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1.
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.  相似文献   

2.
Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV)/phenolic blends are new miscible crystalline/amorphous polymer blends prepared via solution casting method in this work, as evidenced by the single composition dependent glass transition temperature. The measured Tgs can be well fitted by the Kwei equation with a q value of 13.6 for the PHBV/phenolic blends, indicating that the interaction between the two components is strong. The negative polymer–polymer interaction parameter, obtained from the melting depression of PHBV using the Nishi‐Wang equation, indicating the thermal miscibility of PHBV and phenolic. The spherulitic morphology and crystal structure of PHBV/phenolic blends were studied with polar optical microscopy and wide angle X‐ray diffraction compared with those of neat PHBV. It is found that the growth rates of PHBV in the blends are lower than that in neat PHBV at a given crystallization temperature, and the crystal structure of PHBV is not modified by the presence of phenolic in the PHBV/phenolic blends, but the crystallinity decrease with the increasing of phenolic. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

3.
Active biodegradable poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) melt mixed nanocomposites and bilayer structures containing copper oxide (CuO) nanoparticles were developed and characterized. The bilayer structures consisted of a bottom layer of compression molded PHBV3 (3% mol valerate) coated with an active electrospun fibers mat made with CuO nanoparticles and PHBV18 (18% valerate) derived from microbial mixed cultures and cheese whey. The results showed that the water vapor permeability increased with the CuO addition while the oxygen barrier properties were slightly enhanced by the addition of 0.05 wt % CuO nanoparticles to nanocomposite films but a negligible effect was registered for the bilayer structures. However, the mechanical properties were modified by the addition of CuO nanoparticles. Interestingly, by incorporating highly dispersed and distributed CuO nanoparticles in a coating by electrospinning, a lower metal oxide loading was required to exhibit significant bactericidal and virucidal performance against the food‐borne pathogens Salmonella enterica, Listeria monocytogenes, and murine norovirus. The biodisintegration tests of the samples under composting conditions showed that even the 0.05% CuO‐coated structures biodegraded within 35 days. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45673.  相似文献   

4.
Plastic prepared from formulations of cornstarch and poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate) (PHBV) biodegraded in tropical coastal waters. Biodegradation was monitored for 1 year. Starch—PHBV bioplastic appeared to lose weight in two overlapping phases until both biopolymers were entirely consumed. To examine the underlying degradation of starch and PHBV from biphasic weight‐loss profiles, a semiempirical mathematical model was developed from which degradation profiles and lifetimes of the individual biopolymers could be predicted. The model predicted that starch and PHBV in the bioplastic had half‐lives of 19 days and 158 days, respectively. Computed profiles also predicted that the starch in the composite would be completely degraded in 174 days, while residual PHBV would persist in the marine environment for 1107 days. The model further revealed that, for a 30% starch : 70% PHBV composite, PHBV degradation was delayed 46 days until more than 65% of the starch was consumed. This suggested that PHBV degradation was metabolically repressed by glucose derived from starch. Glucose repression of microbial PHBV degradation was substantiated in 91 of 100 environmental isolates. The validity of the elaborated model was proven when its revelations and predictions were later confirmed by chemical analysis of residual bioplastic samples. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1767–1776, 2000  相似文献   

5.
The bioplastic poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV), was isolated from a bioreactor using mixed microbial consortia fed volatile fatty acids (VFA), from fermented dairy manure, as the carbon source. The molar fraction of 3‐hydroxyvalerate (3HV) amounted to 0.33 mol mol?1 for two isolated PHBV samples as determined by GC‐MS and 1H‐NMR spectroscopy. The chemical, thermal, and mechanical properties were determined. The PHBVs had relatively high Mw (~790,000 g mol?1). Only a single glass transition temperature (Tg) and melting point (Tm) were observed. Isolated PHBVs exhibited good flexibility and elongation to break as compared with commercial PHBVs with lower HV. The diad and triad sequence distributions of the monomeric units were determined by 13C‐NMR spectroscopy and followed Bernoullian statistics suggesting that the PHBVs were random. The PHBV sequence distribution was also characterized by electrospray ionization‐mass spectrometry (ESI‐MSn) after partial alkaline hydrolysis to oligomers showing a random 3HV distribution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40333.  相似文献   

6.
Due to the short‐running of mineral oil and the increasing waste problem, biopolymers become more and more important. However, they still suffer from disadvantages, and in many cases, their properties are still insufficient to replace mineral oil based plastics. In this study, the biobased and biodegradable polymer poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) is reinforced by different clay types and their effect on the properties profile is investigated. Natural as well as organomodified montmorillonite and bentonite are dispersed by melt mixing within the PHBV matrix. Thermal stability, crystallization behavior, and dynamic mechanical properties as well as the materials morphology is analyzed. Dispersion state of the nanoclay is found to be crucial for the improvement of the material performance and well dispersed organomodified clays reveal to simultaneously improve different properties of PHBV matrix. POLYM. COMPOS., 34:1033–1040, 2013. © 2013 Society of Plastics Engineers  相似文献   

