Phase transition properties of polyethylene glycol-cellulose blends and their miscibility in mixed solvents

The phase transition properties of blends of polyethylene glycol (PEG) with cellulose (CELL) prepared from solution in N,N-dimethylacetamide/lithium chloride (DMAC/LiCI) and those from solution in dimethylsulfoxide/paraform- aldehyde (DMSO/PF) were found to be completely different. The differences of the phase transition properties were probably related to the different miscibilities of these two polymers in the two solvent systems. In DMAC/LiCl, the miscibility of CELL and PEG was limited; the composite obtained exhibited a solid- liquid phase transition and had a small phase transition enthalpy. However, in DMSO/PF, these two polymers had a high level of miscibility; the composite obtained exhibited a solid-solid phase transition and had a large phase enthalpy. It is suggested that the differences of miscibility and the phase transition properties were caused by the different dissolving mechanisms of CELL and the different interactions in these two solutions.     

Viscosity,Ultrasonic, and Refractometric Studies of Chitosan/Polyethylene Glycol Blend in Solution at 30, 40, and 50°C

Measurements of viscosity, ultrasonic velocity, refractive index, and density of chitosan (CS)/polyethylene glycol (PEG) blends in buffer solution (0.1 M acetic acid+0.2 M sodium acetate) were carried out for different blend compositions at 30, 40, and 50°C. Using the viscosity data, interaction parameters μ and α were computed to determine miscibility. These values revealed that the blend was miscible when the chitosan content was more than 60% of the blend. The results were further confirmed by ultrasonic velocity, density, and refractive index measurements. Further, the results revealed that the change in temperature has no significant effect on the miscibility of CS/PEG polymer blends.     

Effect of Polydispersity on the Phase Behavior of Polystyrene (PS)/Poly (Vinyl Methyl Ether) (PVME)

The thermodynamics and kinetics of phase separation in partially miscible blends of poly (vinyl methyl ether) (PVME) and two kinds of polystyrene (PS) with the same weight average molecular weight but different polydispersity were studied. The miscibility of PS/PVME with the monodisperse PS was better than that of PS/PVME with the polydisperse PS. Different morphology was observed for the two kinds of PS/PVME (10/90) blends during the nonisothermal phase separation process. The blend with monodisperse PS presented a co-continuous structure while the blend with polydisperse PS presented a viscoelastic phase separated network structure at a quench depth of 29°C. With increase of the heating rate, the increase of cloud point of PS/PVME (30/70) with polydisperse PS was smaller than that of PS/PVME (30/70) with monodisperse PS. During the isothermal phase separation of the critical composition (20/80) of PS/PVME with a quench depth of 30°C, it was found that the phase morphology of the two kinds of blends was nearly the same at the early stage of phase separation. However, as the dispersed phase, an approximately spherical droplet structure was observed in the blend with monodisperse PS at the late stage of phase separation, which did not appear in the blend with polydisperse PS.     

Polyvinylidene Fluoride/Acrylonitrile Butadiene Rubber Blends Prepared Via Dynamic Vulcanization

Dynamically vulcanized blends based on polyvinylidene fluoride (PVDF)/acrylonitrile butadiene rubber (NBR) were prepared and characterized. The mixing torque and dynamic rheology analyses showed that the NBR phase increased the viscosity of the blends. Scanning electron microscopy (SEM) results showed that the NBR phase was in the form of spherical particles dispersed in the PVDF phase during dynamic vulcanization. Comparing PVDF-rich and NBR-rich blends, the size of the rubber particles in the NBR-rich blends were larger than those in PVDF-rich blends. Differential scanning calorimetry (DSC) results showed that the addition of the NBR phase reduced the PVDF crystallinity and T_m. Thermal gravimetric analysis (TGA) results showed that the dynamically vulcanized PVDF/NBR blends had a higher residual char mass than the neat PVDF and NBR. For PVDF-rich blends, the PVDF can be highly toughened by NBR; the Izod impact strength of the PVDF/NBR (70/30) blend was 77.5 kJ/m², which was about six times higher than that of pure PVDF. For rubber-rich blends, the PVDF component was beneficial to the mechanical properties of the blends, which can be used as thermoplastic elastomers.     

