Thermogravimetric analysis of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

The thermal degradation of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [P(HB‐HV)] was studied using thermogravimetry (TG). In the thermal degradation of PHB, the temperature at the onset of weight loss (T_o) was derived by T_o = 0.97B + 259, where B represents the heating rate (°C/min). The temperature at which the weight loss rate was maximum (T_p) was T_p = 1.07B + 273, and the final temperature (T_f) at which degradation was completed was T_f = 1.10B + 280. The percentage of the weight loss at temperature T_p (C_p) was 69 ± 1% whereas the percentage of the weight loss at temperature T_f (C_f) was 96 ± 1%. In the thermal degradation of P(HB‐HV) (7:3), T_o = 0.98B + 262, T_p = 1.00B + 278, and T_f = 1.12B + 285. The values of C_p and C_f were 62 ± 7 and 93 ± 1%, respectively. The derivative thermogravimetric (DTG) curves of PHB confirmed only one weight loss step change because the polymer mainly consisted of the HB monomer only. The DTG curves of P(HB‐HV), however, suggested multiple weight loss step changes; this was probably due to the different evaporation rates of the two monomers. The incorporation of 10 and 30 mol % of the HV component into the polyester increased the various thermal temperatures (T_o, T_p, andT_f) by 7–12°C (measured at B = 20°C/min). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2237–2244, 2001     

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     

Thermal degradation of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) in drying treatment

This study examines the isothermal treatment of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) powders and films. The PHB and PHBV crystallinities were determined using X‐ray diffractometry, and shown to increase with temperature (130–150°C) and then decreased from 55% to 45% at 180°C. The crystal morphology of crystal planes (101) and (111) became sharp at a high temperature. The weight average molecular weight (M_w) of PHB decreased from 1,028,000 to 41,800 g/mol when heated at 180°C for 30 min. The molecular weight of PHB decreased more rapidly than that of PHBV with time. No peak signal was observed in gel permeation chromatography after heating at 150°C because the solubility of PHB changed with crystallinity. The thermal behaviors of PHB and PHBV were analyzed by differential scanning calorimetry and thermogravimetric analysis. The roughness, contact angle, and surface morphology of PHB and PHBV films were also measured to determine the surface properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3659–3667, 2013     

Photografting polymerization of polyacrylamide on poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) films. II. Wettability and crystallization behaviors of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)‐graft‐polyacrylamide films

The wettability and crystallization behaviors of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV)‐graft‐polyacrylamide (PAM) films were studied. X‐ray photoelectron spectroscopy analyses illustrated that about 62 atom % of the total polar functionalities on the grafted film with 17% grafting percentage (GP) was amide groups. Wide‐angle X‐ray diffraction results suggest that grafted PAM induced defects in PHBV crystals and influenced their crystal structure. Differential scanning calorimetry (DSC) spectra showed the two melting regions, 60–90 and 145–170°C, of the imperfect PHBV crystals of the grafted films. Grafted PAM could suppress the recrystallization of PHBV, which was consistent with the polarizing optical microscopy results, in which the maximum PHBV spherulite diameter decreased from 350 μm for the PHBV film to 50 μm for the film with 53% GP. In addition, DSC studies revealed that the crystallinity of the grafted films decreased with increasing GP, which facilitated the diffusion of water into the films. The water contact angle of grafted films decreased and the water‐swelling percentage increased as GP went up. These results demonstrate the potential of PHBV‐g‐PAM for wettable surface constructs in tissue engineering applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Hydrolysis of poly(hydroxybutyrate‐co‐hydroxyvalerate) nanoparticles

Poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) is a natural polyester known for its biocompatibility and biodegradability. The hydrolysis of PHBV nanoparticles (90–150 nm) and microparticles (33–58 µm) was investigated. Particles were formulated from preformed polymer(s) by miniemulsification/solvent evaporation technique to obtain nanoparticles or by emulsification/solvent evaporation technique to obtain microparticles. The morphology of the nanoparticles was studied by Field Emission Gun‐Scanning Electron Microscopy (FEG‐SEM). The kinetics of PHBV degradation was followed by gel permeation chromatography. After storage of PHBV nanoparticles for 25 days at 37 °C, the M_n and M_w of PHBV was reduced up to 85 and 80%, respectively. PHBV nanoparticles stored at 4 °C presented a much lower molecular weight reduction. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

Modification of poly(3‐hydroxybutyrate)‐co‐poly(3‐hydroxyvalerate) with natural rubber

