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1.
The miscibility of poly(3‐hydroxyvalerate) (PHV)/poly(p‐vinyl phenol) (PVPh) blends has been studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The blends are miscible as shown by the existence of a single glass transition temperature (Tg) and a depression of the equilibrium melting temperature of PHV in each blend. The interaction parameter was found to be −1.2 based on the analysis of melting point depression data using the Nishi–Wang equation. Hydrogen‐bonding interactions exist between the carbonyl groups of PHV and the hydroxyl groups of PVPh as evidenced by FTIR spectra. The crystallization of PHV is significantly hindered by the addition of PVPh. The addition of 50 wt % PVPh can totally prevent PHV from cold crystallization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 383–388, 1999  相似文献   

2.
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   

3.
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   

4.
The crystallization behaviors, dynamic mechanical properties, tensile, and morphology features of polyamide1010 (PA1010) blends with the high‐impact polystyrene (HIPS) were examined at a wide composition range. Both unmodified and maleic‐anhydride‐(MA)‐grafted HIPS (HIPS‐g‐MA) were used. It was found that the domain size of HIPS‐g‐MA was much smaller than that of HIPS at the same compositions in the blends. The mechanical performances of PA1010–HIPS‐g‐MA blends were enhanced much more than that of PA1010–HIPS blends. The crystallization temperature of PA1010 shifted towards higher temperature as HIPS‐g‐MA increased from 20 to 50% in the blends. For the blends with a dispersed PA phase (≤35 wt %), the Tc of PA1010 shifted towards lower temperature, from 178 to 83°C. An additional transition was detected at a temperature located between the Tg's of PA1010 and PS. It was associated with the interphase relaxation peak. Its intensity increased with increasing content of PA1010, and the maximum occurred at the composition of PA1010–HIPS‐g‐MA 80/20. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 857–865, 1999  相似文献   

5.
In this article, maleated–grafted ethylene‐co‐vinyl acetate (EVA‐g‐MA) was used as the interfacial modifier for polypropylene/polyamide‐6 (PP/PA6) blends, and effects of its concentration on the mechanical properties and the morphology of blends were investigated. It was found that the addition of EVA‐g‐MA improved the compatibility between PP and PA6 and resulted in a finer dispersion of dispersed PA6 phase. In comparison with uncompatibilized PP/PA6 blend, a significant reduction in the size of dispersed PA6 domain was observed. Toluene‐etched micrographs confirmed the formation of interfacial copolymers. Mechanical measurement revealed that the addition of EVA‐g‐MA markedly improved the impact toughness of PP/PA6 blend. Fractograph micrographs revealed that matrix shear yielding began to occur when EVA‐g‐MA concentration was increased upto 18 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3300–3307, 2006  相似文献   

6.
Blends of two biodegradable semicrystalline polymers, poly(p‐dioxanone) (PPDO) and poly(vinyl alcohol) (PVA) were prepared with different compositions. The thermal stability, phase morphology and thermal behavior of the blends were studied by using thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). From the TGA data, it can be seen that the addition of PVA improves the thermal stability of PPDO. DSC analysis showed that the glass transition temperature (Tg) and the melting temperature (Tm) of PPDO in the blends were nearly constant and equal to the values for neat PPDO, thus suggesting that PPDO and PVA are immiscible. It was found from the SEM images that the blends were phase‐separated, which was consistent with the DSC results. Additionally, non‐isothermal crystallization under controlled cooling rates was explored, and the Ozawa theory was employed to describe the non‐isothermal crystallization kinetics. Copyright © 2006 Society of Chemical Industry  相似文献   

