nucleation, whereas the crystallization of PEO in the interlamellar region is still mainly induced by less active heterogeneities or homogeneous nucleation at extreme supercoolings. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2665–2676, 2005     

Correlation between solid-state structures and enzymatic degradability of cocrystallized blends

Solid-state structures and enzymatic degradability have been investigated for cocrystallized blends between poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [PHBV] and poly(3-hydroxybutyrate-co-3-hydroxypropionate) [PHBP]. From wide-angle X-ray diffraction patterns, small-angle X-ray scattering data, and the comparison of the enzymatic degradability of these blends, the solid-state structures of PHBV/PHBP blend samples, in which the PHBV component has higher isothermal crystal growth rate (G) value than the PHBP one, might be similar to those of the component PHBVs; while those of the PHBP/PHBV blend samples, in which PHBP component has higher G value, were similar to the component PHBPs. Normalized one-dimensional correlation functions gamma(x) of PHBV/PHBP binary blends crystallized at 90 degrees C.