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1.
Poly(butylene succinate) (PBSU) and poly(ε-caprolactone) (PCL) blends, both biodegradable chemosynthetic semicrystalline polyesters, were prepared with the ratio of PBSU/PCL ranging from 80/20 to 20/80 by co-dissolving the two polyesters in chloroform and casting the mixture. The miscibility and crystallization behavior of PBSU/PCL blends were investigated by differential scanning calorimetry and optical microscopy. Experimental results indicated that PBSU was immiscible with PCL as evidenced by the composition independent glass transition temperature and the biphasic melt. However, during the crystallization from the melt at a given cooling rate, the crystallization peak temperature of PBSU in the blends decreased slightly with the increase of PCL, while that of PCL in the blends first increased and then decreased with the increase of PBSU. Moreover, both the crystallization peak temperature of PBSU and PCL shifted to the low temperature range with the increase of the cooling rate for a given blend composition. Double melting peaks or one main melting peak with a shoulder were found for both PBSU and PCL after the complete crystallization cooled from the melt, and were ascribed to the melting-recrystallization mechanism. It was found that the subsequent melting behavior of PBSU/PCL blends was influenced apparently by the blend composition and the cooling rate used.  相似文献   

2.
Blends of poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) and poly(butylene succinate) (PBSU), both biodegradable semicrystalline polyesters, were prepared with the ratio of PHBV/PBSU ranging from 80/20 to 20/80 by co-dissolving the two polyesters in chloroform and casting the mixture. Differential scanning calorimetry (DSC) and optical microscopy (OM) were used to study the miscibility and crystallization behaviour of PHBV/PBSU blends. Experimental results indicate that PHBV is immiscible with PBSU as shown by the almost unchanged glass transition temperature and the biphasic melt. Crystallization of PHBV/PBSU blends was studied by DSC using two-step crystallization and analyzed by the Avrami equation. The crystallization rate of PHBV decreases with the increase of PBSU in the blends while the crystallization mechanism does not change. In the case of the isothermal crystallization of PBSU, the crystallization mechanism does not change. The crystallization rate of PBSU in the blends is lower than that of neat PBSU; however, the change in the crystallization rate of PBSU was not so big in the blends. The different content of the PHBV in the blends does not make a significant difference in the crystallization rate of PBSU.  相似文献   

3.
Nonisothermal melt crystallization kinetics of biodegradable PBSU/PVPh blend was investigated with differential scanning calorimetry (DSC) from the viewpoint of practical application. PBSU/PVPh blends were cooled from the melt at various cooling rates ranging from 2.5 to 40°C/min. The crystallization peak temperature decreased with increasing the cooling rate for both neat and blended PBSU. Furthermore, the crystallization peak temperature of PBSU in the blend was lower than that of neat PBSU at a given cooling rate. Two methods, namely the Avrami equation and the Tobin method, were used to describe the nonisothermal crystallization of PBSU/PVPh blend. It was found that the Avrami equation was more suitable to predict the nonisothermal crystallization of PBSU/PVPh blend than the Tobin method. The effects of cooling rate and blend composition on the crystallization behavior of PBSU were studied in detail. It was found that the crystallization rate decreased with decreasing the cooling rate for both neat and blended PBSU. However, the crystallization of PBSU blended with PVPh was retarded compared with that of neat PBSU at the same cooling rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 972–978, 2007  相似文献   