7.
In this work, blends of poly(butylene terephthalate) (PBT) and linear low‐density polyethylene (LLDPE) were prepared. LLDPE was used as an impact modifier. Since the system was found to be incompatible, compatibilization was sought for by the addition of the following two types of functionalized polyethylene: ethylene vinylacetate copolymer (EVA) and maleic anhydride‐grafted EVA copolymer (EVA‐g‐MAH). The effects of the compatibilizers on the rheological and mechanical properties of the blends have been also quantitatively investigated. The impact strength of the PBT–LLDPE binary blends slightly increased at a lower concentration of LLDPE but increased remarkably above a concentration of 60 wt % of LLDPE. The morphology of the blends showed that the LLDPE particles had dispersed in the PBT matrix below 40 wt % of LLDPE, while, at 60 wt % of LLDPE, a co‐continuous morphology was obtained, which could explain the increase of the impact strength of the blend. Generally, the mechanical strength was decreased by adding LLDPE to PBT. Addition of EVA or EVA‐g‐MAH as a compatibilizer to PBT–LLDPE (70/30) blend considerably improved the impact strength of the blend without significantly sacrificing the tensile and the flexural strength. More improvement in those mechanical properties was observed in the case of the EVA‐g‐MAH system than for the EVA system. A larger viscosity increase was also observed in the case of the EVA‐g‐MAH than EVA. This may be due to interaction of the EVA‐g‐MAH with PBT. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 989–997, 1999  相似文献   

8.
Thermal properties and non‐isothermal melt‐crystallization behavior of poly(trimethylene terephthalate) (PTT)/poly(lactic acid) (PLA) blends were investigated using differential scanning calorimetry and thermogravimetric analysis. The blends exhibit single and composition‐dependent glass transition temperature, cold crystallization temperature (Tcc) and melt crystallization peak temperature (Tmc) over the entire composition range, implying miscibility between the PLA and PTT components. The Tcc values of PTT/PLA blends increase, while the Tmc values decrease with increasing PLA content, suggesting that the cold crystallization and melt crystallization of PTT are retarded by the addition of PLA. The modified Avrami model is satisfactory in describing the non‐isothermal melt crystallization of the blends, whereas the Ozawa method is not applicable to the blends. The estimated Avrami exponent of the PTT/PLA blends ranges from 3.25 to 4.11, implying that the non‐isothermal crystallization follows a spherulitic‐like crystal growth combined with a complicated growth form. The PTT/PLA blends generally exhibit inferior crystallization rate and superior activation energy compared to pure PTT at the same cooling rate. The greater the PLA content in the PTT/PLA blends, the lower the crystallization rate and the higher the activation energy. Moreover, the introduction of PTT into PLA leads to an increase in the thermal stability behavior of the resulting PTT/PLA blends. Copyright © 2011 Society of Chemical Industry  相似文献   

9.
The glass‐transition temperature (Tg) of the poly(vinylidene fluoride) (PVF2)‐poly(methyl acrylate) (PMA) blends increase with aging time. The Tg versus log(time) plots are straight lines whose slope values depend on the head to head (H–H) defect content of PVF2 samples and on the composition of the blends. The values of polymer–polymer interaction parameters (χ) increase with an increase in the H–H defect of PVF2 for a fixed composition of the blend. Consequently, the Tg of the blend decreases with an increase in the H–H defect of the PVF2 sample. However, after aging for longer times this decrease of the Tg with H–H defects is lower than those of the unaged blends. The possible reasons are discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1541–1548, 2001  相似文献   

10.
The crystallization kinetics of poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET), and their copolymers poly(1,4‐butylene‐co‐ethylene terephthalate) (PBET) containing 70/30, 65/35 and 60/40 molar ratios of 1,4‐butanediol/ethylene glycol were investigated using differential scanning calorimetry (DSC) at crystallization temperatures (Tc) which were 35–90 °C below equilibrium melting temperature . Although these copolymers contain both monomers in high proportion, DSC data revealed for copolymer crystallization behaviour. The reason for such copolymers being able to crystallize could be due to the similar chemical structures of 1,4‐butanediol and ethylene glycol. DSC results for isothermal crystallization revealed that random copolymers had a lower degree of crystallinity and lower crystallite growth rate than those of homopolymers. DSC heating scans, after completion of isothermal crystallization, showed triple melting endotherms for all these polyesters, similar to those of other polymers as reported in the literature. The crystallization isotherms followed the Avrami equation with an exponent n of 2–2.5 for PET and 2.5–3.0 for PBT and PBETs. Analyses of the Lauritzen–Hoffman equation for DSC isothermal crystallization data revealed that PBT and PET had higher growth rate constant Go, and nucleation constant Kg than those of PBET copolymers. © 2001 Society of Chemical Industry  相似文献   

