Thermal degradation of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) as studied by TG,TG–FTIR,and Py–GC/MS

The thermal degradation kinetics of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [poly(HB–HV)] under nitrogen was studied by thermogravimetry (TG). The results show that the thermal degradation temperatures (T_o, T_p, and T_f) increased with an increasing heating rate (B). Poly(HB–HV) was thermally more stable than PHB because its thermal degradation temperatures, T_o(0), T_p(0), and T_f(0)—determined by extrapolation to B = 0°C/min—increased by 13°C–15°C over those of PHB. The thermal degradation mechanism of PHB and poly(HB–HV) under nitrogen were investigated with TG–FTIR and Py–GC/MS. The results show that the degradation products of PHB are mainly propene, 2‐butenoic acid, propenyl‐2‐butenoate and butyric‐2‐butenoate; whereas, those of poly(HB–HV) are mainly propene, 2‐butenoic acid, 2‐pentenoic acid, propenyl‐2‐butenoate, propenyl‐2‐pentenoate, butyric‐2‐butenoate, pentanoic‐2‐pentenoate, and CO₂. The degradation is probably initiated from the chain scission of the ester linkage. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1530–1536, 2003     

Thermal analyses of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by T_o = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was T_p = 0.91B + 320, and the temperature at which degradation was completed was T_f = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), T_o = 0.96B + 308, T_p = 0.99B + 320, and T_f = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), T_o = 1.11B + 305, T_p = 1.10B + 319, and T_f = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures T_o, T_p, and T_f relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001     

Miscibility and crystallization kinetics of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/ poly(methyl methacrylate) blends

The miscibility and crystallization kinetics of the blends of random poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [P(HB‐co‐HV)] copolymer and poly(methyl methacrylate) (PMMA) were investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that P(HB‐co‐HV)/PMMA blends were miscible in the melt. Thus the single glass‐transition temperature (T_g) of the blends within the whole composition range suggests that P(HB‐co‐HV) and PMMA were totally miscible for the miscible blends. The equilibrium melting point (T°_m) of P(HB‐co‐HV) in the P(HB‐co‐HV)/PMMA blends decreased with increasing PMMA. The T°_m depression supports the miscibility of the blends. With respect to the results of crystallization kinetics, it was found that both the spherulitic growth rate and the overall crystallization rate decreased with the addition of PMMA. The kinetics retardation was attributed to the decrease in P(HB‐co‐HV) molecular mobility and dilution of P(HB‐co‐HV) concentration resulting from the addition of PMMA, which has a higher T_g. According to secondary nucleation theory, the kinetics of spherulitic crystallization of P(HB‐co‐HV) in the blends was analyzed in the studied temperature range. The crystallizations of P(HB‐co‐HV) in P(HB‐co‐HV)/PMMA blends were assigned to n = 4, regime III growth process. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3595–3603, 2004     

Thermal analysis of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) irradiated under vacuum

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was irradiated by ⁶⁰Co γ‐rays (doses of 50, 100 and 200 kGy) under vacuum. The thermal analysis of control and irradiated PHBV, under vacuum was carried out by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The tensile properties of control and irradiated PHBV were examined by using an Instron tensile testing machine. In the thermal degradation of control and irradiated PHBV, a one‐step weight loss was observed. The derivative thermogravimetric curves of control and irradiated PHBV confirmed only one weight‐loss step change. The onset degradation temperature (T_o) and the temperature of maximum weight‐loss rate (T_p) of control and irradiated PHBV were in line with the heating rate (°C min^?1). T_o and T_P of PHBV decreased with increasing radiation dose at the same heating rate. The DSC results showed that ⁶⁰Co γ‐radiation significantly affected the thermal properties of PHBV. With increasing radiation dose, the melting temperature (T_m) of PHBV shifted to a lower value, due to the decrease in crystal size. The tensile strength and fracture strain of the irradiated PHBV decreased, hence indicating an increased brittleness. Copyright © 2004 Society of Chemical Industry     

Miscibility and crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/poly(vinyl acetate) blends