Isothermal lamellar thickening in blends of linear and low-density polyethylene

Polyethylene blends were studied by differential scanning calorimetry (DSC) and transmission electron microscopy (TEM). Binary blends of commercial linear polyethylene (LPE) with two low-density polyethylenes (LDPEs) of melt indexes, about 20 and about 0.27 g/10 minutes, were investigated. The blends, with 10% and 50% LPE contents, and the pure LPE were isothermally crystallized at 124°C for up to 48 h under solid-liquid phase segregation conditions. Double melting endotherms were obtained for the blends. Results show that, despite differences in crystallization kinetics between both types of blends, the same depression in the LPE melting temperature and approximately the same LPE crystal thicknesses were found for the blend compositions. In addition, the extent of occurrence of lamellar thickening in LPE during crystallization is a function of its content in the blend.     

Compositional effect on thermo-mechanical,thermal and tensile properties of cis-polyisoprene and chloroprene rubber blends

Blends of cis-polyisoprene (CPI) and chloroprene rubber (CR) have been prepared in different blend compositions by solution casting. Structural characterization of these blends has been done using X-ray diffraction and scanning electron microscopy. The experimental values of thermo-mechanical properties, mechanical properties and thermal conductivity of so-prepared blends determined using dynamic mechanical analyzer and thermal constant analyzer have been presented. Crosslink density has been determined using different models. Experimental results from thermo-mechanical properties show that all the blends are immiscible. Tensile strength, toughness, Young's modulus and thermal conductivity of these blends were found to be higher than that of pure CPI and pure CR. However, mechanical properties of 25/75(V/V) of CPI/CR blend and thermal conductivity of 75/25(V/V) of CPI/CR blend have been found to be highest.     

Miscibility and Isothermal Crystallization Behavior of Poly (Butylene Succinate-co-Adipate) (PBSA)/Poly (Trimethylene Carbonate) (PTMC) Blends

Poly(butylene succinate-co-adipate) (PBSA)/poly (trimethylene carbonate) (PTMC) blend samples with different weight ratios were prepared by solution blending. The morphologies after isothermal crystallization and in the melt were observed by optical microscopy (OM). Differential scanning calorimetry (DSC) was used to characterize the isothermal crystallization kinetics and melting behaviors. According to the OM image before and after melting, it was found that the blends formed heterogenous morphologies. When the PTMC content was low (20%), PBSA formed the continuous phase, while when the PTMC contents was high (40%), PBSA formed the dispersed phase. The glass transition temperatures (T_g) of the blends were determined by DSC and the differences of the T_g values were smaller than the difference between those of pure PBSA and PTMC. In addition, the equilibrium melting points were depressed in the blends. According to these results, the PBSA/PTMC blends were determined as being partially miscible blends. The crystallization kinetics was investigated according to the Avrami equation. It was found that the incorporation of PTMC did not change the crystallization mechanism of PBSA. However, the crystallization rate decreased with the increase of PTMC contents. The change of crystallization kinetics is related with the existences of amorphous PTMC, the partial miscibility between PLLA and PTMC, and the changes of phase structures.     

Unusual Phase Separation Kinetics in Poly(Methyl Methacrylate)/Poly(Styrene-co-Acrylonitrile) (PMMA/SAN) Blends with PMMA of Different Molecular Weights

The influence of molecular weight of poly (methyl methacrylate) (PMMA) on the thermodynamics and dynamics of phase separation in PMMA/poly (styrene-co-acrylonitrile) (SAN) blends was investigated via optical microscopy, time-resolved small-angle light scattering (SALS), and dynamic rheological measurements. It was found that the cloud point temperature of the blends decreased with an increase in the molecular weight of the PMMA. The phase separation rates of PMMA 48K/SAN and PMMA 85K/SAN blends with the near-critical composition were almost the same at small quench depths due to the limited mobility of molecular chains at low temperatures. However, an unexpected phase separation dynamics was observed at larger quench depths. Not only the morphology evolution but also the apparent diffusion coefficient D_app calculated from SALS revealed that the phase separation rate was faster in the PMMA 85K/SAN blend than in the PMMA 48K/SAN blend. The possible reasons for this unusual rapid kinetics of phase separation observed in the higher molecular weight blend were discussed in terms of molecular mobility and viscoelasticity.     