11.
Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMAs) (designated as iPMMA, aPMMA, and sPMMA) with approximately the same molecular weight were mixed separately with poly(styrene‐co‐acrylonitrile) (abbreviated as PSAN) containing 25 wt % of acrylonitrile in tetrahydrofuran to make three polymer blend systems. Differential scanning calorimetry (DSC) was used to study the miscibility of these blends. The results showed that the tacticity of PMMA has a definite impact on its miscibility with PSAN. The aPMMA/PSAN and sPMMA/PSAN blends were found to be miscible because all the prepared films were transparent and showed composition dependent glass transition temperatures (Tgs). The glass transition temperatures of the two miscible blends were fitted well by the Fox equation, and no broadening of the glass transition regions was observed. The iPMMA/PSAN blends were found to be immiscible, because most of the cast films were translucent and had two glass transition temperatures. Through the use of a simple binary interaction model, the following comments can be drawn. The isotactic MMA segments seemed to interact differently with styrene and with acrylonitrile segments from atactic or syndiotactic MMA segments. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2894–2899, 1999  相似文献   

12.
Dynamic viscoelastic properties for miscible blends of poly(?‐caprolactone) (PCL) and poly(styrene‐co‐acrylonitrile) (SAN) were measured. It was found that the time–temperature superposition principle is applicable over the entire temperature range studied for the blends. The temperature dependency of the shift factors aT can be expressed by the Williams–Landel–Ferry equation: log aT = ?8.86(T ? Ts)/(101.6 + T ? Ts). The compositional dependency of Ts represents the Gordon–Taylor equation. The zero‐shear viscosities are found to increase concavely upward with an increase in weight fraction of SAN at constant temperature, but concavely downward at constant free volume fraction. It is concluded that the relaxation behavior of the PCL/SAN blends is similar to that of a blend consisting of homologous polymers. It is emphasized that the viscoelastic functions of the miscible blends should be compared in the iso‐free volume state. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2037–2041, 2001  相似文献   

13.
The calorimetric characteristics of carbon black (CB)/poly(ethylene‐co‐alkyl acrylate) composites depend on both the CB and acrylate contents. An increase of the acrylate content in the pure copolymers tends to decrease all the crystalline characteristics: Tc,n, the nonisothermal crystallization temperature; Tm, the melting temperature, and ΔHm, the melting enthalpy. CB modifies the crystallization kinetics of poly(ethylene‐co‐ethyl acrylate) (EEA) alone and in blends with poly(ethylene‐co‐24% w/w methyl acrylate) (24EMA) and poly(ethylene‐co‐35% w/w methyl acrylate) (35EMA). In the presence of CB, Tc,n, the nonisothermal crystallization temperature of EEA, increases and t1/2, the half‐crystallization time, decreases for a given isothermal crystallization temperature, Tc,i. The thermograms obtained during the melting of EEA after isothermal crystallization show multiple endotherms, suggesting that crystalline‐phase segregation has occurred. The existence of different crystalline species can be explained by the presence of fractions of different acrylate content in the copolymers as shown by SEC. Therefore, CB does not seem to have much effect on the subsequent melting temperature of EEA, Tm,s. CB also induces a lower melting enthalpy, Δ Hm, in the blends. This decrease of ΔHm appears to be constant whatever the compound, but when reported to the melting enthalpy of the polymer without CB, δΔHmHm increases with the acrylate content. A slight increase of the amorphous phase stiffness after CB introduction is noticed: The Tg of EEA/24EMA and EEA/35EMA blends increases by several degrees. Therefore, plotting ΔHm versus ΔCp shows that for the same ΔHm the ΔCp is lower in CB‐filled samples, suggesting there is some kind of rigid amorphous phase not contributing to the glass transition. We propose to explain the CB activity during the crystallization process by the existence of molecular interactions between CB and acrylate groups rather than by a pure nucleating effect. Thus, the increase of Tc,n and the decrease of ΔHm could be explained by the fact that CB separates acrylate‐rich chains from the crystallization medium, accelerating the crystallization of the acrylate‐poor chains. During such a crystallization process, CB may be preferentially localized in the more polar amorphous phase and scattered between the two crystalline phases of EEA and EXA. These blends of poly(ethylene‐co‐alkyl acrylate) copolymers with CB provide interesting materials with adjustable properties depending on the acrylate and CB contents and on the thermomechanical treatments. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 779–793, 2001  相似文献   

