Thermal properties and non‐isothermal crystallization behavior of biodegradable poly(p‐dioxanone)/poly(vinyl alcohol) blends

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 (T_g) and the melting temperature (T_m) 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     

Casting solvent effect on crystallization behavior and morphology of poly(ethylene oxide)/poly(methyl methacrylate)

Poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends were prepared by casting from either chloroform or benzene solvents. After casting from solvents, all samples used in this study were preheated to 100°C and held for 10 min. Then, the solvent effect on the crystallization behavior and thermodynamic properties were studied by differential scanning calorimeter (DSC). Also, the morphology of spherulite of casting film was studied by polarized optical microscope. From the DSC and polarizing optical microscopy (POM) results, it was found that PEO/PMMA was miscible in the molten state no matter which casting solvent was used. However, the crystallization of PEO in the chloroform‐cast blend was more easily suppressed than it was in the benzene‐cast blend. Relatively, the chloroform‐cast blend showed the greater melting‐point depressing of PEO crystals. Also, the spherulite of chloroform‐cast film showed a coarser birefringence. It was supposed that the chloroform‐cast blend had more homogeneous morphology. It is fair to say that polymer blends, cast from solvent, are not necessarily in equilibrium. However, the benzene‐cast blends still were not in equilibrium even after preheating at 100°C for 10 min. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1627–1636, 2000     

Casting solvent effect on crystallization behavior of poly(vinyl acetate)/poly(ethylene oxide) blends: DSC study

Poly(vinyl acetate) (PVAc)/poly(ethylene oxide) (PEO) blends were prepared by casting from either benzene or chloroform. The solvent effects on the crystallization behavior and thermodynamic properties of the blends were studied by the differential scanning calorimeter (DSC). Two grades of PEO with different molecular weights (PEO200 with M_w = 200,000 g/mol and PEO2 with M_n = 2000 g/mol) were used in this work. The thermal analysis revealed that the blends cast from either benzene or chloroform were miscible in the molten state. The crystallization of PEO in the benzene-cast blends was more easily suppressed than it was in the chloroform-cast blends. Furthermore, the benzene-cast blends showed a greater negative value of Flory-Huggins interaction parameter than those cast from chloroform in the PVAc/PEO200 poly-blend system. It was supposed that the benzene-cast blends had more homogeneous morphology. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 411–421, 1997     

A dynamic mechanical and thermal analysis of unplasticized and plasticized poly(vinyl alcohol)/methylcellulose blends

The miscibility of poly(vinyl alcohol) (PVA)/methylcellulose (MC) blends was investigated over the entire composition range using the dynamic mechanical analyzer (DMA) and the differential scanning calorimeter (DSC). On the basis of the glass transition temperature, determined by DMA, one could conclude that the blends exhibited some miscibility below 80 wt % of MC and a good miscibility above 80 wt % of MC. The highest depressions of the melting and crystallization temperatures of the blends compared to those of PVA, determined via DSC analysis, were observed for MC contents greater than 80 wt %. The miscibility between PVA and MC can be attributed to the hydrogen bonds formed between the two components. The DMA studies showed that water is a good plasticizer for PVA and poly(ethylene glycol) 400 (PEG 400), a good plasticizer for MC. The inclusion of both water and PEG 400 in the blends revealed a synergistic plasticizing effect, which resulted in an increased miscibility between PVA and MC over a greater range of MC compositions (>60 wt %). The elongations of PVA, MC, and their blends were found to increase with the addition of PEG 400, but the tensile strengths to decrease. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1825–1834, 2001     

Blends of polypropylene with poly(vinyl butyral)

The thermal stability, crystallization behavior, and morphology of poly(vinyl butyral) (PVB) with differing compositions of vinyl alcohol and butyral units were investigated. It was found that the glass‐transition temperature of PVB decreases with increasing concentration of butyral units, mainly because of the reduced number of hydrogen bonds between hydroxyl groups of the chains. PVB samples with high vinyl alcohol content (≥63.3% by weight) are crystallizable and present an endothermic melting peak in the range 170–220°C. The thermal stability of PVB is also influenced by composition and increases with the number of butyral units. The thermal and crystallization characteristics of PVB were compared with those of neat polyvinyl alcohol (PVA), and the differences explained in terms of molecular structure. Two amorphous PVB samples, containing 31 and 14 wt % of vinyl alcohol units, respectively, were blended with isotactic polypropylene grafted with maleic anhydride (PP–MA), the latter of which was present to favor compatibilization of the components through chemical reaction or dipolar interactions involving the anhydride groups of the PP–MA and the hydroxyl groups of PVB. Properties of PP–MA/PVB 90/10 blends, prepared by melt extrusion, were compared to those of neat PP–MA. Both the PVBs used were immiscible with PP–MA, as indicated by the invariance of glass‐transition temperatures with the composition of the blends. However, a high level of compatibility between the components was achieved because the blends showed good mechanical properties that were comparable to, or even superior to, those of neat PP–MA. The analysis of the crystallization kinetics, performed both in isothermal and nonisothermal modes, showed that crystallization of polypropylene is only slightly influenced by the presence of the PVB phase. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2934–2946, 2001     

