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1.
Biopolyesters poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) with an 11 mol % 4HB content [P(3HB‐co‐11%‐4HB)] and a 33 mol % 4HB content [P(3HB‐co‐33%‐4HB)] were blended by a solvent‐casting method. The thermal properties were investigated with differential scanning calorimetry. The single glass‐transition temperature of the blends revealed that the two components were miscible when the content of P(3HB‐co‐33%‐4HB) was less than 30% or more than 70 wt %. The blends, however, were immiscible when the P(3HB‐co‐33%‐4HB) content was between 30 and 70%. The miscibility of the blends was also confirmed by scanning electron microscopy morphology observation. In the crystallite structure study, X‐ray diffraction patterns demonstrated that the crystallites of the blends were mainly from poly(3‐hydroxybutyrate) units. With the addition of P(3HB‐co‐33%‐4HB), larger crystallites with lower crystallization degrees were induced. Isothermal crystallization was used to analyze the melting crystallization kinetics. The Avrami exponent was kept around 2; this indicated that the crystallization mode was not affected by the blending. The equilibrium melting temperature decreased from 144 to 140°C for the 80/20 and 70/30 blends P(3HB‐co‐11%‐4HB)/P(3HB‐co‐33%‐4HB). This hinted that the crystallization tendency decreased with a higher P(3HB‐co‐33%‐4HB) content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

2.
Miscibility and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST)/poly(hydroxyl ether biphenyl A) (phenoxy) blends were investigated with various techniques in this work. PBST and phenoxy are completely miscible as evidenced by the single composition‐dependent glass transition temperature over the entire blend compositions. Nonisothermal melt crystallization peak temperature is higher in neat PBST than in the blends at a given cooling rate. Isothermal melt crystallization kinetics of neat and blended PBST was studied and analyzed by the Avrami equation. The overall crystallization rate of PBST decreases with increasing crystallization temperature and the phenoxy content in the PBST/phenoxy blends; however, the crystallization mechanism of PBST does not change. Moreover, blending with phenoxy does not modify the crystal structure but reduces the crystallinity degree of PBST in the PBST/phenoxy blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

3.
Natural amorphous polymer poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P3HB4HB) containing 41 mol % of 4HB was blended with poly(3‐hydroxybutyrate) (PHB) with an aim to improve the properties of PHB. The influence of P3HB4HB contents on thermal and mechanical properties of the blends was evaluated with differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, stress–strain measurement and thermo gravimetric analyzer. Miscibility of PHB/P3HB4HB blends was mainly decided by the contents of P3HB4HB. When P3HB4HB exceeded 50 wt %, the two polymer phases separated and showed immiscibility. The addition of P3HB4HB did not alter the crystallinity of PHB, yet it diluted the PHB crystalline phase as revealed by DSC studies. DSC and FTIR results showed that the overall crystallinity of the blends decreased remarkably with increasing of P3HB4HB contents. Decreased glass transition temperature and crystallinity imparted desired flexibility for the blends. The ductility of the blends increased progressively with increasing of P3HB4HB content. Thus, the PHB mechanical properties can be modulated by changing the blend composition. P3HB4HB did not significantly improve the thermal stability of PHB, yet it is possible to melt process PHB without much molecular weights loss via blending it with suitable amounts of P3HB4HB. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

4.
Blends of synthetic poly(propylene carbonate) (PPC) with a natural bacterial copolymer of 3‐hydroxybutyrate with 3‐hydroxyvalerate (PHBV) containing 8 mol % 3‐hydroxyvalerate units were prepared with a simple casting procedure. PPC was thermally stabilized by end‐capping before use. The miscibility, morphology, and crystallization behavior of the blends were investigated by differential scanning calorimetry, polarized optical microscopy, wide‐angle X‐ray diffraction (WAXD), and small‐angle X‐ray scattering (SAXS). PHBV/PPC blends showed weak miscibility in the melt, but the miscibility was very low. The effect of PPC on the crystallization of PHBV was evident. The addition of PPC decreased the rate of spherulite growth of PHBV, and with increasing PPC content in the PHBV/PPC blends, the PHBV spherulites became more and more open. However, the crystalline structure of PHBV did not change with increasing PPC in the PHBV/PPC blends, as shown from WAXD analysis. The long period obtained from SAXS showed a small increase with the addition of PPC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4054–4060, 2003  相似文献   