14.
Thermal properties of blends of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) and poly(styrene‐co‐acrylonitrile) (SAN) prepared by solution casting were investigated by differential scanning calorimetry. In the study of PHBV‐SAN blends by differential scanning calorimetry, glass transition temperature and melting point of PHBV in the PHBV‐SAN blends were almost unchanged compared with those of the pure PHBV. This result indicates that the blends of PHBV and SAN are immiscible. However, crystallization temperature of the PHBV in the blends decreased approximately 9–15°. From the results of the Avrami analysis of PHBV in the PHBV‐SAN blends, crystallization rate constant of PHBV in the PHBV‐SAN blends decreased compared with that of the pure PHBV. From the above results, it is suggested that the nucleation of PHBV in the blends is suppressed by the addition of SAN. From the measured crystallization half time and degree of supercooling, interfacial free energy for the formation of heterogeneous nuclei of PHBV in the PHBV‐SAN blends was calculated and found to be 2360 (mN/m)3 for the pure PHBV and 2920–3120 (mN/m)3 for the blends. The values of interfacial free energy indicate that heterogeneity of PHBV in the PHBV‐SAN blends is deactivated by the SAN. This result is consistent with the results of crystallization temperature and crystallization rate constant of PHBV in the PHBV‐SAN blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 673–679, 2000  相似文献   

15.
The imidization of poly(styrene‐co‐maleic anhydride) (SMA) was conducted, and the glass‐transition temperatures (Tg's) of the resulting products were measured with differential scanning calorimetry. The contributions from functional groups of maleic anhydride, N‐phenylmaleamic acid, and N‐phenylmaleimide to Tg were examined. Tg increased in the order of SMA < styrene–N‐phenyl maleimide copolymer < styrene–N‐phenyl maleamic acid copolymer and followed the Fox equation. Tg of the imidized products of SMA could be controlled by the conversions of both ring‐opening and ring‐closing reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2418–2422, 2007  相似文献   

16.
Amylopectin (AP), a potato‐starch‐based polymer with a molecular weight of 6,000,000 g/mol, was blended with poly(ε‐caprolactone) (PCL) and characterized with inverse gas chromatography (IGC), differential scanning calorimetry (DSC), and X‐ray diffraction (XRD). Five different compositions of AP–PCL blends ranging from 0 to 100% AP were studied over a wide range of temperatures (80–260°C). Nineteen solutes (solvents) were injected onto five chromatographic columns containing the AP–PCL blends. These solutes probed the dispersive, dipole–dipole, and hydrogen‐bonding interactions, acid–base characteristics, wettability, and water uptake of the AP–PCL blends. Retention diagrams of these solutes in a temperature range of 80–260°C revealed two zones: crystalline and amorphous. The glass‐transition temperature (Tg) and melting temperature (Tm) of the blends were measured with these zones. The two zones were used to calculate the degree of crystallinity of pure AP and its blends below Tm, which ranged from 85% at 104°C to 0% at Tm. IGC complemented the DSC method for obtaining the Tg and Tm values of the pure AP and AP–PCL blends. These values were unexpectedly elevated for the blends over that of pure AP and ranged from 105 to 152°C for Tg and from 166 to 210°C for Tm. The Tm values agreed well with the XRD analysis data. This elevation in the Tg and Tm values may have been due to the change in the heat capacity at Tg and the dependence of Tg on various variables, including the molecular weight and the blend composition. Polymer blend/solvent interaction parameters were measured with a variety of solutes over a wide range of temperatures and determined the solubility of the blends in the solutes. We were also able to determine the blend compatibility over a wide range of temperatures and weight fractions. The polymer–polymer interaction coefficient and interaction energy parameter agreed well on the partial miscibility of the two polymers. The dispersive component of the surface energy of the AP–PCL blends was measured with alkanes and ranged from 16.09 mJ/m2 for pure AP to 38.26 mJ/m2 when AP was mixed with PCL in a 50/50% ratio. This revealed an increase in the surface energy of AP when PCL was added. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3076–3089, 2006  相似文献   