Thermomechanical properties and morphology of polyethylene oxide and phenolic resole blends

Blends of poly(ethylene oxide) (PEO) and resole type phenolic resin were prepared by a solution cast method using water as a solvent. The cured blends were made by heat curing without using any catalyst. The blends were characterized by dynamic mechanical analysis (DMA), which indicated that PEO forms compatible blend with the resole. The glass transition values, read from the DMA traces, showed a positive shift as compared to the theoretical values calculated by the Fox equation. This suggests a strong H‐bonding interaction between the phenolic resole and PEO as established by Fourier transformed infrared spectroscopy. Flexural test indicated an enhanced flexibility of the blends when compared to the neat phenolic resin. The fracture surface analysis by using a scanning electron microscope (SEM) revealed an increase in plastic deformation with increasing PEO concentration in the blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Miscibility and phase structure of binary blends of poly(L‐lactide) and poly(vinyl alcohol)

Blend films of poly(L ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA) were obtained by evaporation of hexafluoroisopropanol solutions of both components. The component interaction, crystallization behavior, and miscibility of these blends were studied by solid‐state NMR and other conventional methods, such as Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The existence of two series of isolated and constant glass‐transition temperatures (T_g's) independent of the blend composition indicates that PLLA and PVA are immiscible in the amorphous region. However, the DSC data still demonstrates that some degree of compatibility related to blend composition exists in both PLLA/atactic‐PVA (a‐PVA) and PLLA/syndiotactic‐PVA (s‐PVA) blend systems. Furthermore, the formation of interpolymer hydrogen bonding in the amorphous region, which is regarded as the driving force leading to some degree of component compatibility in these immiscible systems, is confirmed by FTIR and further analyzed by ¹³C solid‐state NMR analyses, especially for the blends with low PLLA contents. Although the crystallization kinetics of one component (especially PVA) were affected by another component, WAXD measurement shows that these blends still possess two isolated crystalline PLLA and PVA phases other than the so‐called cocrystalline phase. ¹³C solid‐state NMR analysis excludes the interpolymer hydrogen bonding in the crystalline region. The mechanical properties (tensile strength and elongation at break) of blend films are consistent with the immiscible but somewhat compatible nature of these blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 762–772, 2001     

Effect of the crystallization conditions on the phase behavior of syndiotactic polystyrene/poly(phenylene oxide) blends

Syndiotactic polystyrene (sPS) and poly(phenylene oxide) (PPO) blends, miscible in the melt state, were crystallized from the melt and the quenched state at different temperatures. The effect of the crystallization temperature on the phase behavior of the blends and the polymorphic changes in sPS was investigated by dynamic mechanical analysis (DMA), wide‐angle X‐ray diffraction (WAXD), and density measurements. In most blends, the crystallization of sPS induced segregation into two homogeneous amorphous phases of different compositions. The temperatures of the DMA relaxations of the neat homopolymers and crystallized blends were fit by the Gordon–Taylor relation to calculate the compositions of these phases. In melt‐crystallized blends, with slower crystallization, the major amorphous phase became sPS‐rich, whereas the minor phase became PPO‐rich. These major and minor amorphous phases could be tentatively assigned to interfibrillar and interlamellar regions, respectively. In cold‐crystallized blends, slower crystallization decreased the sPS concentration in both phases, and the scale of segregation was much smaller. WAXD studies and density measurements indicated a complex polymorphic behavior of sPS after it was blended with PPO. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1975–1983, 2003     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and poly(DL-lactide)-co-poly(ethylene glycol)

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     

Miscibility and crystallization of poly(ethylene succinate)/poly(vinyl phenol) blends

Miscibility of biodegradable poly(ethylene succinate) (PES)/poly(vinyl phenol) (PVPh) blends has been studied by differential scanning calorimetry (DSC) in this work. PES is found to be miscible with PVPh as shown by the existence of single composition dependent glass transition temperature over the entire composition range. Spherulitic morphology and the growth rates of neat and blended PES were investigated by optical microscopy (OM). Both neat and blended PES show a maximum growth rate value in the crystallization temperature range of 45-65 °C, with the growth rate of neat PES being higher than that of blended PES at the same crystallization temperature. The overall crystallization kinetics of neat and blended PES was also studied by DSC and analyzed by the Avrami equation at 60 and 65 °C. The crystallization rate decreases with increasing the temperature for both neat and blended PES. The crystallization rate of blended PES is lower than that of neat PES at the same crystallization temperature. However, the Avrami exponent n is almost the same despite the blend composition and crystallization temperature, indicating that the addition of PVPh does not change the crystallization mechanism of PES but only lowers the crystallization rate.     

