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1.
For investigating the relationship between thermal properties and biodegradability of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), several films of PHBV containing different polyhydroxyvalerate (HV) fractions were subjected to degradation in different conditions for up to 49 days. Differential scanning calorimetry (DSC), thermogravimetry (TG), specimen weight loss and scanning electron microscopy (SEM) were performed to characterize the thermal properties and enzymatic biodegradability of PHBV. The experimental results suggest that the degradation rates of PHBV films increase with decreasing crystallinity; the degradability of PHBV occurring from the surface is very significant under enzymatic hydrolysis; the crystallinity of PHBV decreased with the increase of HV fraction in PHBV; and no decrease in molecular weight was observed in the partially-degraded polymer.  相似文献   

2.
The aim of this study was the assessment of high energy ball milling technique to develop poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanocomposites containing bacterial cellulose nanowhiskers (BCNW). Crystallization behaviour of PHBV/BCNW nanocomposites was studied under non-isothermal and isothermal conditions using differential scanning calorimetry. The changes in PHBV crystalline structure were also studied using X-ray diffraction. The results confirmed that BCNW acted as nucleating agents and, hence, favored the crystallization of the PHBV. The oxygen permeability of the nanocomposites was reduced by ~22 % when compared to that of the neat PHBV. This work provides a new insight into the development of polyhydroxyalkanoate composites by means of the high energy ball milling technique.  相似文献   

3.
Poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) is a biodegradable polymer synthesized in microorganisms. The application of PHBV is limited by certain material disadvantages. Poly(ε-caprolactone) (PCL) possesses excellent thermodynamic and mechanical properties and was used to modify PHBV in the presence of triethyl citrate (TEC) and dicumyl peroxide (DCP), which was used as plasticizer and grafting agent, respectively. The effects of PCL and additive agents on the mechanical, thermal, amphipathic and degradability behaviors of the blends were investigated. The results showed that the mechanical properties of the PHBV blends improved by PCL incorporation and improved even further after TEC and DCP addition. The addition of DCP could not induce an increase in crystallization temperature but improved the crystallization degree of the blends. The presence of hydrophilic groups in TEC leads to an apparent increases in the hydrophilicity of the PHBV blends. A PHBV/PCL blend (40/60) with TEC (20 wt.%) and DCP (0.5 wt.%) was chosen for its good mechanical properties and hydrophilicity. The chosen ratio of the blends was also shown a preferable degradation activity by biodegradation assay using Pseudomonas mendocina. The addition of TEC and DCP has no conspicuous negative effect on the biodegradation.  相似文献   

4.
In this study, poly(l-lactide) (PLA) films were fabricated by melt processing and the plasticizing effect of hexadecyl lactate (HL) (0, 5, 7.5, 10, and 12.5 wt% on PLA were investigated by scanning electron microscopy (SEM), differential scanning calorimetry, thermogravimetric analysis, tensile, transparency, and water vapor permeability tests. The SEM analysis revealed that PLA with 10 wt% HL appeared uniform with extra small bumps, confirmed the interaction between PLA and HL. The thermal analysis revealed a glass transition temperature of 57.4 °C for neat PLA film, but the addition of HL elicited a decrease in the temperature of the peak (43.8 °C). The incorporation of plasticizer into PLA resulted in the increase of elongation at break, as well as the decrease of tensile strength and tensile modulus. Even though a decrease in transparency was recorded, the PLA/HL blend films appeared transparent by visually observation. The water vapor permeability of PLA/HL blend films increased with the increase of HL. The PLA/HL blend films could effectively extend the shelf-life of fresh-cut pears as the commercial low density polyethylene films. The results indicated that the properties of PLA films can be modified with the addition of HL and PLA/HL blend films could serve as an alternative as food packaging materials to reduce environmental problems associated with synthetic packaging films.  相似文献   

5.
A poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) degrading bacterial strain designated as AF-111 was isolated from sewage sludge sample. The bacterium was identified by 16S rRNA gene sequencing. The results revealed that strain AF-111 showed 99 % similarity with Streptomyces althioticus strain NRRL B-3981 and designated as Streptomyces sp. strain AF-111. An extracellular PHBV depolymerase enzyme was produced under optimized conditions and purified through ammonium sulphate fractionation and column chromatography. The enzyme was purified to homogeneity, indicated by sodium dodecyl sulfate–polyacrylamide gel electrophoresis and molecular weight was found to be approximately 51 kDa. Effect of temperature, pH, metal ions and inhibitors on the PHBV depolymerase activity was determined. The enzyme was stable at wide range of temperature (35–55 °C) and pH (6–8). PHBV depolymerase was stable in the presence of different metal ions except iron and zinc which had inhibitory effect on depolymerase activity. Both ethylenediamine teteracetic acid and phenylmethyl sulphonyl fluoride strongly inhibited enzyme activity which indicates that this enzyme belongs to the serine hydrolase family like other polyhydroxyalkanoate depolymerases. The results show that a depolymerase from strain AF-111 can effectively degrade PHBV, therefore, it can be applied in the process of biochemical monomer recycling.  相似文献   