5.
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   

6.
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   

7.
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   

8.
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 (Tg) 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 Tg. 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  相似文献   

9.
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 (Tg), 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 Tg 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  相似文献   

10.
Structure and mechanical properties for binary blends composed of a poly(3‐hydroxybutyrate) (PHB) and a cellulose derivative, such as cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB), have been studied by means of dynamic mechanical analysis, isothermal crystallization measurements, and tensile testing. It is found that β relaxation temperature due to glass transition of PHB or PHB‐rich phase in the blends, in which the cellulose derivative has lower molecular weight, is almost the same as that of the pure PHB. On the other hand, the peak location is shifted to even lower temperature than that of the pure PHB by blending the cellulose derivative with higher molecular weight, although the cellulose derivative is a glassy polymer with high glass transition temperature. Further, the blend with lower β relaxation temperature exhibits ductile behavior with low modulus in uniaxial deformation. The difference in the structure and mechanical properties for the blends are found to be determined by the crystallization rate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3447–3452, 2007  相似文献   

11.
Blends of two biodegradable and semicrystalline polymers, poly(L ‐lactic acid) (PLLA) and poly(butylene succinate‐co‐adipate) (PBSA), were prepared by solvent casting in different compositions. The miscibility, morphology, and thermal behavior of the blends were investigated using differential scanning calorimetry and optical microscopy. PLLA was found to be immiscible with PBSA as evidenced by two independent glass transitions and biphasic melt. Nonisothermal crystallization measurements showed that fractionated crystallization behavior occurred when PBSA was dispersed as droplets, evidenced by multiple crystallization peaks at different supercooling levels. Crystallization and morphology of the blends were also investigated through two‐step isothermal crystallization. For blends where PLLA was the major component, different content of PBSA did not make a significant difference in the crystallization mechanism and rate of PLLA. For blends where PBSA was the major component, the crystallization rate of PBSA decreased with increasing PLLA content, while the crystallization mechanism did not change. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

12.
Biodegradable polymer blends based on poly(lactic acid) (PLA) and poly[(butylene succinate)‐co‐adipate] (PBSA) were prepared with a laboratory internal mixer. An epoxy‐based, multifunctional chain extender was used to enhance the melt strength of the blends. The morphology of the blends was observed with field emission scanning electron microscopy. The elongational viscosities of the blends, with and without chain extender, were measured with a Sentmanat extensional rheometer universal testing platform. The blends with chain extender exhibited strong strain‐hardening behavior, whereas the blends without chain extender exhibited only weak strain‐hardening behavior. Measurements of the linear viscoelastic properties of the melts suggested that the chain extender promoted the development of chain branching. The results show that PBSA contributed to significant improvements in the ductility of the PLA/PBSA blends, whereas the chain extender did not have a significant effect on the elastic modulus and strain at break of the blends. The combined blending of PLA with PBSA and the incorporation of the chain extender imparted both ductility and melt strength to the system. Thus, such an approach yields a system with enhanced performance and processability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