The miscibility and crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (P(HB‐co‐HV))/poly(vinyl acetate) (PVAc) blends have been investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that P(HB‐co‐HV)/PVAc blends were miscible in the melt over the whole compositions. Thus the blend exhibited a single glass transition temperature (T_g), which increased with increasing PVAc composition. The spherulitic morphologies of P(HB‐co‐HV)/PVAc blends indicated that the PVAc was predominantly segregated into P(HB‐co‐HV) interlamellar or interfibrillar regions during P(HB‐co‐HV) crystallization because of the volume‐filled spherulites. As to the crystallization kinetics study, it was found that the overall crystallization and crystal growth rates decreased with the addition of PVAc. The kinetics retardation was primarily attributed to the reduction of chain mobility and dilution of P(HB‐co‐HV) upon mixing with higher T_g PVAc. The overall crystallization rate was predominantly governed by the spherulitic growth rate and promoted by the samples treated with the quenched state because of the higher nucleation density. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 980–988, 2006     

Water transport properties in poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) biopolymers

Water sorption and diffusion have been investigated in poly(3‐hydroxybutyrate) (PHB) and three poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) copolymers [P(HB‐HV)] by means of a Cahn electromicrobalance. Permeability of these samples have been determined using a gravimetric permeation cell. Two experimental setups were used for the gravimetric sorption measurements, under dynamic and static conditions, respectively. The differences observed in the results obtained using these techniques are discussed. The sorption measurements have evidenced the tendency of water molecules to form aggregates or clusters in the polymer. In addition, the static sorption method revealed the potential of PHB and P(HB‐HV) to undergo molecular relaxations, eventually leading to a partial desorption of the previously sorbed water after an induction period. The clustering effect was adequately described by the polycondensation model. On the other hand, the interpretation of the diffusivity in terms of mobility coefficients has revealed a competition between a plasticization effect and clustering. As a whole, water transport properties in PHB and its copolymers can be considered to be very close in magnitude to those of common thermoplastics such as PVC and PET. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 455–468, 1999     

Blends of bacterial poly[(R)‐3‐hydroxybutyrate] with oligo[(R,S)‐3‐hydroxybutyrate]‐diol

The miscibility, melting and crystallization behaviour of poly[(R)‐3‐hydroxybutyrate], PHB, and oligo[(R,S)‐3‐hydroxybutyrate]‐diol, oligo‐HB, blends have been investigated by differential scanning calorimetry: thermograms of blends containing up to 60 wt% oligo‐HB showed behaviour characteristic of single‐phase amorphous glasses with a composition dependent glass transition, T_g, and a depression in the equilibrium melting temperature of PHB. The negative value of the interaction parameter, determined from the equilibrium melting depression, confirms miscibility between blend components. In parallel studies, glass transition relaxations of different melt‐crystallized polymer blends containing 0–20 wt% oligo‐HB were dielectrically investigated between ?70 °C and 120 °C in the 100 Hz to 50 kHz range. The results revealed the existence of a single α‐relaxation process for blends, indicating the miscibility between amorphous fractions of PHB and oligo‐HB. © 2002 Society of Chemical Industry     

Tailoring the surface architecture of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) scaffolds

This study was designed to determine whether the surface modifications of the various poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) [P(3HB‐co‐4HB)] copolymer scaffolds fabricated would enhance mouse fibroblast cells (L929) attachment and proliferation. The P(3HB‐co‐4HB) copolymer with a wide range of 4HB monomer composition (16–91 mol %) was synthesized by a local isolate Cupriavidus sp. USMAA1020 by employing the modified two‐stage cultivation and by varying the concentrations of 4HB precursors, namely γ‐butyrolactone and 1,4‐butanediol. Five different processing techniques were used in fabricating the P(3HB‐co‐4HB) copolymer scaffolds such as solvent casting, salt‐leaching, enzyme degradation, combining salt‐leaching with enzyme degradation, and electrospinning. The increase in 4HB composition lowered melting temperatures (T_m) but increased elongation to break. P(3HB‐co‐91 mol % 4HB) exhibited a melting point of 46°C and elongation to break of 380%. The atomic force analysis showed an increase in the average surface roughness as the 4HB monomer composition increased. The mouse fibroblasts (L929) cell attachment was found to increase with high 4HB monomer composition in copolymer scaffolds. These results illustrate the importance of a detailed characterization of surface architecture of scaffolds to provoke specific cellular responses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The kinetics of the thermal decomposition of poly(3‐hydroxybutyrate) and maleated poly(3‐hydroxybutyrate)