6.
The effect of lignosulfonate on poly(3-hydroxybutyrate-co-3-hydroxyvalerate), PHBV, was studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The PHBV/lignosulfonate samples were prepared by melt mixing in an internal mixer. SEM showed that PHBV/lignosulfonate samples present a cracked surface that is more intense in mixtures with high lignosulfonate proportions. According to DSC, melting and glass transition temperatures of the PHBV matrix decrease with lignosulfonate addition. The same effect was observed for melting enthalpies (ΔHm), which indicates a decrease of crystallinity. TGA showed that thermal stability of PHBV/lignosulfonate samples was shifted to lower temperatures, which indicates the existence of an interaction between the thermal decomposition processes of PHBV and lignosulfonate.  相似文献   

7.
Cellulose gel films were prepared by regeneration process using pre-cooled aq.(8 wt% LiOH + 15 wt% urea) mixture as solvent and ethyl alcohol as non solvent. The Terminus cattapa leaf extract diffused wet cellulose films were then dipped in 1–5 mM aq.AgNO3 solutions to allow in situ generation of silver nanoparticles (AgNPs). Besides the in situ generation, some AgNPs were also formed outside the wet films in the solution. The AgNPs formed outside the films were observed under transmission electron microscope and scanning electron microscope. The nanocomposite films were also characterized by Fourier transform infrared spectroscopy, X-ray diffraction and thermogravimetric analysis and tensile test. The thermal stability of the composite films was lower than that of the matrix up to a temperature of ~300 °C and afterwards showed a reverse trend. The tensile strength of the nanocomposite films was found to be higher than the matrix but decreased with increasing concentration of aq.AgNO3. The cellulose/AgNPs composite films showed good antibacterial activity against E. coli (gram positive) and Bacillus sp. (gram negative). Based on the aforementioned properties, the cellulose/AgNPs composite films can be considered for antibacterial packaging and medical applications.  相似文献   

8.
Poly(hydroxybutyrate-co-valerate) (PHBV) and poly(ε-caprolactone) (PCL) PCL/PHBV (4:1) blend films were prepared by melt-pressing. The biodegradation of the films in response to burial in soil for 30 days was investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG). The PHBV film was the most susceptible to microbial attack, since it was rapidly biodegraded via surface erosion in 15 days and completely degraded in 30 days. The PCL film also degraded but more slowly than PHBV. The degradation of the PCL/PHBV blend occurred in the PHBV phase, inducing changes in the PCL phases (interphase) and resulting in an increase of its crystalline fraction.  相似文献   

9.
The aim of this work was to evaluate the effect of different plasticizers on the morphology, crystallization, and mechanical properties of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV)/organomodified montmorillonite (OMt) nanocomposites. We investigated three different plasticizers: dioctyl phthalate (DOP), a commonly used additive in the polymer industry, and two natural and biodegradable plasticizers: epoxidized soybean oil (ESO) and triethyl citrate (TEC). The nanocomposites with 3 wt% OMt were obtained by melt processing in an internal mixer. The plasticizers were used alone or in combination with clay in a concentration of 10 wt%. X-ray diffraction and scanning electron microscopy results revealed a partially intercalated structure. The degree of crystallinity was higher for all of the samples compared to neat PHBV, although the melting temperature decreased with the use of plasticizers combined with OMt. The impact strength results were dependent on the interaction between the components of the system. Triethyl citrate was the most effective plasticizer due to its more pronounced interaction with the PHBV matrix, which yielded improvements in processing conditions and PHBV’s flexibility and impact properties.  相似文献   