4.
The melting and crystallization behavior and phase morphology of poly(3-hydroxybutyrate) (PHB) and poly(DL-lactide)-co-poly(ethylene glycol) (PELA) blends were studied by DSC, SEM, and polarizing optical microscopy. The melting temperatures of PHB in the blends showed a slight shift, and the melting enthalpy of the blends decreased linearly with the increase of PELA content. The glass transition temperatures of PHB/PELA (60/40), (40/60), and (20/80) blends were found at about 30°C, close to that of the pure PELA component, during DSC heating runs for the original samples and samples after cooling from the melt at a rate of 20°C/min. After a DSC cooling run at a rate of 100°C/min, the blends showed glass transitions in the range of 10–30°C. Uniform distribution of two phases in the blends was observed by SEM. The crystallization of PHB in the blends from both the melt and the glassy state was affected by the PELA component. When crystallized from the melt during the DSC nonisothermal crystallization run at a rate of 20°C/min, the temperatures of crystallization decreased with the increase of PELA content. Compared with pure PHB, the cold crystallization peaks of PHB in the blends shifted to higher temperatures. Well-defined spherulites of PHB were found in both pure PHB and the blends with PHB content of 80 or 60%. The growth of spherulites of PHB in the blends was affected significantly by 60% PELA content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1849–1856, 1997  相似文献   

5.
Yun Hu  Jianming Zhang  Isao Noda 《Polymer》2008,49(19):4204-4210
The miscibility, crystallization and subsequent melting behavior in binary biodegradable polymer blends of poly(l-lactic acid) (PLLA) and low molecular weight poly(3-hydroxybutyrate) (PHB) have been investigated by differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and wide-angle X-ray diffraction (WAXD). DSC analysis results indicted that PLLA showed no miscibility with high molecular weight PHB (Mw = 650,000 g mol−1) in the 80/20, 60/40, 40/60, 20/80 composition range of the PHB/PLLA blends. On the other hand, it showed some limited miscibility with low molecular weight PHB (Mw = 5000 g mol−1) when the PHB content was below 25%, as evidenced by small changes in the glass transition temperature of PLLA. The partial miscibility was further supported by changes of cold-crystallization behavior of PLLA in the blends. During the nonisothermal crystallization, it was found that the addition of a small amount of PHB up to 30% made the cold-crystallization of PLLA occur in the lower temperature. Meanwhile, the crystallization of PHB and PLLA was observed in the heating process by monitoring characteristic IR bands of each component for the low molecular weight PHB/PLLA 20/80 and 30/70 blends. The temperature-dependent IR and WAXD results also revealed that for PLLA component crystallization, the disorder (α′) phase of PLLA was produced, and that the α′ phase changed to the order (α) phase just prior to the melting point.  相似文献   

6.
The melting behavior of poly(butylene succinate) (PBSU) in miscible blends with poly(ethylene oxide) (PEO), which is a newly found polymer blends of two crystalline polymers by our group, has been investigated by conventional differential scanning calorimetry (DSC). It was found that PBSU showed double melting behavior after isothermal crystallization from the melt under certain crystallization conditions, which was explained by the model of melting, recrystallization and remelting. The influence of the blend composition, crystallization temperature and scanning rate on the melting behavior of PBSU has been studied extensively. With increasing any of the PEO composition, crystallization temperature and scanning rate, the recrystallization of PBSU was inhibited. Furthermore, temperature modulated differential scanning calorimetry (TMDSC) was also employed in this work to investigate the melting behavior of PBSU in PBSU/PEO blends due to its advantage in the separation of exotherms (including crystallization and recrystallization) from reversible meltings (including the melting of the crystals originally existed prior to the DSC scan and the melting of the crystals formed through the recrystallization during the DSC scan). The TMDSC experiments gave a direct evidence of this melting, recrystallization and remelting model to explain the multiple melting behavior of PBSU in PBSU/PEO blends.  相似文献   

7.
The morphology and miscibility of commercial poly(lactide) (PLA)/poly(β‐hydroxybutyrate) (PHB, from 5 to 20 wt %) blends prepared by melt extrusion method, were investigated using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) observations. The results show that for all the studied blend contents, PLA/PHB blends are immiscible. The effects of PHB and talc on the nonisothermal cold crystallization kinetics of PLA were examined using a differential scanning calorimetry (DSC) at different heating rates. PHB acted as a nucleating agent on PLA and the addition of talc to the blend yielded further improvement, since significant increase in the enthalpy peak was observed for samples containing 10 wt % PHB and talc (from 0.5 to 5 phr). The crystallization kinetics were then examined using the Avrami–Jeziorny and Liu–Mo approach. The simultaneous presence of PHB and talc induced a decrease of the crystallization half time. The evolution of activation energies determined with Kissinger's equation suggests that blending with PHB and incorporating talc promote nonisothermal cold crystallization of PLA. The synergistic nucleating effect of PHB and talc was also observed on isothermal crystallization of PLA from the melt. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