The thermal decomposition mechanism of maleated poly(3‐hydroxybutyrate) (PHB) was investigated by FTIR and ¹H NMR. The results of experiments showed that the random chain scission of maleated PHB obeyed the six‐membered ring ester decomposition process. The thermal decomposition behavior of PHB and maleated PHB with different graft degree were studied by thermogravimetry (TGA) using various heating‐up rates. The thermal stability of maleated PHB was evidently better than that of PHB. With increase in graft degree, the thermal decomposition temperature of maleated PHB gradually increased and then declined. Activation energy E_a as a kinetic parameter of thermal decomposition was estimated by the Flynn‐Wall‐Ozawa and Kissinger methods, respectively. It could be seen that approximately equal values of activation energy were obtained by both methods. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1789–1796, 2002; DOI 10.1002/app.10463     

Dielectric relaxation analysis of biopolymer poly(3‐hydroxybutyrate)

Poly(3‐hydroxybutyrate), PHB, is a widely distributed carbon storage polymer among prokaryotes including Rhizobium. Capacities of Rhizobium etli R13 to produce the bioplastic during growth on media with different carbon sources appeared to be specific carbon‐source. In fed batch fermentation, R. etli R13 resulted in cell dry weight 6.2 g/L and PHB 51.4%. Gas chromatography‐mass spectrometry and gel permeation chromatography analysis revealed that PHB produced from R. etli R13 was solely composed of 3‐hydroxybutyric acid and the molecular mass of the purified PHB was 3.4 × 10⁵ Da with polydispersity 1.47. Dielectric relaxation of PHB has been studied in the temperature and frequency ranges 300–440 K and 10 kHz–4 MHz, respectively. A clear dielectric α and ρ‐relaxation processes are observed in these studied ranges of temperature and frequency. The first process is due to the dipole relaxation in the crystalline phase of PHB. The second one is due to the space‐charge formation or Maxwell‐Wagner‐polarization. The α‐relaxation process has been investigated by semiempirical Havriliak‐Negami relaxation function. The activation energy (E_a) and the relaxation time (τ₀) are calculated using the Arrhenius equation. The dielectric relaxation strength (Δε) is strongly temperature dependent. The calculated values of E_a for ac conductivity, ln(σ), of PHB provide information about the presence of electronic conduction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fast crystallization of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) with talc and boron nitride as nucleating agents

The crystallization behavior of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) induced by two kinds of nucleating agents, boron nitride (BN) and talc, was investigated by differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. Both BN and talc have good nucleating ability in the crystallization of PHB and PHBV. From these results, combined with molecular weight measurement by gel permeation chromatography, the mechanism of nucleation by BN and talc in the crystallization of PHB and PHBV has been proposed. BN acts as a nucleating agent itself and initiates nucleation in the crystallization of PHB and PHBV. Talc acts in a different way. It reacts as a chemical reagent with the molten chains of PHB/PHBV, while the reaction product acts as the true nucleating agent, which lowers the crystallization barriers of PHB and PHBV. ¹H NMR spectroscopy provides evidence for the reaction between PHB and talc and supports the proposed nucleation mechanism. Copyright © 2005 Society of Chemical Industry     

The synthesis of poly(3‐hydroxybutyrate)‐g‐poly(methylmethacrylate) brush type graft copolymers by atom transfer radical polymerization method