10.
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), a semi-polycrystalline biopolymer from the polyhydroxyalkanonate family has in recent years become a commercial bioplastic with mechanical properties comparable to isotactic polypropylene and enhanced O2, CO2 and H2O barrier properties. However, its brittleness and sensitivity to thermal and hydrolysis degradations restrict its applications. To overcome the problems associated with degradation during processing blending of PHBV and an epoxy-functionalized chain extender (Joncryl® ADR-4368 S) was conducted in a twin screw extruder. The effect of concentration of the chain extender on thermal, crystallization and rheological behaviours of PHBV was investigated. Thermal gravimetric analysis results indicated improvement in the resistance to thermal decomposition of PHBV by introducing the chain extender. This was accompanied with calculation of thermal degradation activation energy (Ea) using the Flyn–Walls–Ozawa method which confirmed increase of Ea with the increase in content of the chain extender. The rheological behaviour and crystallization of modified PHBV was characterized by rotational rheometry and differential scanning calorimetry techniques, respectively. The results show that addition of chain extender enhanced viscosity of PHBV and also reduce the rate of crystallization.  相似文献   

11.
Studies have shown that the copolymer poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB-co-HHx)] possesses favorable mechanical properties for use in medical supplies and products (e.g., sutures, scaffolds, bone plates). One of the major under-addressed issues associated with the use of biodegradable, bio-based PHA polymers in resorbable medical products is the correlation between the mechanical properties and the in vivo material degradation over time. In this study, P(HB-co-17 mol% HHx) matrices were mechanically tested after either incubation in cultures of human embryonic kidney cells (HEK) for in vitro degradation studies for up to 4 weeks, or inserted into Danio rerio (zebrafish) tissues for in vivo degradation studies for up to 7 weeks. The mechanical properties and scanning electron microscopy (SEM) images of the degraded materials were examined and later correlated to understand the degradation phenomenon. Our results show that Young’s modulus of P(HB-co-17 mol%HHx) during in vitro studies decreased from 3.26 to 2.42 GPa within 4 weeks, and in vivo breakdown resulted in a significant decrease in Young’s modulus with a decrease from 3.26 to 0.51 GPa and a mass loss of 59 % within 7 weeks. SEM images showed the development of pores and cracks on the surface of the material over time. Plasticization and recrystallization were observed and likely play a role in the alteration of mechanical properties.  相似文献   

12.
A series of polyhydroxyalkanoates (PHA), all containing 1% nucleating agent but varying in structure, were melt-processed into films through single screw extrusion techniques. This series consisted of three polyhydroxybutyrate (PHB) and three polyhydroxybutyrate-valerate (PHBV) resins with varying valerate content. Processing parameters of temperature in the barrel (165–173 °C) and chill rolls (60 °C) were optimized to obtain cast films. The gel-permeation chromatography (GPC) results showed a loss of 8–19% of the polymer’s initial molecular weight due to extrusion processing. Modulated differential scanning calorimetry (MDSC) displayed glass transition temperatures of the films ranging from −4.6 to 6.7 °C depending on the amount of crystallinity in the film. DSC data were also used to calculate the percent crystallinity of each sample and slightly higher crystallinity was observed in the PHBV series of samples. X-ray diffraction patterns did not vary significantly for any of the samples and crystallinity was confirmed with X-ray data. Dynamic mechanical analysis (DMA) verified the glass transition trends for the films from DSC while loss modulus (E′) reported at 20 °C showed that the PHBV (3,950–3,600 MPa) had the higher E′ values than the PHB (3,500–2,698 MPa) samples. The Young’s modulus values of the PHB and PHBV samples ranged from 700 to 900 MPa and 900 to 1,500 MPa, respectively. Polarized light microscopy images revealed gel particles in the films processed through single-screw extrusion, which may have caused diminished Young’s modulus and tensile strength of these films. The PHBV film samples exhibited the greatest barrier properties to oxygen and water vapor when compared to the PHB film samples. The average oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) for the PHBV samples was 247 (cc-mil/m2-day) and 118 (g-mil/m2-day), respectively; while the average OTR and WVTR for the PHB samples was 350 (cc-mil/m2-day) and 178 (g-mil/m2-day), respectively. Biodegradation data of the films in the marine environment demonstrated that all PHA film samples achieved a minimum of 70% mineralization in 40 days when run in accordance with ASTM 6691. For static and dynamic incubation experiments in seawater, microbial action resulting in weight loss as a function of time showed all samples to be highly biodegradable and correlated with the ASTM 6691 biodegradation data.  相似文献   

13.
Films of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) and poly(propylene) (PP), PP/PHBV (4:1), blends were prepared by melt-pressing and investigated with respect to their microbial degradation in soil after 120 days. Biodegradation of the films was evaluated by Fourier transform infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, and X-ray diffraction. The biodegradation and/or bioerosion of the PP/PHBV blend was attributed to microbiological attack, with major changes occurring at the interphases of the homopolymers. The PHBV film was more strongly biodegraded in soil, decomposing completely in 30 days, while PP film presented changes in amorphous and interface phase, which affected the morphology.  相似文献   