13.
Silica nanoparticles and poly(butylene succinate) (PBS) nanocomposites were prepared by a melt‐blending process. The influence of silica nanoparticles on the nonisothermal crystallization behavior, crystal structure, and mechanical properties of the PBS/silica nanocomposites was investigated. The crystallization peak temperature of the PBS/silica nanocomposites was higher than that of neat PBS at various cooling rates. The half‐time of crystallization decreased with increasing silica loading; this indicated the nucleating role of silica nanoparticles. The nonisothermal crystallization data were analyzed by the Ozawa, Avrami, and Mo methods. The validity of kinetics models on the nonisothermal crystallization process of the PBS/silica nanocomposites is discussed. The approach developed by Mo successfully described the nonisothermal crystallization process of the PBS and its nanocomposites. A study of the nucleation activity revealed that the silica nanoparticles had a good nucleation effect on PBS. The crystallization activation energy calculated by Kissinger's method increased with increasing silica content. The modulus and yield strength were enhanced with the addition of silica nanoparticles into the PBS matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

14.
Two series of biodegradable polymer blends were prepared from combinations of poly(L ‐lactide) (PLLA) with poly(?‐caprolactone) (PCL) and poly(butylene succinate‐co‐L ‐lactate) (PBSL) in proportions of 100/0, 90/10, 80/20, and 70/30 (based on the weight percentage). Their mechanical properties were investigated and related to their morphologies. The thermal properties, Fourier transform infrared spectroscopy, and melt flow index analysis of the binary blends and virgin polymers were then evaluated. The addition of PCL and PBSL to PLLA reduced the tensile strength and Young's modulus, whereas the elongation at break and melt flow index increased. The stress–strain curve showed that the blending of PLLA with ductile PCL and PBSL improved the toughness and increased the thermal stability of the blended polymers. A morphological analysis of the PLLA and the PLLA blends revealed that all the PLLA/PCL and PLLA/PBSL blends were immiscible with the PCL and PBSL phases finely dispersed in the PLLA‐rich phase. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

15.
In this study, melt blends of poly(butylene terephthalate) (PBT) with epoxy resin were characterized by dynamic mechanical analysis, differential scanning calorimetry, tensile testing, Fourier transform infrared spectroscopy, and wide‐angle X‐ray diffraction. The results indicate that the presence of epoxy resin influenced either the mechanical properties of the PBT/epoxy blends or the crystallization of PBT. The epoxy resin was completely miscible with the PBT matrix. This was beneficial to the improvement of the impact performance of the PBT/epoxy blends. The modification of the PBT/epoxy blends were achieved at epoxy resin contents from 1 to 7%. The maximum increase of the notched Izod impact strength (≈ 20%) of the PBT/epoxy blends was obtained at 1 wt % epoxy resin content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

16.
The miscibility, crystallization behavior, tensile properties, and environmental biodegradability of poly(β‐hydroxybutyrate) (PHB)/cellulose acetate butyrate (CAB) blends were studied with differential scanning calorimetry, scanning electron microscopy, wide‐angle X‐ray diffraction, and polarizing optical microscopy. The results indicated that PHB and CAB were miscible in the melt state. With an increase in the CAB content, the degree of crystallinity and melting temperature of the PHB phase decreased, and this broadened the narrow processability window of PHB. As the elongation at break increased from 2.2 to 7.3%, the toughness and ductility of PHB improved. From the degradation test, it could be concluded that degradation occurred gradually from the surface to the inside and that the degradation rate could be adjusted by the addition of the CAB content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2116–2122, 2003  相似文献   

17.
Completely biodegradable blends of poly (propylene carbonate) (PPC) and poly(butylene succinate) (PBS) were melt‐prepared and then compression‐molded. The miscibilities of the two aliphatic polyesters, that is, PPC and PBS, were investigated by dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM). The static mechanical properties, thermal behaviors, crystalline behavior, and melt flowability of the blends were also studied. Static tensile tests showed that the yield strength and the strength at break increased remarkably up to 30.7 and 46.3 MPa, respectively, with the incorporation of PBS. The good ductility of the blends was maintained in view of the large elongation at break. SEM observation revealed a two‐phase structure with good interfacial adhesion. The immiscibility of the two components was verified by the two independent glass‐transition temperatures obtained from DMA tests. Moreover, thermogravimetric measurements indicated that the thermal decomposition temperatures (T?5% and T?10%) of the PPC/PBS blends increased dramatically by 30–60°C when compared with PPC matrix. The melt flow indices of the blends showed that the introduction of PBS improved the melt flowability of the blends. The blending of PPC with PBS provided a practical way to develop completely biodegradable blends with applicable comprehensive properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