Brush type of poly (3‐hydroxy butyrate), PHB, copolymer synthesis has been reported. Natural PHB was chlorinated by passing chlorine gas through PHB solution in CHCl₃/CCl₄ mixture (75/25 v/v) to prepare chlorinated PHB, PHB‐Cl, with the chlorine contents varying between 2.18 and 39.8 wt %. Toluene solution of PHB‐Cl was used in the atom transfer radical polymerization (ATRP) of methyl methacrylate, MMA, in the presence of cuprous bromide (CuBr)/2,2′‐bipyridine complex as catalyst, at 90°C. This “grafting from” technique led to obtain poly (3‐hydroxybutyrate)‐g‐poly(methylmethacrylate) (PHB‐g‐PMMA) brush type graft copolymers (cylindrical brush). The polymer brushes were fractionated by fractional precipitation methods and the γ values calculated from the ratio of the volume of nonsolvent to volume of solvent of brushes were ranged between 2.8 and 9.5 depending on the molecular weight, grafting density, and side chain length of the brushes, while the γ values of PHB, PHB‐Cl, and homo‐PMMA were 2.7–3.8, 0.3–2.4, and 3.0–3.9, respectively. The fractionated brushes were characterized by gel permeation chromatography, ¹H‐NMR spectrometry, thermogravimetric analysis (TGA), and differential scanning calorimetry techniques. PHB‐g‐PMMA brush type graft copolymers showed narrower molecular weight distribution (mostly in range between 1.3 and 2.2) than the PHB‐Cl macroinitiator (1.6–3.5). PHB contents in the brushes were calculated from their TGA thermograms and found to be in range between 22 and 42 mol %. The morphologies of PHB‐g‐PMMA brushes were also studied by scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of orotic acid as a nucleating agent on the crystallization of bacterial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) copolymers

The kinetics of crystallization induced by orotic acid (OA) and boron nitride (BN) as nucleating agents were investigated for bacterial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)s (P(HB‐co‐HH)s) containing from 0 to 18% HH monomer units. The nucleation efficiency of these two chemicals was investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that both orotic acid and boron nitride are able to nucleate the crystallization of PHB. In the case of P(HB‐co‐HH) copolymers, orotic acid showed an outstanding nucleating effect. The comparison of half‐crystallization times shows that for P(HB‐co‐10% HH), the crystallization initiated by orotic acid is more than three time faster than the one induced by boron nitride (t_1/2BN/t_1/2OA(60°C) = 3.7 and t_1/2BN/t_1/2OA(90°C) = 4.5). According to the fact that orotic acid is a biodegradable, biocompatible and a nontoxic chemical, this nucleating agent is a promising solution for PHAs used in medical applications such as implants. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Improvement of the production of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxybutyrate) terpolyester by manipulating the culture condition

BACKGROUND: The aim of this work is to enhance the production of terpolyester poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate‐co‐4‐hydroxybutyrate) (P(3HB‐co‐3HV‐co‐4HB)) produced by a locally isolated bacterium, Cupriavidus sp. USMAA2‐4. The monomer composition was varied by supplementing different carbon precursors and by manipulating the culture condition through one‐stage cultivation. The effect of C/N ratio and different concentrations of carbon source and precursors were investigated in order to produce higher content of this terpolyester. Although research on this biodegradable polyester is abundant, studies on terpolyester P(3HB‐co‐3HV‐co‐4HB) are still limited. RESULTS: Supplementation of oleic acid in accumulation medium increased the bacterial growth and polyhydroxyalkanoate (PHA) accumulation. It was also shown that medium consisting of assorted carbon precursors at C/N 20 gave relatively high dry cell weight and P(3HB‐co‐3HV‐co‐4HB) content. Various compositions of terpolyester were obtained when the concentration of oleic acid and 4HB precursors were manipulated. The combination of oleic acid with γ‐butyrolactone and 1‐pentanol was found to be the best combination to produce high PHA content (81 wt%). The composition of monomer in P(3HB‐co‐3HV‐co‐4HB) was produced in the range 8–13 mol% for 3HV and 9–24 mol% for 4HB, respectively. CONCLUSIONS: The production of P(3HB‐co‐3HV‐co‐4HB) in shake‐flasks successfully produced 81 wt% of PHA content. This manipulated culture condition can be used at larger scale to provide modeling for the production of terpolyester in a bioreactor. Copyright © 2012 Society of Chemical Industry     