14.
We intended to find thermophilic degraders of terephthalate-containing Biomax® films. Films in mesh bags were buried in composts (inside temperature: approximately 55–60 °C), resulting in the degradation of them in 2 weeks. Fluorescent microscopy of films recovered from composts showed that microorganisms gradually covered the surface of a film during composting. DGGE analysis of microorganisms on the composted film indicated the presence of Bacillus species as main species (approximately 80% of microbial flora) and actinomycetes (approximately 10–20%) as the second major flora. Isolation of Biomax®-utilizing bacteria was focused on these two genera: two actinomycetes and one Bacillus species were isolated as pure best degraders from the composted polymer films, which were fragmented into small pieces. All the strains were thermophilic and identified, based on their 16S rDNA analyses. Degradation of polymer films was confirmed by (1) accelerated fragmentation of films in composts, compared with a control (no inoculum) and resultant decrease in molecular weights, (2) growth in a powdered Biomax® medium, compared with a control without powdered Biomax®, and (3) production of terephthalate in a powdered Biomax® medium. In this way, we concluded that these bacteria were useful for degradation of thermostable Biomax® products.  相似文献   

15.
There is great interest in developing eco-friendly green biocomposites from plant-derived natural fibers and crop-derived bioplastics attributable to their renewable resource-based origin and biodegradable nature. Fully biodegradable composites, made from both biodegradable polymeric matrices and natural fibers, should be advantageous in some applications, such as one way packaging. Polyhydroxyalkanoates (PHAs) are naturally occurring biodegradable polymers produced from a wide range of microorganisms, with poly(3-hydroxybutyrate) P(3HB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) being important examples of PHAs. In this work, biocomposites of PHBV consisting of a PHBV matrix incorporating peach palm particles (PPp), [i.e., 100/0, 90/10, 80/20 and 75/25 (%w/w) PHBV/PPp] were processed by injection molding at 160 °C. The effect of PPp loading on the thermal and the mechanical properties, as well as on the morphological behavior of the PHBV/PPp biocomposites was investigated. Soil biodegradation tests were carried out by burying specimen beakers containing aged soil and kept under controlled temperature and humidity in accordance with ASTM G160-98. Degradation of the biocomposites was evaluated by visual analysis, scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) following test exposures of up to 5 months. The addition of PPp reduced the maximum strength and the elongation at break of the biocomposites. On the other hand, the Young’s modulus improved with the PPp content. Micrographs of the fracture surfaces following tensile strength testing revealed a large distance between the PHBV matrix and PPp particles although a low interaction is expected. Where measured, these distances tended increase as the PPp content of the biocomposites increased. Soil biodegradation tests indicated that the biocomposites degraded faster than the neat polymer due to the presence of cavities that resulted from introduction of the PPp and that degradation increased with increasing PPp content. These voids allowed for enhanced water adsorption and greater internal access to the soil-borne degrader microorganisms.  相似文献   

16.
Blends of the bacterially produced polyester poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with cellulose acetate esters (CAE) further substituted with propionyl or butyryl groups (degree of substitution: 2.60 propionyl and 0.36 acetyl or 2.59 butyryl and 0.36 acetyl, respectively) were exposed for 4 months to activated sludge to determine their biodegradability. Samples of such blends made by solution-mixing and solvent-casting had complex morphologies in which both individual components as well as a miscible blend phase were present. Additionally, the two opposite surfaces of solvent-cast films showed both physical and chemical differences. After 2 months, samples of pure PHBV had degraded by more than 98% (15 mg/cm2 of surface area), whereas a pure CAE sample had degraded less than 1% (<0.2 mg/cm2). Samples containing 25% CAE lost less than 40% of their initial weights (6 mg/cm2) over the total 4-month period. Samples with 50% CAE lost up to 16% weight (2 mg/cm2), whereas those containing 75% CAE lost only slightly more weight than corresponding sterile control samples (1 mg/cm2). NMR results confirm that weight loss from samples containing 25% CAE resulted only from degradation of PHBV and that the surface of samples became enriched in CAE. Solvent-cast film samples containing equal amounts of PHBV and CAE degraded preferentially on the surface which formed at the polymer-air interface. Scanning electron microscopy and attenuated total reflectance infrared spectroscopy revealed this surface to have a rougher texture and a greater PHBV content.  相似文献   