18.
Partially crosslinked poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)/poly(butylene succinate) (PHBV/PBS) and poly(β‐hydroxybutyrate)/poly(butylene succinate) (PHB/PBS) blends were prepared by melt compounding with dicumyl peroxide. The effect of partial crosslinking on crystallization of the PHBV/PBS and PHB/PBS blends was investigated systematically. Differential scanning calorimetry results showed that the overall crystallization rates of both PHBV and PBS in their blends were enhanced considerably by the partial crosslinking. Similar results were also detected in the PHB/PBS blends. The polarized optical microscope observation displayed that the nuclei density of PHBV was increased while the spherulitic morphology did not change much. Conversely, the PBS spherulites turned into cloud‐like morphology after the partial crosslinking which is a result of the decrease in spherulite size, the reduction in interspherulite distance and the interconnection of fine PBS domains. Wide angle X‐ray diffraction patterns confirmed the enhancement in crystallization of the PHBV/PBS blends after the partial crosslinking without modification on crystalline forms of the PHBV and PBS components. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41020.  相似文献   

19.
Four blends of poly(hydroxybutyrate) (PHB) and poly(butylene succinate) (PBSU), both biodegradable semicrystalline polyesters, were prepared with the ratio of PHB/PBSU ranging from 80/20 to 20/80 by co-dissolving the two polyesters in N,N-dimethylformamide and casting the mixture. Differential scanning calorimetry (DSC) and optical microscopy (OM) were used to probe the miscibility of PHB/PBSU blends. Experimental results indicated that PHB showed some limited miscibility with PBSU for PHB/PBSU 20/80 blend as evidenced by the small change in the glass transition temperature and the depression of the equilibrium melting point temperature of the high melting point component PHB. However, PHB showed immiscibility with PBSU for the other three blends as shown by the existence of unchanged composition independent glass transition temperature and the biphasic melt. Nonisothermal crystallization of PHB/PBSU blends was investigated by DSC using various cooling rates from 2.5 to 10 °C/min. During the nonisothermal crystallization, despite the cooling rates used two crystallization peak temperatures were found for PHB/PBSU 40/60 and 60/40 blends, corresponding to the crystallization of PHB and PBSU, respectively, whereas only one crystallization peak temperature was observed for PHB/PBSU 80/20 and 20/80 blends. However, it was found that after the nonisothermal crystallization the crystals of PHB and PBSU actually co-existed in PHB/PBSU 80/20 and 20/80 blends from the two melting endotherms observed in the subsequent DSC melting traces, corresponding to the melting of PHB and PBSU crystals, respectively. The subsequent melting behavior was also studied after the nonisothermal crystallization. In some cases, double melting behavior was found for both PHB and PBSU, which was influenced by the cooling rates used and the blend composition.  相似文献   

20.
In order to improve some inferior physical properties of bacterial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) [P(3HB‐co‐3HHx)] by blending with PEO, the miscibility, spherulite morphology, crystallization behavior and mechanical properties of P(3HB‐co‐3HHx)/PEO binary biodegradable polymer blends were investigated. A good miscibility between P(3HB‐co‐3HHx) with a 3HHx unit content of 11 mol‐% and PEO in the amorphous state was found when the PEO weight fraction was 10 wt.‐%, while the miscibility decreased dramatically when the PEO weight fraction exceeded 20 wt.‐%. Strongly depending on the blend composition, the mechanical properties of P(3HB‐co‐3HHx) was found to be significantly improved by blending with PEO with a weight fraction of ≈5–17.5 wt.‐%.

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