Effect of organoclay in an immiscible poly(ethylene terephtalate) waste/poly(methyl methacrylate) blend

Blends of organically modified montmorillonite (OMMT) with poly(ethylene terephtalate) (PET) waste and poly(methyl methacrylate) (PMMA) were prepared by melt mixing. The morphology of PET/PMMA nanocomposites with different OMMT contents was characterized by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). The nonisothermal crystallization temperatures of nanocomposites were also examined by DSC. TEM observations and XRD patterns revealed that silicate layers were intercalated and well dispersed in the blend. Nanocomposites displayed better mechanical properties when compared with the unfilled blend. DMA analyses also showed efficient mixing of the two immiscible polymers and changes in glass transition temperature with the presence of OMMT. DSC analysis showed an enhancement in crystallization rate of nanocomposites and a decrease in cristallinity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Miscibility and crystallization in crystalline/crystalline blends of poly(butylene succinate)/poly(ethylene oxide)

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-T_m 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-T_m 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.     

PLA/PEO共混物的结晶行为研究

共沉积技术制备了聚乳酸(PLA)/聚氧化乙烯(PEO)共混物,通过DMA和相差显微镜考察了共混物的相行为。用DSC研究了PLA/PEO共混物的结晶形貌及其动力学,由于部分相容的熔融态PEO提高了PLA分子链的运动能力,导致显著促进了PLA的结晶速率;结合偏光显微镜(POM)观察分析,结晶速率的提高源于结晶生长速率的促进,而且在低的结晶温度时的结晶速率的增加更为明显。     

Crystallization and melting behavior of poly(ether ether ketone)/poly(aryl ether sulfone) blends

The crystallization and melting behavior of poly(ether ether ketone) (PEEK) in blends with poly(aryl ether sulfone) (PES) prepared by melt mixing are investigated by differential scanning calorimetry (DSC) and wide‐angle X‐ray scattering (WAXS). The presence of PES is found to have a notable influence on the crystallization behavior of PEEK, especially when present in low concentrations in the PEEK/PES blends. The PEEK crystallization kinetics is retarded in the presence of PES from the melt and in the rubbery state. An analysis of the melt crystallization exotherm shows a slower rate of nucleation and a wider crystallite size distribution of PEEK in the presence of PES, except at low concentrations of PES, where, because of higher miscibility and the tendency of PES to form ordered structures under suitable conditions, a significantly opposite result is observed. The cold crystallization temperature of the blends at low PES concentration is higher then that of pure PEEK, whereas at a higher PES concentration little change is observed. In addition, the decrease in heat of cold crystallization and melting, which is more prevalent in PEEK‐rich compositions than in pure PEEK, shows the reduction in the degree of crystallinity because of the dilution effect of PES. Isothermal cold crystallization studies show that the cold crystallization from the amorphous glass occurs in two stages, corresponding to the mobilization of the PEEK‐rich and PES‐rich phases. The slower rate of crystallization of the PEEK‐rich phase, even in compositions where a pure PEEK phase is observed, indicates that the presence of the immobile PES‐rich phase has a constraining influence on the crystallization of the PEEK‐rich phase, possibly because of the distribution of individual PEEK chains across the two phases. The various crystallization parameters obtained from WAXS analysis show that the basic crystal structure of PEEK remains unaffected in the blend. Further, the slight melting point depression of PEEK at low concentrations of PES, apart from several other morphological reasons, may be due to some specific interactions between the component homopolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2906–2918, 2003     

High molecular weight poly( -lactide) and poly(ethylene oxide) blends: thermal characterization and physical properties

The miscibility of high molecular weight poly( -lactide) PLLA with high molecular weight poly(ethylene oxide) PEO was studied by differential scanning calorimetry. All blends containing up to 50 weight% PEO showed single glass transition temperatures. The PLLA and PEO melting temperatures were found to decrease on blending, the equilibrium melting points of PLLA in these blends decreased with increasing PEO fractions. These results suggest the miscibility of PLLA and PEO in the amorphous phase. Mechanical properties of blends with up to 20 weight% PEO were also studied. Changes in mechanical properties were small in blends with less than 10 weight% PEO. At higher PEO concentrations the materials became very flexible, an elongation at break of more than 500% was observed for a blend with 20 weight% PEO. Hydrolytic degradation up to 30 days of the blends showed only a small variation in tensile strength at PEO concentrations less than 15 weight%. As a result of the increased hydrophilicity, however, the blends swelled. Mass loss upon degradation was attributed to partial dissolution of the PEO fraction and to an increased rate of degradation of the PLLA fraction. Significant differences in degradation behaviour between PLLA/PEO blends and (PLLA/PEO/PLLA) triblock-copolymers were observed.     