7.
Poly(N‐vinylpyrrolidone) (PVP) groups were grafted onto poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) backbone to modify the properties of PHBV and synthesize a new novel biocompatible graft copolymer. The effect of graft modification with PVP on the thermal and mechanical properties of PHBV was investigated. The thermal stability of grafted PHBV was remarkably improved while the melting temperature (Tm) was almost not affected by graft modification. The isothermal crystallization behavior of samples was observed by polarized optical microscopy and the results showed that the spherulitic radial growth rates (G) of grafted PHBV at the same crystallization temperature (Tc) decreased with increasing graft yield (graft%) of samples. Analysis of isothermal crystallization kinetics showed that both the surface free energy (σe) and the work of chain‐folding per molecular fold (q) of grafted PHBV increased with increasing graft%, implying that the chains of grafted PHBV are less flexible than ungrafted PHBV. This conclusion was in agreement with the mechanical testing results. The Young's modulus of grafted PHBV increased while the elongation decreased with increasing graft%. The hydrophilicity of polymer films was also investigated by the water contact angle measurement and the results revealed that the hydrophilicity of grafted PHBV was enhanced. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

8.
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 (To) and the temperature of maximum weight‐loss rate (Tp) of control and irradiated PHBV were in line with the heating rate (°C min?1). To and TP 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 (Tm) 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  相似文献   

9.
Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/thermoplastic polyurethane (PHBV/TPU) composites were prepared by solution blending combined with melt processing in an effort to improve the toughness of PHBV and overcome the coalescence phenomena of TPU at the same time. The compatibility, cross‐section morphology, crystal structure, thermal behaviour, and mechanical properties of composites were investigated. Field emission scanning electron microscopy results showed that no distinct interface was found in composites, uniformly dispersed PHBV/TPU composites were obtained. The incorporation of TPU did not change the basic crystalline structure of PHBV, but decreased its crystallinity. What's more, the integrity of PHBV spherulites structure was destroyed and the radial growth rate of spherulites was inhibited. Differential scanning calorimetry results analyzed by Jeziorny method indicated that the nucleation mode of composites did not change. Besides, when TPU content was up to 40 wt%, the initial degradation temperature of PHBV/TPU composite was increased by 5°C, and the elongation‐at‐break was increased by 225% compared with those of PHBV. POLYM. ENG. SCI., 54:1113–1119, 2014. © 2013 Society of Plastics Engineers  相似文献   

10.
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 (Tc) 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  相似文献   

11.
The effect of nucleating agents on the crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was studied. A differential scanning calorimeter was used to monitor the energy of the crystallization process from the melt and melting behavior. During the crystallization process from the melt, nucleating agent led to an increase in crystallization temperature (Tc) of PHBV compared with that for plain PHBV (without nucleating agent). The melting temperature of PHBV changed little with addition of nucleating agent. However, the areas of two melting peaks changed considerably with added nucleating agent. During isothermal crystallization, dependence of the relative degree of crystallization on time was described by the Avrami equation. The addition of nucleating agent caused an increase in the overall crystallization rate of PHBV, but did not influence the mechanism of nucleation and growth of the PHB crystals. The equilibrium melting temperature of PHBV was determined as 187°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. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2145–2152, 2002  相似文献   

12.
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.  相似文献   

13.
In this study, multiwalled carbon nanotubes (MWCNTs) were dispersed into a poly(3‐hydroxybutyrate‐co?3‐hydroxyvalerate) (PHBV) matrix, in which PHBV was either covalently attached to the nanotubes through an esterification reaction between the carboxylic groups of functionalized MWCNTs and the hydroxyl groups of PHBV with toluene diisocyanate as a coupling agent or physically mixed to result in only noncovalent interactions. The structure, crystallization behavior, and thermal properties of the resulting nanocomposites were studied. We found that the crystallization of PHBV grafted onto the MWCNTs (PHBV‐g‐MWCNTs) was markedly hindered and exhibited an exothermic peak caused by cold crystallization, whereas the nonisothermal crystallization of PHBV was enhanced because a heterogeneous nucleation effect appeared in the PHBV/MWCNTs. Moreover, the maximum decomposition temperature of the PHBV‐g‐MWCNTs was improved by about 14.4°C compared with that of the PHBV/MWCNTs and by about 23.7°C compared with that of the original PHBV. Furthermore, the PHBV‐g‐MWCNTs exhibited the wider melt‐processing window than the PHBV/MWCNTs and original PHBV. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4299–4307, 2013  相似文献   