17.
Neat poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) films and PLLA/PDLA blend films were prepared by solution casting, and their photodegradation by UV-irradiation was investigated using wide-angle X-ray scattering (WAXS), gel permeation chromatography, differential scanning calorimetry, tensile testing, and polarized optical microscopy. The PLLA/PDLA blend film was more photodegradation-resistant than the neat PLLA and PDLA films when photodegradation was monitored by molecular weight, melting temperature, and WAXS crystalline peak positions. This indicates that the chains in both amorphous and crystalline regions of the PLLA/PDLA blend film were photo-cleavage-resistant compared to those of the neat PLLA and PDLA films. The changes in melting temperature and WAXS crystalline peak positions before and after photodegradation respectively indicated the increased crystalline lattice disorder and the decreased crystalline lattice sizes of the neat PLLA and PDLA films, whereas these changes were insignificant for the blend films. Photodegradation caused no significant change in tensile properties, with the exception of significant decreases in the tensile strength and elongation at break of PLLA/PDLA blend film. However, the tensile strength and elongation at break of the PLLA/PDLA blend film retained higher values compared to those of the neat PLLA and PDLA films during photodegradation. In spite of the slower photodegradation of the PLLA/PDLA blend film traced by M n, T m, and WAXS crystalline peak positions than that of neat PLLA and PDLA films, the rapid decrease in tensile strength and elongation at break of the former than that of the latter should be due to the highly-ordered structural difference between them, i.e., the three dimensional dry gel of the former and the spherulites of the latter.  相似文献   

18.
A new type of designed hyperbranched ethylenediamine trazine polymer (HBETP) is successfully synthesized and characterized based upon NMR and GPC. The prepared HBETP is used to modify the poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV)/poly(butylene adipate-co-terephthalate) (PBAT) blends. The effect of HBETP on the microstructure, mechanical properties and thermal properties of the blends is studied. The results indicate that upon addition of 1.0 wt% of HBETP, the impact strength of the PHBV/PBAT blends is increased by 47.1%; ?Tg of the blends decreases from 53.2 to 49.9 °C. These results, together with the morphology analysis of the fractured surface of the blends, conclude the formation of the transition layer between PHBV and PBAT. Also, the XRD result shows that the addition of HBETP can limit the growth of the PHBV crystals and causes the decrease of both the crystallinity and the grain crystalline size. The DSC result demonstrates that the addition of HBETP mainly affects the crystallization of the HB-HV binary eutectic region within PHBV. The mechanism of PHBV/PBAT toughening is due to the formation of the strong physical hydrogen bonding and the chemical micro-crosslinking between HBETP and PHBV/PBAT, which is proposed based on XPS characterization.  相似文献   

19.
Magnetic nanoparticles (MNPs) synthesised by chemical co-precipitation method was subjected to dextran coating by sonication method. The dextran was enzymatically synthesised by extracellular dextransucrase isolated from Weissella cibaria JAG8. The crystalline nature of MNPs and dextran coated MNPs were confirmed by X-ray diffraction studies with average particle size of 25 nm, which was confirmed further by high resolution transmission electron microscopy. The surface morphology of MNPs and dextran coated MNPs were monitored by scanning electron microscopy studies. The vibrating sample magnetometer investigation displayed the super paramagnetic nature of MNPs and dextran coated MNPs. FT-IR analysis of MNPs and dextran coated MNPs, displayed characteristic band of Fe–O bond at 582 cm?1. Thermo-gravimetric analysis of MNPs and dextran coated MNPs (1:1) ratio displayed a weight loss of 15 and 18 %, which clearly indicated 3.0 % of dextran was coated on to the MNPs. The elemental composition study by scanning electron microscopy confirmed the association of dextran with MNPs. The in vitro effect of MNPs and dextran coated MNPs was performed on human colon cancer (HT-29) cell lines and the results showed that dextran coated: MNPs (2:1) displayed good biocompatibility results over dextran coated: MNPs (1:1) and un-coated MNPs.  相似文献   

20.
In this study, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)/bamboo pulp fiber (BPF) composites were prepared by melt compounding and injection molding. The crystallization ability, tensile strength and modulus, flexural strength and modulus, and impact strength were found substantially increased by the addition of BPF. Tensile and flexural elongations were also moderately increased at low fiber contents (<20%). BPF demonstrated not only higher strength and modulus, but also higher failure strain than the PHBV8 matrix. Boron nitride (BN) was also investigated as a nucleation agent for PHBV8 and maleic anhydride grafted PHBV8 (MA-PHBV8) as a compatibilizer for the composite system. BN was found to increase the overall properties of the neat polymer and the composites due to refined crystalline structures. MA-PHBV8 improved polymer/fiber interactions and therefore resulted in increased strength and modulus. However, the toughness of the composites was substantially reduced due to the hindrance to fiber pullout, a major energy dissipation source during the composite deformation.  相似文献   

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