Structure and mechanical properties of poly(sulfone of bisphenol A)/poly(butylene terephthalate) blends

Blends of poly(sulfone of bisphenol A) (PSU) with poly(butylene terephthalate) (PBT) were obtained by direct injection moulding across the composition range. The two components of the blends reacted slightly in the melt state, producing linear copolymers. The slight changes observed in the two glass transition temperatures indicate that the copolymers were present in the two amorphous phases of the blends. The observed reactions and the high viscosity of the matrix of the PSU‐rich compositions led to a very fine morphology which could not be attained in the PBT‐rich compositions due to the low viscosity of the matrix and the direct injection moulding procedure used. This procedure is fast and economically advantageous, but leads to poor mixing. The different morphologies influenced neither the modulus nor the yield stress, which tended to follow the rule of mixtures. However, the low fracture properties of the PBT‐rich compositions contrasted with the ductility behaviour, and even the impact strength of the PSU‐rich blends, which also tended to be proportional to the blend composition. Copyright © 2004 Society of Chemical Industry     

Crystallization and melting behavior of blends comprising poly(3‐hydroxy butyrate‐co‐3‐hydroxy valerate) and poly(ethylene oxide)

Blends of poly(3‐hydroxy butyrate‐co‐3‐hydroxy valerate) (PHBV) and poly(ethylene oxide) (PEO) were prepared by casting from chloroform solutions. Crystallization kinetics and melting behavior of blends have been studied by differential scanning calorimetry and optical polarizing microscopy. Experimental results reveal that the constituents are miscible in the amorphous state. They form separated crystal structures in the solid state. Crystallization behavior of the blends was studied under isothermal and nonisothermal conditions. Owing to the large difference in melting temperatures, the constituents crystallize consecutively in blends; however, the process is affected by the respective second component. PHBV crystallizes from the amorphous mixture of the constituents, at temperatures where the PEO remains in the molten state. PEO, on the other hand, is surrounded during its crystallization process by crystalline PHBV regions. The degree of crystallinity in the blends stays constant for PHBV and decreases slightly for PEO, with ascending PHBV content. The rate of crystallization of PHBV decreases in blends as compared to the neat polymer. The opposite behavior is observed for PEO. Nonisothermal crystallization is discussed in terms of a quasi‐isothermal approach. Qualitatively, the results show the same tendencies as under isothermal conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2776–2783, 2006     

Crystallization and melting behavior of poly(p‐phenylene sulfide) in blends with poly(ether sulfone)

Crystallization and melting behaviors of poly(p‐phenylene sulfide) (PPS) in blends with poly(ether sulfone) (PES) prepared by melt‐mixing were investigated by differential scanning calorimetry (DSC). The blends showed two glass transition temperatures corresponding to PPS‐ and PES‐rich phases, which increased with increasing PES content, indicating that PPS and PES have some compatibility. The cold crystallization temperature of the blended PPS was a little higher than that of pure PPS. Also, the heats of crystallization and melting of the blended PPS decreased with increasing PES content, indicating that the degree of crystallinity decreased with an increase of PES content. The isothermal crystallization studies revealed that the crystallization of PPS is accelerated by blending PPS with 10 wt % PES and further addition results in the retardation. The Avrami exponent n was about 4 independent on blend composition. The activation energy of crystallization increased by blending with PES. The equilibrium melting point decreased linearly with increasing PES content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1686–1692, 1999     

不同PEG含量对PLA/PEG共混物结晶动力学的影响

采用溶液共混法制备了一系列不同配比的聚乳酸(PLA)/聚乙二醇(PEG)共混物。通过偏光显微镜(POM)、扫描电镜(SEM)和差式扫描量热仪(DSC)研究了不同PEG含量的PLA/PEG共混物在不同结晶温度下,聚乳酸的晶体形貌、球晶生长速率及热力学性能。研究发现,PEG能够显著提高聚乳酸球晶的生长速率。当PEG含量为60%时,PLA/PEG共混物中聚乳酸球晶的生长速率最快,达到23.6μm/min,比纯聚乳酸的最快球晶生长速率(0.5μm/min)高47倍。但是,当PEG含量高于60%时,聚乳酸球晶的生长速率有所降低。同时,PLA/PEG共混物中聚乳酸球晶速率随结晶温度变化的取向,均向低温移动。另外,PLA/PEG共混物中聚乳酸球晶呈现环状花纹。DSC测试结果表明,随着PEG含量的增加,PLA/PEG共混物的玻璃化转变温度明显降低。     

Effect of tacticity of poly(methyl methacrylate) on the miscibility with poly(styrene‐co‐acrylonitrile)

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 (T_gs). 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