Production and characterization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) co‐polymer by a N2‐fixing cyanobacterium,Nostoc muscorum Agardh

BACKGROUND: Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [P(3HB‐co‐3HV)] co‐polymer has immense potential in the field of environmental and biomedical sciences as biodegradable and biocompatible material. The present study examines a filamentous N₂‐fixing cyanobacterium, Nostoc muscorum Agardh as a potent feedstock for P(3HB‐co‐3HV) co‐polymer production and characterization of co‐polymer film for commercial applications. RESULTS: Under photoautotrophic growth conditions, N. muscorum Agardh accumulated the homopolymer of poly‐β‐hydroxybutyrate (PHB), whereas synthesis of P(3HB‐co‐3HV) co‐polymer was detected under propionate‐ and valerate‐supplemented conditions. Exogenous carbons such as acetate, fructose and glucose supplementation with propionate/valerate was found highly stimulatory for the co‐polymer accumulation; the content reached 58–60% of dry cell weight (dcw) under P‐/N‐deficiencies with 0.4% acetate + 0.4% valerate supplementation, the highest value reported so far for P(3HB‐co‐3HV) co‐polymer‐producing cyanobacterial species. The material properties of the films were studied by mechanical tests, surface analysis and differential scanning calorimetry (DSC). CONCLUSION: N. muscorum Agardh, a photoautotrophic N₂‐fixing cyanobacterium, emerged as a potent host for production of P(3HB‐co‐3HV) co‐polymer with polymer content 60% of dry cell weight. The material properties of the films were found to be comparable with that of the commercial polymer, thus advocating its potential applications in various fields. Copyright © 2012 Society of Chemical Industry     

Blending and characterizations of microbial poly(3‐hydroxybutyrate) with dendrimers

Blending of microbial polyester poly(3‐hydroxybutyrate) (PHB) with various dendritic polyester oligomers or dendrimers was achieved by solution casting to improve the film forming ability of PHB. Films of the blends were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron micrograph (SEM), and Fourier transform infrared spectroscopy (FTIR). It was revealed that there were mainly two types of interactions in the blending system: the plasticizing or lubricating effect of the low melting spherical dendrimers molecules improved the polymer chain mobility through the suppression of PHB crystallization in the blends; The dendrimers also functioned as crosslinking agents or antiplasticizing agents via weak hydrogen bonding to enhance the overall intermolecular interactions which decrease the chain mobility and thus cause the increase of glass transition temperature (T_g) of PHB. TGA results concluded that incorporating the dendrimers could retard the thermal decomposition of PHB and enhanced its thermal stability accordingly. With the above blend processes, the so‐obtained PHB possessed better film forming ability and even patterned surface structures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3782–3790, 2006     

Atactic poly(methyl methacrylate) blended with poly(3‐D(−)hydroxybutyrate): Miscibility and mechanical properties

Atactic poly(methylmethacrylate), aPMMA, was blended with poly(3‐D(−)hydroxybutyrate), PHB, up to a maximum composition of 25% of polyester, at 190°C in a Brabender‐like apparatus. The resulting blends quenched from the melt to room temperature were completely amorphous, and exhibited a single glass transition using DSC and DMTA, indicating miscibility of the components for this time–temperature history. Tensile experiments showed that at room temperature the 10/90 and 20/80 PHB/aPMMA blends exhibited higher values of strain at break, and slight decreases of the modulus and stress at break compared to neat aPMMA. The tensile energy at break was almost twice that of neat aPMMA. Tensile tests were also performed at 80°C, at which point the 25/75 and 20/80 PHB/aPMMA blends are above T_g, while the 10/90 and neat aPMMA are below T_g. The stress–strain curves obtained were functions of the physical state of the amorphous phase, and also depended on the difference between the test temperatures and T_g. In particular, comparing the neat aPMMA and the blends, decreases of the modulus and stress at break and a respectable increase in the strain at break were observed in the latter. Finally, the results were commented considering the thermal degradation of PHB in the melt during the blend preparation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 746–753, 2000     