14.
Orthopedic implant failure due to bacterial infection has been a concern in bone tissue engineering. Here, we have formulated a composite made of biodegradable polymer, i.e., poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV), and silver chloride. Ag+ ions released from the AgCl/PHBV film can promote an aseptic environment by promoting inhibition of bacterial growth while maintaining bone cell growth, depending on AgCl loading. The objective of this study is to formulate AgCl/PHBV film(s) of varying composition so as to evaluate the dependence of AgCl loading in the film on antimicrobial activity and cytotoxicity. The release kinetics of silver ions from AgCl/PHBV film in aqueous and Dulbecco's Modified Eagle Medium showed similarity in the initial burst of ions during the first day of desorption followed by a gradual release of ions over extended time period. The antibacterial efficacy of AgCl/PHBV film against Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa was evaluated by microbiological assay, while cytotoxicity of the film toward MC3T3‐E1 cells was determined by MTT assay. For all compositions studied, a clear zone of inhibition around AgCl/PHBV film was noticed on a modified Kirby‐Bauer disk diffusion assay. We established that MC3T3‐E1 cell attachment on AgCl/PHBV film is strongly related to loading of AgCl in the film. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45162.  相似文献   

15.
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 (Tg), 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  相似文献   

16.
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  相似文献   

17.
The packaging industry is searching for alternative materials to attain environmental sustainability. Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate (PHBV) is a semicrystalline polymer that meets this sustainability goal since it is bioderived and biodegradable. However, its brittle nature and relatively high water permeation and transmission rates make it unsuitable for packaging applications. In addition, PHBV has poor mechanical, thermal, and rheological properties above 160 °C, limiting its use in cast sheets and thermo‐formed packaging applications. To improve these properties, new blends of PHBV with high molecular weight natural rubber at 5, 10, 15, and 25% by weight were fabricated, and physico‐chemical properties of the blends were characterized. The rubber in the blends aided in the following: increased thermal stability since the complex viscosities of the blends were improved by one log over pure PHBV at 170 °C, created more uniform melting peaks attesting to improved homogeneity, decreased water permeation to a level similar to that of traditional thermoplastics; increased the elongation at break, and stabilized the Young's modulus. Therefore, these blends can potentially be used in‐place of traditional, petroleum‐based thermoplastics in cast sheets and thermoforms. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43937.  相似文献   

18.
An important strategy used in the polymer industry in recent years is blending two bio‐based polymers to attain desirable properties similar to traditional thermoplastics, thus increasing the application potential for bio‐based and bio‐degradable polymers. Miscibility of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) with poly(L ‐lactic acid) (PLA) were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Three different grades of commercially available PLAs and one type of PHBV were blended in different ratios of 50/50, 60/40, 70/30, and 80/20 (PHBV/PLA) using a micro‐compounder at 175°C. The DSC and TGA analysis showed the blends were immiscible due to different stereo configuration of PLA polymer and two distinct melting temperatures. However, some compatibility between PHBV and PLA polymers was observed due to decreases in PLA's glass transition temperatures. Additionally, the blends do not show clear separation by SEM analysis, as observed in the thermal analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

19.
Polyhydroxybutyrate‐co‐valerate (PHBV) is attracting interest as a new material for packaging applications and nanoparticulate layered silicates are being increasingly explored as a way to improve PHBV film properties. In this context, it is essential to understand how different types of nanofillers could influence polymer properties. PHBV was processed with three‐layered clay types using different mixing methods, and we examined the effect of processing time, clay type, and clay content on polymer molecular weight and composite morphology. PHBV molecular weight (Mw) decreased by 38% after extrusion processing and was further reduced in the presence of montmorillonite (MMT). However, when PHBV was processed with kaolinite as the additive, no further reduction in polymer molecular weight was observed. Molecular weight also decreased as the MMT clay content increased from 1 to 5 wt %. The results suggest that release of tightly bound water from clay surfaces at elevated temperature may be responsible for PHBV degradation during processing. Evidence also points to the possibility that the surface modifier present in organically modified MMT may catalyze PHBV degradation in some way. X‐ray diffraction studies indicated an intercalated morphology in the presence of modified montmorillonite but good dispersion was also achieved when unmodified kaolinite was blended with PHBV. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

20.
Biodegradable polymer blends of poly(butylene succinate) (PBS) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) were prepared with different compositions. The mechanical properties of the blends were studied through tensile testing and dynamic mechanical thermal analysis. The dependence of the elastic modulus and strength data on the blend composition was modeled on the basis of the equivalent box model. The fitting parameters indicated complete immiscibility between PBS and PHBV and a moderate adhesion level between them. The immiscibility of the parent phases was also evidenced by scanning electron observation of the prepared blends. The thermal properties of the blends were studied through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The DSC results showed an enhancement of the crystallization behavior of PBS after it was blended with PHBV, whereas the thermal stability of PBS was reduced in the blends, as shown by the TGA thermograms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42815.  相似文献   

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