Solid electrolyte membranes from semi-interpenetrating polymer networks of PEG-grafted polymethacrylates and poly(methyl methacrylate)

Solid polymer electrolyte membranes were prepared as semi-interpenetrating networks by photo-induced polymerization of mixtures of poly(ethylene glycol) (PEG) methacrylate macromonomers in the presence of poly(methyl methacrylate) (PMMA) and lithium bis(trifluoromethanesulfonyl)imide salt. The composition of the membranes was varied with respect to the PMMA content, the degree of cross-linking, and the salt concentration. Infrared analysis of the membranes indicated that the lithium ions were coordinated by the PEG side chains. Calorimetry results showed a single glass transition for the blend membranes. However, dynamic mechanical measurements, as well as a closer analysis of the calorimetry data, revealed that the blends were heterogeneous systems. The ionic conductivity of the membranes increased with the content of PEG-grafted polymethacrylate, and was found to exceed 10^− 5 S cm^− 1 at 30 °C for membranes containing more than 85 wt.% of this component in the polymer blend.     

Study on Phase‐Change Characteristics of PET‐PEG Copolymers

Polyethylene glycol (PEG) was selected as a phase‐change material (PCM) and the phase‐change fibers of its copolymers with polyethylene terephalate (PET), PET‐PEG, were successfully prepared by melt spinning. The PET‐PEG copolymers have solid‐solid phase change characteristics at 10–60°C without obvious liquid substance appearing, while PET/PEG blends will lose their phase‐change characteristics since the PEG of the blends may melt and leak under high temperature. By controlling the molecular weight and relavent proportion of PEG added, the phase‐change temperature range and the enthalpy can be adjusted.     

Formation of β-iPP in Isotactic Polypropylene/Acrylonitrile–Butadiene–Styrene Blends: Effect of Resin Type,Phase Composition,and Thermal Condition

The formation of β-iPP (β-modification of isotactic polypropylene) in the iPP/ABS (acrylonitrile–butadiene–styrene), iPP/styrene–butadiene (K resin), and iPP/styrene–acrylonitrile (SAN) blends were studied using differential scanning calorimery (DSC), wide angle X-ray diffraction (WAXD), and scanning electron microscopy (SEM). It was found that α-iPP (α-modification of isotactic polypropylene) and β-iPP can simultaneously form in the iPP/ABS blend, whereas only α-iPP exists in the iPP/K resin and iPP/SAN blend samples. The effects of phase composition and thermal conditions on the β-iPP formation in the iPP/ABS blends were also investigated. The results showed that when the ABS content was low, the ABS dispersed phase distributed in the iPP continuous phase, facilitating the growth of β-iPP, and the maximum amount of β-iPP occurred when the composition of iPP/ABS blend approached 80:20 by weight. Furthermore, it was found that the iPP/ABS blend showed an upper critical temperature T _c * at 130°C for the formation of β-iPP. When the crystallization temperature was higher than the T _c *, the β-iPP did not form. Interestingly, the iPP/ABS blend did not demonstrate the lower critical temperature T _c ** previously reported for pure iPP and its blends. Even if the crystallization temperature decreased to 90°C, there was still β-iPP generation, indicating that ABS has a strong ability to induce the β-iPP. However, the annealing experiments results revealed that annealing in the melt state could eliminate the susceptibility to β-crystallization of iPP.     

Phase Morphology and Mechanical Properties of Polyamide-6/Polyolefin Elastomer-g-Maleic Anhydride Blends

The effects of addition of varying amounts of polyolefin elastomers (POE) (with and/or without grafted maleic anhydride) on the morphology and mechanical properties of polyamide-6 (PA6)-based blends were studied. Scanning electron microscopy (SEM) was employed to obtain some detailed quantitative analyses of the morphology of the fracture behavior for the blends containing 80 wt% PA6 and 20 wt% total elastomer. Impact strength, tensile strength, and flexural strength were also measured for these blends. The results showed that POE and PA6 were an incompatible system, but the POE-g-MAH was compatible and had a toughening effect on PA6. PA6-g-POE was formed through the reaction between POE-g-MAH and PA6 during the melt extrusion process, which reduced the size of the dispersed phase and improved the impact and tensile strength of the blends. The impact strength was improved by nine times compared with the pure PA6 or the binary blend PA6/POE when the blend ratio of the ternary blend PA6/POE/POE-g-MAH was 80/16/4.     