8.
The melting, crystallization behaviors, and nonisothermal crystallization kinetics of the ternary blends composed of poly(ethylene terephthalate), poly(trimethylene terephthalate) (PTT) and poly(buthylene terephthalate) (PBT) were studied with differential scanning calorimeter (DSC). PBT content in all ternary blends was settled invariably to be one‐third, which improved the melt‐crystallization temperature of the ternary blends. All of the blend compositions in amorphous state were miscible as evidenced by a single, composition‐dependent glass transition temperature (Tg) observed in DSC curves. DSC melting thermograms of different blends showed different multiple melting and crystallization peaks because of their various polymer contents. During melt‐crystallization process, three components in blends crystallized simultaneously to form mixed crystals or separated crystals depending upon their content ratio. The Avrami equation modified by Jeziorny and the Ozawa theory were employed to describe the nonisothermal crystallization process of two selected ternary blends. The results spoke that the Avrami equation was successful in describing the nonisothermal crystallization process of the ternary blends. The values of the t1/2 and the parameters Zc showed that the crystallization rate of the ternary blends with more poly(ethylene terephthalate) content was faster than that with the lesser one at a given cooling rate. The crystal morphology of the five ternary blends investigated by polarized optical microscopy (POM) showed different size and distortional Maltese crosses or light spots when the PTT or poly(ethylene terephthalate) component varied, suggesting that the more the PTT content, the larger crystallites formed in ternary blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

9.
The melting, isothermal and nonisothermal crystallization behaviors of poly(3‐hydroxybutyrate) (PHB) have been studied by means of temperature modulated differential scanning calorimetry (TMDSC) and conventional DSC. Various experimental conditions including isothermal/annealing temperatures (80, 90, 100, 105, 110, 120, 130, and 140°C), cooling rates (2, 5, 10, 20, and 50°C/min) and heating rates (5, 10, 20, 30, 40, and 50°C/min) have been investigated. The lower endothermic peak (Tm1) representing the original crystals prior to DSC scan, while the higher one (Tm2) is attributed to the melting of the crystals formed by recrystallization. Thermomechanical analysis (TMA) was used to evaluate the original melting temperature (Tmelt) and glass transition temperature (Tg) as comparison to DSC analysis. The multiple melting phenomenon was ascribed to the melting‐recrystallization‐remelting mechanism of the crystallites with lower thermal stability showing at Tm1. Different models (Avrami, Jeziorny‐modified‐Avrami, Liu and Mo, and Ozawa model) were utilized to describe the crystallization kinetics. It was found that Liu and Mo's analysis and Jeziorny‐modified‐Avrami model were successful to explain the nonisothermal crystallization kinetic of PHB. The activation energies were estimated in both isothermal and nonisothermal crystallization process, which were 102 and 116 kJ/mol in respective condition. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42412.  相似文献   

10.
Biodegradable polymer blends of high-molecular-weight poly(3-hydroxybutyrate) (PHB) and poly(lactic acid) (PLA) are not miscible in general. Yet, by decreasing the molecular weight of PHB, the low-molecular-weight PHB could have improved miscibility with the PLA. In this study, a melt-induced degradation process of PLA/PHB blends was therefore implemented, termed the in-situ self-compatibilization approach, to produce low-molecular-weight PHB during melt blending process. The solution blends of PLA and oligomer PHB (PLA/OPHB) were also prepared as a basis to understand the role of low-molecular-weight PHB to improve its miscibility with PLA in PLA/PHB blends. Only one single glass transition temperature (Tg) was found for the resulting PLA/PHB blends at compositions of 95/05 to 80/20, proving that the miscibility was greatly improved by decreasing molecular weight of PHB. Because the degraded PHB had a relatively lower Tg, it thus provided plasticization effect to the PLA and resulted in the decreased crystallization temperature. Moreover, with increasing PHB content to 20% in the blend, the elongation at break increased significantly from 7.2% to 227%, more than 30-fold. The extensive shear yielding and necking behavior were observed during tensile testing for the blend of 80/20. The localized plasticization within PLA/PHB matrix with the reduction of local yield stress and the well-dispersed PHB crystallites were the major contributing factors to trigger shear yielding phenomenon. Moreover, initial modulus decreased only 20%, from 1.68 to 1.35 GPa. A common problem of severely reduced stiffness from the added plasticizer encountered in the plasticized PLA blends was therefore not perceived here.  相似文献   