Synthesis and characterization of biodegradable poly(ester‐urethanes) based on bacterial poly(R‐3‐hydroxybutyrate)

A series of poly(R‐3‐hydroxybutyrate)/poly(ε‐caprolactone)/1,6‐hexamethylene diisocyanate‐segmented poly(ester‐urethanes), having different compositions and different block lengths, were synthesized by one‐step solution polymerization. The molecular weight of poly(R‐3‐hydroxybutyrate)‐diol, PHB‐diol, hard segments was in the range of 2100–4400 and poly(ε‐caprolactone)‐diol, PCL‐diol, soft segments in the range of 1080–5800. The materials obtained were investigated by using differential scanning calorimetry, wide angle X‐ray diffraction and mechanical measurements. All poly(ester‐urethanes) investigated were semicrystalline with T_m varying within 126–148°C. DSC results showed that T_g are shifted to higher temperature with increasing content of PHB hard segments and decreasing molecular weight of PCL soft segments. This indicates partial compatibility of the two phases. In poly(ester‐urethanes) made from PCL soft segments of molecular weight (M_n ≥ 2200), a PCL crystalline phase, in addition to the PHB crystalline phase, was observed. As for the mechanical tensile properties of poly(ester‐urethane) cast films, it was found that the ultimate strength and the elongation at the breakpoint decrease with increasing PHB hard segment content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 703–718, 2002     

Carbon dioxide sorption and diffusion in poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐CO‐3‐hydroxyvalerate)

CO₂ sorption and diffusion in poly(3‐hydroxybutyrate) and three poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) copolymers were investigated gravimetrically at temperatures from 25° to 50°C and pressures up to 1 atm. The sorption behavior proved to be linear for all the copolymers studied. An additional set of measurements performed in a pressure decay apparatus at 35°C showed that the linearity could be extrapolated to pressures up to 25 atm. The sorption results obtained from both techniques were in good agreement. The poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) sorption kinetics were increasingly non‐Fickian at the higher temperatures, thus preventing the calculation of diffusion coefficients above 35°C. Interestingly, this was not the case for poly(3‐hydroxybutyrate), and diffusion coefficients and permeabilities could be calculated at all of the investigated temperatures. The 35°C permeabilities were fairly low, which is attributed to the high degree of crystallinity of this polyester family. Finally, the poly(3‐hydroxybutyrate) barrier properties against CO₂ are successfully compared with those of some selected common thermoplastics. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2391–2399, 1999     

Effect of lignin particles as a nucleating agent on crystallization of poly(3‐hydroxybutyrate)

The effect of lignin fine powder, as a new kind of nucleating agent, on the crystallization process of poly(3‐hydroxybutyrate) (PHB) was studied. The kinetics of both isothermal and nonisothermal crystallization processes from the melt for both pure PHB and PHB/lignin blend was studied by means of differential scanning calorimetry. Lignin shortened the crystallization half‐time t_1/2 for isothermal crystallization. The activation energy ΔE for PHB/lignin and pure PHB in the isothermal crystallization process was ?237.40 and ?131.22 kJ/mol, respectively, clearly indicating that the crystallization of the PHB/lignin blend was more favorable than that of pure PHB from a thermodynamic perspective. At the same time, according to polarized optical microscopy, the rate of spherulitic growth from the melt increased with the addition of lignin, which is ascribed to the reduction of surface fold energy σ_e, that is, σ_e is 59.2 × 10^?3 and 41.6 × 10^?3 J m^?2 for pure PHB and PHB/lignin, respectively. Polarized optical microscopy also showed that the spherulites found in PHB with lignin were smaller in size and greater in number than those found in pure PHB. The wide‐angle X‐ray diffraction indicated that an addition of lignin caused no change in the crystal structure and degree of crystallinity. These results indicated that lignin is a good nucleating agent for the crystallization of PHB. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2466–2474, 2004