Morphological Aspects of In-Situ Compatiblized Binary Polymer Blends With Variable Viscosity Ratios of Components

The in-situ compatiblized binary polymer blend polypropylene(PP)/polystyrene(PS)/ anhydrous aluminum chloride(AlCl₃) was selected as a model system of a reactive polymer blend to investigate the effect of viscosity ratio of components at a constant shear rate on the phase morphological behavior in in-situ compatibilized systems. The results showed that the well-known interfacial compatibilization effect was related to variations of viscosity ratios of components in the reactive PP/PS blends with different contents of AlCl₃ catalyst. The phase morphology evolution of the in-situ compatiblized reactive blend was determined by both the interfacial compatibilization and the variation of the viscosity ratio of components under the fixed mixing conditions, which showed characteristics obviously different from and much more complex than those in binary polymer blends generally compatiblized by added compatiblizers. The results implied that the variation of the viscosity ratio of components should be checked carefully and taken into account if necessary, when the phase morphology of binary polymer blends is investigated, especially in complex in-situ compatiblized reactive polymer blends.     

Effect of PMMA on crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate) blend prepared in semi-dilute solutions

Films of poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blend were derived from a special procedure of casting semi-dilute solutions. Hydrophilic character and crystallization of PVDF were optimized by variation of PMMA concentration in PVDF/PMMA blends. It was found that a PVDF/PMMA blend containing 70 wt% PMMA has a good performance for the potential application of hydrophilic membranes via thermally induced phase separation. The films presented β crystalline phase regardless of PMMA content existed in the blends. Thermal analysis of the blends showed a promotion of crystallization of PVDF with small addition of PMMA which induced larger lamellar thickness of PVDF, leading to the largest spherulitic crystal of PVDF (10 wt% PMMA) is about 8 μm. SEM micrographs illustrated no phase separation occurred in blends, due to the high compatibility between PVDF and PMMA.     

Effect of Nanoclay on the Morphology and Properties of Nylon 6 and Poly(Methyl Methacrylate) (PMMA) Blends

The effect of organomodified nanoclay on the morphology and properties of a (70/30 w/w) nylon 6/poly(methyl methacrylate) (PMMA) blend prepared by a melt processing method was investigated. The number average domain diameter (D_n ) of the dispersed PMMA phase was found to decrease with the addition of a small amount [0.5 per hundred resin (phr)] of clay in the blend. A much finer dispersion of the minor phase in the presence of a higher amount (5 phr) of clay indicated better mixing efficiency and improved morphology in the blend. X-ray diffraction indicated the exfoliation of the clays in the nylon 6 matrix, whereas PMMA chains only intercalated into the clay layers. However, the same effect of the clay was not observed in a (30/70 w/w) nylon 6/PMMA blend when nylon 6 became the dispersed domains. In the (30/70 w/w) nylon 6/PMMA blend, the addition of organomodified nanoclay (up to 2 phr) increased the D_n of the nylon 6 domains by preferential location of the clays inside the nylon 6 domains. Addition of styrene-maleic anhydride (SMA) copolymer effectively reduced the D_n of disperse phases in both compositions of the nylon 6/PMMA blends. Thus, in nylon 6/PMMA blends, clay platelets could prevent the coalescence of dispersed domains during melt mixing as long as it was dispersed in the matrix phase of the blend. Mechanical properties and thermal stability of the blends were also improved in the presence of clay.     

Melt blends of san with phenoxy

Melt blends of styrene-co-acrylonitrile (SAN) with phenoxy were prepared over a full range of compositions and were evaluated in terms of morphological, rheological, thermal, and mechanical properties. Viscosity-composition plots showed a crossover with the additivity line at 50/50 (SAN/phenoxy by weight), and deviations from semicircles in Cole‐Cole plots were seen for 70/30, 50/50, and 30/70 blends. Scanning electron micrographs (SEM) of the blends showed a two-phase morphology with a finer dispersion and well-elongated fibrils seen when SAN formed the dispersed phase. The glass transition temperature (T _g) of SAN was almost unchanged in the blends, whereas T _g of phenoxy was increased over 5°C. Tensile modulus and strength generally showed synergistic effects in phenoxy-rich blends. In the 10/90 blend, the ultimate elongation was greater than for pure phenoxy, and a dramatic drop of Izod impact strength was observed.     