11.
The miscibility, thermal behaviour, morphology and mechanical properties of poly[(R)‐3‐hydroxybutyrate] (PHB) with poly(γ‐benzyl‐L ‐glutamate) (PBLG) are investigated by means of differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and tensile tests. The DSC results show that PHB and PBLG are immiscible in the melt state. Such immiscibility also exists in the amorphous state due to a clear two‐phase separated structure observed by SEM measurements. The blend samples with different thermal history, namely as original and melt samples separately, display differences in thermal behaviour such as the DSC scan profile, the crystallinity and the melting temperature of PHB. The crystallization of PHB both from the molten state and the amorphous state is retarded on addition of the second component. The SEM measurements reveal that a phase inversion occurs between the PHB/PBLG (60/40) and PHB/PBLG (40/60) blends. Except for the PHB/PBLG (40/60) blend, a microphase separated structure is observed for all blend compositions. The mechanical properties vary considerably with blend composition. Compared with pure components, the PHB/PBLG (20/80) blend shows a certain improvement in mechanical properties. © 2001 Society of Chemical Industry  相似文献   

12.
Zhaobin Qiu  Wantai Yang  Toshio Nishi 《Polymer》2005,46(25):11814-11819
Biodegradable polymer blends of poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) and poly(ε-caprolactone) (PCL) blends were prepared with the ratio of PHBV/PCL ranging from 80/20-20/80 by co-dissolving the two polyesters in chloroform and casting the mixture. Differential scanning calorimetry (DSC) and optical microscopy (OM) were used to investigate the miscibility and crystallization of PHBV/PCL blends. Experimental results indicated that PHBV showed no miscibility with PCL for PHBV/PCL blends as evidenced by the existence of unchanged composition independent glass transition temperature and the biphasic melt. Crystallization of PHBV and PCL was studied with DSC and analyzed by the Avrami equation by using two-step crystallization in the PHBV/PCL blends. The crystallization rate of PHBV at 70 °C decreased with the increase of PCL in the blends, while the crystallization mechanism did not change. In the case of the isothermal crystallization of PCL at 42 °C, the crystallization rate increased with the addition of PHBV, and the crystallization mechanism changed, too, indicating that the crystallization of PHBV at 70 °C had an apparent influence on the crystallization of PCL at 42 °C.  相似文献   

13.
The subsequent melting behaviour of poly(butylene succinate) (PBSU) and poly(ethylene succinate) (PES) was investigated using DSC and temperature modulated DSC (TMDSC) after they finished nonisothermal crystallization from the melt. PBSU exhibited two melting endotherms in the DSC traces upon heating to the melt, which was ascribed to the melting and recrystallization mechanism. However, one melting endotherm with one shoulder and one crystallization exotherm just prior to the melting endotherm were found for PES. The crystallization exotherm was ascribed to the recrystallization of the melt of the crystallites with low thermal stability, and the shoulder was considered to be the melting endotherm of the crystallites with high thermal stability. The final melting endotherm was ascribed to the melting of the crystallites formed through the reorganization of the crystallites with high thermal stability during the DSC heating process. TMDSC experiments gave the direct evidences to support the proposed models to explain the melting behaviour of PBSU and PES crystallized nonisothermally from the melt.  相似文献   