Composites of poly(3‐hydroxybutyrate)‐co‐poly(3‐hydroxyvalerate) (PHBHV) with 6% of 3‐hydroxyvalerate (HV) and natural rubber (NR) were prepared by a solvent‐casting method. Different approaches were tested for the composite preparation. Both PHBHV and NR were dissolved in chloroform, followed by its evaporation, giving various layers. The mechanical properties and morphology of the obtained composites were evaluated by tensile tests and scanning electron microscopy (SEM), respectively. The obtained results demonstrated that the final composite has excellent mechanical properties when compared with PHBHV. SEM analysis unequivocally showed the excellent adhesion between the two polymeric layers. This new material was also tested as a drug delivering system using flurbiprofen as a model drug, and then the diffusion coefficients were determined. This article describes an easy method to produce a desirable composite from PHBHV and NR. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Photothermal methods and atomic force microscopy images applied to the study of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) dense membranes

Thermal and transport properties of some polyhydroxyalkanoates (PHAs), poly‐3‐hydroxybutyrate and poly‐3‐hydroxybutyrate‐co‐3‐hydroxyvalerate copolymers at different concentrations (8, 14, and 22%), were studied by using photoacoustic and photothermal techniques. Mass diffusion coefficients were obtained for carbon dioxide and oxygen by using a gas analyzer. Specific heat capacity measurements were performed by monitoring temperature of the samples under white light illumination against time. Thermal diffusivities were determined by using the open photoacoustic cell configuration. The results were discussed considering the incorporation of hydroxyvalerate units in the poly(3‐hydroxybutyrate) unit cell and were correlated with atomic force microscopy images of the upper surface of membranes. New information on transport properties of PHAs is provided. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1491–1497, 2005     

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     

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     

The morphology and degradation behavior of electrospun poly(3‐hydroxybutyrate)/Magnetite and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/Magnetite composites

Electrospinning of biodegradable poly(3‐hydroxybutyrate) (PHB)/magnetite and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV)/magnetite composites in 2,2,2‐trifluoroethanol (TFE) and chloroform are investigated to develop nonwoven nanofibrous structure. Ultrafine PHB/magnetite fibers are obtained and the resulting fiber diameters are in the range of 690–710 nm and 8.0–8.4 µm for the polymer dissolved in TFE and chloroform. The surface of PHB composites fiber fabricated in chloroform contains porous structures, which are not observed for the sample of PHB composites fiber dissolved in TFE. The fiber diameters for PHBV5/magnetite composites are in the range of 500–540 nm and 2.3–2.5 µm, depending on the use of TFE and chloroform. The average diameters of PHBV5/magnetite composite fibers are smaller than those of PHB/magnetite composites fiber. All electrospun PHB/magnetite and composite fibers are superparamagnetic. The degradation behaviors of PHB/magnetite and PHBV5/magnetite composite fibers were investigated using Caldimonas manganoxidans. For the fabricated composite fibers, it is found that the degradation rate increased with the increasing loading of magnetite nanoparticles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41070.     

Biobased blends of poly(propylene carbonate) and poly(hydroxybutyrate‐co‐hydroxyvalerate): Fabrication and characterization

Poly(propylene carbonate) (PPC), a CO₂‐based bioplastic and poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) were melt blended followed by injection molding. Fourier transform infrared spectroscopy detected an interaction between the macromolecules from the reduction in the OH peak and a shift in the C?O peak. The onset degradation temperature of the polymer blends was improved by 5% and 19% in comparison to PHBV and PPC, respectively. Blending PPC with PHBV reduced the melting and crystallization temperatures and crystallinity of the latter as observed through differential scanning calorimetry. The amorphous nature of PPC affected the thermal properties of PHBV by hindering the spherulitic growth and diluting the crystalline region. Scanning electron micrographs presented a uniform dispersion and morphology of the blends, which lead to balanced mechanical properties. Incorporating PHBV, a stiff semi‐crystalline polymer improved the dimensional stability of PPC by restricting the motion of its polymer chains. © 2016 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44420.     

Compatibility of poly(butadiene‐co‐acrylonitrile) with poly(L‐lactide) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

Poly(L ‐lactide) (PLLA) and poly(3‐hydrobutyrate‐co‐3‐hydroxyvalerate) (PHBV) were blended with poly(butadiene‐co‐acrylonitrile) (NBR). Both PLLA/NBR and PHBV/NBR blends exhibited higher tensile properties as the content of acrylonitrile unit (AN) of NBR increased from 22 to 50 wt %. However, two separate glass transition temperatures (T_g) appeared in PLLA/NBR blends irrespective of the content of NBR, revealing that PLLA was incompatible with NBR. In contrast, a single T_g, which shifted along with the blend composition, was observed for PHBV/NBR50 blends. Moreover NBR50 suppressed the crystallization of PHBV, indicating that PHBV was compatible with NBR50. Decrease of both elongation modulus and stress at maximum load was less significant and increase of elongation at break was more pronounced in PHBV/NBR50 blends than in PLLA/NBR50 blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3508–3513, 2004     