Properties and Structure of Dynamically Vulcanized TPU/EVM Blends

The preparation of dynamically vulcanized TPU (thermoplastic polyurethane)/EVM (ethylene-vinyl acetate copolymer rubber) blends and the effect of two peroxide curing agents, DCP (dicumyl peroxide) and BIPB (bis(tert-butyl peroxy isopropyl)benzene) on the mechanical properties, hot air aging, and oil resistance were investigated. Fourier transform infrared spectroscopy (FTIR), phase-contrast microscopy (PCM), and magnetic resonance crosslink density spectroscopy (MR-CDS) were used to analyze the curing reaction, phase structure, and crosslink density of dynamic vulcanizates. The results showed that the optimum parameters for dynamically vulcanized TPU/EVM by peroxide-DCP or BIPB in a HAAKE rheometer were: mixing temperature 140–150°C and rotor speed 30 rpm. The mechanical properties and oil resistance of these blends were improved by dynamic vulcanization. It was found that BIPB is a better curing agent than DCP for the dynamic vulcanization of TPU/EVM and its optimum content was 0.8 phr in the blend. FTIR spectra showed EVM and TPU could both be cured by peroxide in the blend and the curing reaction occurred at -CH₂- groups that were linked with -C- instead of -O- and -CH₃ groups in the blend. PCM photographs showed that dynamically vulcanized TPU/EVM blends had “sea-island” phase structure when the curing agent content was low and it had “interlocked/co-continuous” phase structure as the curing agent content was increased. The spin-lattice relaxation constant, T_21, measured with MR-CDS proved that the crosslink density of the cured blends increased with increasing curing agent content.     

Thin-layer chromatography of copolyesters from blends of poly(ethylene terephthalate)/polycarbonate

Copolymers made by ester exchange reaction have been obtained from poly(ethylene terephthalate) (PET)/poly(bis-phenol-A carbonate) (PC) blends during melt mixing. The copolyesters were isolated by thin-layer chromatography (TLC) and identified by infrared spectroscopy. It was found that the quantity of copolymer formed was increased by the temperature and duration of melt mixing. The PET/PC blend was found to react at 270°C within 10 min, as detected by TLC. After 60 min, the pure PC had disappeared. The miscibility of PET/PC blends was found to be markedly aided by the addition of as little as 2% of the copolymer isolated by TLC.     

Morphology of mechanically dispersed SBR—cis-polybutadiene elastomer blends

The transient morphological development of blends of sytrene-butadiene rubber (SBR) and cis-polybutadiene (BR) is investigated as a function of the viscosity of the individual rubbers and also the energy input (using a power integrator) during the mixing process. The gum rubber blends consist of SBR:BR = 80:20 and 20:80 by weight ratio. The ebonite technique is used to prepare specimens for electron microscopic (EM) morphological study. The EM results reveal that these 80:20 and 20:80 weight ratio blends always consist of two phases. The minor component always forms the dispersed phase throughout the major component matrix. The viscosity of each blend, as well as the energy input during the mixing operation, strongly governs the resultant blend morphology. In the initial mixing stages, the domain sizes of the dispersed phase vary over a broad range. As more energy is introduced to the system, the range of domain

sizes narrows and these domains eventually approach a limiting size of approximately 0.1-0.5 μm and are uniformly distributed throughout the blend. The most efficient rate of domain development does not necessarily occur in a blend systems in which the viscosities of each component are matched. Higher-viscosity blends require more energy to attain an even domain distribution than do blends of lower viscosity. An equation relating the power integrator and also to the rheological properties is proposed. Its correlation with experimental results is also discussed.     

Natural rubber blends with epoxidized natural rubber

Blends of NR with ENR have been prepared in full composition following the polymer blend technique. Basic properties (mastication behavior and thermal degradation of each rubber and Mooney viscosity, Flory-Huggins interaction parameters, and cure characteristics of the blends) of the uncured blends were determined, in addition to the reversion, cross-linking density, mechanical and dynamic mechanical properties, rebound, and solvent swell of the blend vulcanizates. It was found that the NR ENR blends are immiscible, showing two glass transition temperatures (T_g's) that showed outward migration in the blends. This was interpreted in terms of preferred migration of the curatives into the ENR phase. Retention of mechanical properties on aging, solvent resistance, and heat buildup were greater in NR-rich blends due probably to the higher cross-link density of the blends.