14.
Melting behavior and crystal morphology of poly(3‐hydroxybutyrate)‐poly(D ,L ‐lactic acid) (PHB‐RPLA) blends with various compositions have been investigated by modulated temperature differential scanning calorimetry (mt‐DSC), polarized optical thermomicroscopy (POTM), modulated force thermomechanometry (mf‐TM), and small angle X‐ray scattering (SAXS). Thermal properties were investigated after fast cooling crystallization treatment. Multiple melting peak behavior was observed for all polymers. mt‐DSC data revealed that PHB‐RPLA blends undergo melting‐recrystallization‐remelting during heating, as evidenced by exothermic peaks in the nonreversing heat capacity. A decrease in degree of crystallinity due to significant melt‐recrystallization was observed for blends. PHB‐RPLA showed different crystal morphologies for various compositions. POTM results showed that the crystallization rates and sizes of spherulites were significantly reduced as RPLA content increased. mf‐TM results confirmed miscibility of these two polymers. SAXS data provided evidence of lamella thickness of blends, which increased with increasing RPLA content. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers  相似文献   

15.
A series of blends of furan‐based green polyesters, for eco‐friendly packaging materials, are synthesized. Poly(ethylene 2,5‐furandicarboxylate) (PEF), poly(propylene 2,5‐furandicarboxylate) (PPF), and poly(butylene 2,5‐furandicarboxylate) (PBF) are synthesized by applying melt polycondensation. Blends of the above polyesters with 50/50 w/w composition as well as blends of furanoate/terephthalate (PPF/PPT) are also prepared. The glass temperature along with the crystallization and melting behaviors of melt quenched blends are studied aiming at understanding their dynamic state and miscibility. Based on their Tg and crystallization behavior, PEF/PPF shows dynamic homogeneity and miscibility whereas PPF/PBF and PEF/PBF exhibit partial miscibility and immiscibility, respectively. In an effort to dynamically homogenize the compounds, reactive blending is applied and the behavior of the resulting blends is monitored following quenching. A profound improvement in blend homogenization is observed with increasing melt mixing time for the PPF/PPT sample, evidenced by the single glass temperature and by the narrowing in liquid‐to‐glass regime. The obtained single glass temperature together with the suppressed tendency for crystallization with increasing mixing time are taken as evidences of dynamic and thermodynamic homogeneity.  相似文献   

16.
Miscibility and crystallization behavior have been investigated in blends of poly(butylene succinate) (PBSU) and poly(ethylene oxide) (PEO), both semicrystalline polymers, by differential scanning calorimetry and optical microscopy. Experimental results indicate that PBSU is miscible with PEO as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer-polymer interaction parameter, obtained from the melting depression of the high-Tm component PBSU using the Flory-Huggins equation, is composition dependent, and its value is always negative. This indicates that PBSU/PEO blends are thermodynamically miscible in the melt. The morphological study of the isothermal crystallization at 95 °C (where only PBSU crystallized) showed the similar crystallization behavior as in amorphous/crystalline blends. Much more attention has been paid to the crystallization and morphology of the low-Tm component PEO, which was studied through both one-step and two-step crystallization. It was found that the crystallization of PEO was affected clearly by the presence of the crystals of PBSU formed through different crystallization processes. The two components crystallized sequentially not simultaneously when the blends were quenched from the melt directly to 50 °C (one-step crystallization), and the PEO spherulites crystallized within the matrix of the crystals of the preexisted PBSU phase. Crystallization at 95 °C followed by quenching to 50 °C (two-step crystallization) also showed the similar crystallization behavior as in one-step crystallization. However, the radial growth rate of the PEO spherulites was reduced significantly in two-step crystallization than in one-step crystallization.  相似文献   