Layer double hydroxides for enhanced poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) crystallization

Enabling the widespread utilization of poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] (PHBV) is strongly associated with enhancing its crystallization kinetics. In this article, we utilize a highly surface active (one reactive group per nanometer square) anion exchanged layered‐double hydroxide (LDH) functionalized by stearic acid to probe the crystallization kinetics of PHBV. Our prior work has shown that the addition of LDH decreases the cold crystallization and induces a melt recrystallization peak in PHBV. Since the melt‐recrystallization temperature shifted to higher temperature and its corresponding enthalpy increased with increasing LDH loading, this article is focused on understanding the effect of LDH on kinetics and energetics of PHBV crystallization. Both Avrami and Lauritzen–Hoffman modeling are utilized to develop a comprehensive understanding of thermal history effects through differential scanning calorimetry and polarized optical microscopy measurements. Five concentrations by weight of LDH are used: 1, 3, 5, and 7%. The results show that the addition of LDH promoted both primary and secondary nucleation at low concentrations but additional LDH resulted in primary nucleation alone. The crystallization rate and activation energy show a significant increase, which is accompanied by a decrease in the nucleation constant, the surface energy and the work of chain folding for PHBV crystallization. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2013     

Miscibility,crystallization kinetics,and mechanical properties of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)(PHBV)/poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate)(P3/4HB) blends

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)(PHBV)/poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P3/4HB) blend films were prepared by solvent‐cast method. The nonisothermal crystallization results showed that PHBV and P3/4HB are miscible due to a single glass transition temperature (T_g), which is dependent on blend composition. The isothermal crystallization results demonstrate that the crystallization rate of PHBV becomes slower after adding amorphous P3/4HB with 19.2 mol% 4HB, which could be proved through depression of equilibrium melt point ($T_m^o$ ) from 183.7°C to 177.6°C. For pure PHBV and PHBV/P3/4HB (80/20) blend, the maximum crystallization rate appeared at 88°C and 84°C, respectively. FTIR analysis showed that PHBV/P3/4HB blend films would maintain the helical structure, similar to pure PHBV. Meanwhile, with increasing P3/4HB content, the inter‐ and intra‐interactions of PHBV and P3/4HB decrease gradually. Besides, a lower elastic modulus and a higher elongation at break were obtained, which show that the addition of P3/4HB would make the brittle PHBV to ductile materials. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Compatibilization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)–poly(lactic acid) blends with diisocyanates

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was blended with poly(lactic acid) (PLA) with various reactive processing agents to decrease its brittleness and enhance its processability. Three diisocyanates, namely, hexamethylene diisocyanate, poly(hexamethylene diisocyanate), and 1,4‐phenylene diisocyanate, were used as compatibilizing agents. The morphology, thermomechanical properties, and rheological behavior were investigated with scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, tensile testing, dynamomechanical thermal analysis in torsion mode (dynamic mechanical analysis), and oscillatory rheometry with a parallel‐plate setup. The presence of the diisocyanates resulted in an enhanced polymer blend compatibility; this led to an improvement in the overall mechanical performance but did not affect the thermal stability of the system. A slight reduction in the PHBV crystallinity was observed with the incorporation of the diisocyanates. The addition of diisocyanates to the PHBV–PLA blend resulted in a notable increase in the final complex viscosity at low frequencies when compared with the same system without compatibilizers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44806.     

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     

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     

Crystallization kinetics of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/clay nanocomposites

The preparation and properties of nanocomposites, consisting of a poly(3‐Hydroxybutyrate‐co‐3‐hydroxyvalerate) and an organophilic clay are described. The effect of organophilic clay on the crystallization behavior of (PHBV) was studied. A differential scanning calorimeter (DSC) was used to monitor the energy of the crystallization process from the melt. During the crystallization process from the melt, the organophilic clay led to an increase in crystallization temperature (T_c) of PHBV compared with that for plain PHBV. During isothermal crystallization, dependence of the relative degree of crystallization on time was described by the Avrami equation. The addition of organophilic clay caused an increase in the overall crystallization rate of PHBV, but did not influence the mechanism of nucleation, and growth of the PHBV crystals and the increase caused by a small quantity of clay is move effective than that large one. The equilibrium melting temperature of PHBV was determined as 186°C. Analysis of kinetic data according to nucleation theories showed that the increase in crystallization rate of PHBV in the composite is due to the decrease in surface energy of the extremity surface. The mechanical test shows that the tensile strength of hybrid increased to 35.6 MPa, which is about 32% higher than that of the original PHBV with the incorporation of 3 wt % clay, and the tensile modulus was also increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 655–661, 2004