17.
The low‐temperature physical aging of amorphous poly(L ‐lactide) (PLLA) at 25–50°C below glass transition temperature (Tg) was carried out for 90 days. The physical aging significantly increased the Tg and glass transition enthalpy, but did not cause crystallization, regardless of aging temperature. The nonisothermal crystallization of PLLA during heating was accelerated only by physical aging at 50°C. These results indicate that the structure formed by physical aging only at 50°C induced the accelerated crystallization of PLLA during heating, whereas the structure formed by physical aging at 25 and 37°C had a negligible effect on the crystallization of PLLA during heating, except when the physical aging at 37°C was continued for the period as long as 90 days. The mechanism for the accelerated crystallization of PLLA by physical aging is discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

18.
The nonisothermal crystallization kinetics of polypropylene (PP), PP/polystyrene (PS), and PP/PP‐g‐PS/PS blends were investigated with differential scanning calorimetry at different cooling rates. The Jeziorny modified Avrami equation, Ozawa method, and Mo method were used to describe the crystallization kinetics for all of the samples. The kinetics parameters, including the half‐time of crystallization, the peak crystallization temperature, the Avrami exponent, the kinetic crystallization rate constant, the crystallization activation energy, and the F(T) and a parameters were determined. All of the results clearly indicate that the PP‐g‐PS copolymer accelerated the crystallization rate of the PP component in the PP/PP‐g‐PS/PS blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

19.
Summary: Blends of poly(propylene) (PP) were prepared with poly[ethylene‐co‐(methyl acrylate)] (EMA) having 9.0 and 21.5% methyl acrylate comonomer. A similar series of blends were compatibilized by using maleic anhydride grafted PP. The morphology and mechanical properties of the blends were investigated using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) in tensile mode. The DMA method and conditions were optimized for polymer film specimens and are discussed in the experimental section. The DSC results showed separate melting that is indicative of phase‐separated blends, analogous to other PP‐polyethylene blends but with the added polarity of methyl acrylate pendant side groups that may be beneficial for chemical resistance. Heterogeneous nucleation of PP was decreased in the blends because of migration of nuclei into the more polar EMA phase. The crystallinity and peak‐melting temperature did not vary significantly, although the width of the melting endotherm increased in the blends indicating a change had occurred to the crystals. DMA analysis showed the crystal‐crystal slip transition and glass transition (Tg) for PP as well as a Tg of the EMA copolymer occurring chronologically toward lower temperatures. The storage modulus of PP and the blends was generally greater with annealing at 150 °C compared with isothermal crystallization at 130 °C. The storage modulus of the blends for isothermally crystallized PP increased with 5% EMA, then decreased for higher amounts of EMA. Annealing caused a decrease with increasing copolymer content. The extent of the trend was greater for the compatibilized blends. The Tg of the blends varied over a small range, although this change was less for the compatibilized blends.

Storage modulus for PP and EMA9.0 blends annealed at 150 °C.  相似文献   


20.
The thermal properties of blends of poly(ether ether ketone) (PEEK) and poly(ether imide) (PEI) prepared by screw extrusion were investigated by differential scanning calorimetry. From the thermal analysis of amorphous PEEK–PEI blends which were obtained by quenching in liquid nitrogen, a single glass transition temperature (Tg) and negative excess heat capacities of mixing were observed with the blend composition. These results indicate that there is a favorable interaction between the PEEK and PEI in the blends and that there is miscibility between the two components. From the Lu and Weiss equation and a modified equation from this work, the polymer–polymer interaction parameter (χ12) of the amorphous PEEK–PEI blends was calculated and found to range from −0.058 to −0.196 for the extruded blends with the compositions. The χ12 values calculated from this work appear to be lower than the χ12 values calculated from the Lu and Weiss equation. The χ12 values calculated from the Tg method both ways decreased with increase of the PEI weight fraction. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 733–739, 1999  相似文献   

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