17.
The miscibility and effect of physical aging on the crystallization behavior of poly(l ‐lactic acid) (PLLA)/poly(3‐hydroxybutyrate) (PHB) blends with a small amount of PHB (≤10 wt%) have been investigated using differential scanning calorimetry and Fourier transform infrared spectroscopy. It is found that the miscibility of PLLA/PHB blends with a very small percentage of PHB can be modulated by varying the molecular weight of the PHB. That is, a PLLA/PHB blend with low‐molecular‐weight PHB is miscible, whereas that with high‐molecular‐weight PHB is immiscible. It is found that physical aging at temperatures far below the glass transition temperature can promote the cold crystallization kinetics of PLLA in PLLA/PHB blends with high‐molecular‐weight PHB rather than in those with low‐molecular‐weight PHB. These findings suggest that the effect of physical aging on the crystallization behavior of the main component in a crystalline/crystalline blend with a small percentage of the second component is strongly dependent on the miscibility of the blend system. Enhanced chain mobility of PLLA in the interface region of PLLA matrix and PHB micro‐domains is proposed to explain the physical aging‐enhanced crystallization rate in immiscible PLLA/PHB blends with high‐molecular‐weight PHB. © 2013 Society of Chemical Industry  相似文献   

18.
The thermal behaviour and phase morphology of poly(3-hydroxybutyrate) (PHB) and starch acetate (SA) blends have been studied by differential scanning calorimetry, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy and polarizing optical microscopy. PHB/SA blends were immiscible. The melting temperatures of PHB in the blends showed some shift with increase of SA content. The melting enthalpy of the PHB phase in the blend was close to the value for pure PHB. The glass transition temperatures of PHB in the blends remained constant at 9°C. The FTIR absorptions of hydroxyl groups of SA and carbonyl groups of PHB in the blends were found to be independent of the second component at 3470cm-1 and 1724cm-1, respectively. The crystallization of PHB was affected by the addition of the SA component both from the melt on cooling and from the glassy state on heating. The temperature and enthalpy of non-isothermal crystallization of PHB in the blends were much lower than those of pure PHB. The crystalline morphology of PHB crystallized from the melt under isothermal conditions varied with SA content. The cold crystallization peaks of PHB in the blends shifted to higher temperatures compared with that of pure PHB. ©1997 SCI  相似文献   

19.
The miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) (PEO/PVA) blends were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and polarizing optical microscopy. Because the glass‐transition temperature of PVA was near the melting point of PEO crystalline, an uncommon DSC procedure was used to determine the glass‐transition temperature of the PVA‐rich phase. From the DSC and DMA results, two glass‐transition temperatures, which corresponded to the PEO‐rich phase and the PVA‐rich phase, were observed. It was an important criterion to indicate that a blend was immiscible. It was also found that the preparation method of samples influenced the morphology and crystallization behaviors of PEO/PVA blends. The domain size of the disperse phase (PVA‐rich) for the solution‐cast blends was much larger than that for the coprecipitated blends. The crystallinity, spherulitic morphology, and isothermal crystallization behavior of PEO in the solution‐cast blends were similar to those of the neat PEO. On the contrary, these properties in the coprecipitated blends were different from those of the neat PEO. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1562–1568, 2004  相似文献   

20.
The influences of the glass fiber (GF) content and the cooling rate for nonisothermal crystallization process of poly(butylene terephthalate)/poly(ethylene terephthalate) (PBT/PET) blends were investigated. The nonisothermal crystallization kinetics of samples were detected by differential scanning calorimetry (DSC) at cooling rates of 5°C/min, 10°C/min, 15°C/min, 20°C/min, 25°C/min, respectively. The Jeziony and Mozhishen methods were used to analyze the DSC data. The crystalline morphology of samples was observed with polarized light microscope. Results showed that the Jeziony and Mozhishen methods were available for the analysis of the nonisothermal crystallization process. The peaks of crystallization temperature (Tp) move to low temperature with the cooling rate increasing, crystallization half‐time (t1/2) decrease accordingly. The crystallization rate of PBT/PET blends increase with the lower GF contents while it is baffled by higher GF contents. POLYM. COMPOS. 36:510–516, 2015. © 2014 Society of Plastics Engineers  相似文献   

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