Surface phase separations of PMMA/SAN blends investigated by atomic force microscopy

The thin films of poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (SAN) and their blends were prepared by means of spin-coating their corresponding solutions onto silicon wafers, followed by being annealed at different temperatures. The surface phase separations of PMMA/SAN blends were characterized by virtue of atomic force microscopy (AFM). By comparing the tapping mode AFM (TM-AFM) phase images of the pure components and their blends, surface phase separation mechanisms of the blends could be identified as the nucleation and growth mechanism or the spinodal decomposition mechanism. Therefore, the phase diagram of the PMMA/SAN system could be obtained by means of TM-AFM. Contact mode AFM was also used to study the surface morphologies of all the samples and the phase separations of the blends occurred by the spinodal decomposition mechanism could be ascertained. Moreover, X-ray photoelectron spectroscopy was used to characterize the chemical compositions on the surfaces of the samples and the miscibility principle of the PMMA/SAN system was discussed.

Morphology, structure, and properties of in situ compatibilized linear low-density polyethylene/polystyrene and linear low-density polyethylene/high-impact polystyrene blends

Blends of linear low-density polyethylene (LLDPE) with polystyrene (PS) and blends of LLDPE with high-impact polystyrene (HIPS) were prepared through a reactive extrusion method. For increased compatibility of the two blending components, a Lewis acid catalyst, aluminum chloride (AlCl3), was adopted to initiate the Friedel-Crafts alkylation reaction between the blending components. Spectra data from Raman spectra of the LLDPE/PS/AlCl3 blends extracted with tetrahydrofuran verified that LLDPE segments were grafted to the para position of the benzene rings of PS, and this confirmed the graft structure of the Friedel-Crafts reaction between the polyolefin and PS. Because the in situ generated LLDPE-g-PS and LLDPE-g-HIPS copolymers acted as compatibilizers in the relative blending systems, the mechanical properties of the LLDPE/PS and LLDPE/HIPS blending systems were greatly improved. For example, after compatibilization, the Izod impact strength of an LLDPE/PS blend (80/20 w/w) was increased from 88.5 to 401.6 J/m, and its elongation at break increased from 370 to 790%. For an LLDPE/HIPS (60/40 w/w) blend, its Charpy impact strength was increased from 284.2 to 495.8 kJ/m(2). Scanning electron microscopy micrographs showed that the size of the domains decreased from 4-5 to less than 1 mum, depending on the content of added AlCl3.

Morphology and thermal and mechanical properties of PBT/HIPS and PBT/HIPS-g-GMA blends

The modification of high-impact polystyrene (HIPS) was accomplished by melt-grafting glycidyl methacrylate (GMA) on its molecular chains. Fourier transform infrared spectroscopy and electron spectroscopy for chemical analysis were used to characterize the formation of HIPS-g-GMA copolymers. The content of GMA in HIPS-g-GMA copolymer was determined by using the titration method. The effect of the concentrations of GMA and dicumyl peroxide on the degree of grafting was studied. A total of 1.9% of GMA can be grafted on HIPS. HIPS-g-GNU was used to prepare binary blends with poly(buthylene terephthalate) (PBT), and the evidence of reactions between the grafting copolymer and PBT in the blends was confirmed by scanning electron microscopy (SEM), dynamic mechanical analysis, and its mechanical properties. The SEM result showed that the domain size in PBT/HIPS-g-GMA blends was reduced significantly compared with that in PBT/HIPS blends; moreover, the improved strength was measured in PBT/HIPS-g-GMA blends and results from good interfacial adhesion. The reaction between ester groups of PBT and epoxy groups of HIPS-g-GMA can depress crystallinity and the crystal perfection of PBT.

Compatibilization effects of block copolymers in high density polyethylene/syndiotactic polystyrene blends

Three triblock copolymers of poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) of different molecular weights and one diblock copolymer of poly[styrene-b-(ethylene-co-butylene)] (SEB) were used to compatibilize high density polyethylene/syndiotactic polystyrene (HDPE/sPS, 80/20) blend. Morphology observation showed that phase size of the dispersed sPS particles was significantly reduced on addition of all the four copolymers and the interfacial adhesion between the two phases was dramatically enhanced. Tensile strength of the blends increased at lower copolymer content but decreased with increasing copolymer content. The elongation at break of the blends improved and sharply increased with increments of the copolymers. Drop in modulus of the blend was observed on addition of the rubbery copolymers. The mechanical performance of the modified blends is strikingly dependent not only on the interfacial activity of the copolymers but also on the mechanical properties of the copolymers, particularly at the high copolymer concentration. Addition of compatibilizers to HDPE/sPS blend resulted in a significant reduction in crystallinity of both HDPE and sPS. Measurements of Vicat softening temperature of the HDPE/sPS blends show that heat resistance of HDPE is greatly improved upon incorporation of 20 wt% sPS.

Morphology, thermal behavior, and mechanical properties of PA6/UHMWPE blends with HDPE-g-MAH as a compatibilizing agent

A functionalized high-density polyethylene (HDPE) with maleic anhydride (MAH) was prepared using a reactive extruding method. This copolymer was used as a compatibilizer of blends of polyamide 6 (PA6) and ultrahigh molecular weight polyethylene (UHMWPE). Morphologies were examined by a scanning electron microscope. It was found that the dimension of UHMWPE and HDPE domains in the PA6 matrix decreased dramatically, compared with that of the uncompatibilized blending system. The size of the UHMWPE domains was reduced from 35 mu m (PA6/UHMWPE, 80/20) to less than 4 mu m (PA6/UHMWPE/HDPE-g-MAH, 80/20/20). The tensile strength and Izod impact strength of PA6/UHMWPE/HDPE-g-MAH (80/20/20) were 1.5 and 1.6 times as high as those of PA6/UHMWPE: (80/20), respectively. This behavior could be attributed to chemical reactions between the anhydride groups of HDPE-g-MAH and the terminal amino groups of PA6 in PA6/UHMWPE/HDPE-g-MAH blends. Thermal analysis was performed to confirm that the above chemical reactions took place during the blending process. (C) 2000 John Wiley & Sons, Inc.

Effects of pressure and molecular weight on the miscibility of polystyrene and cyclohexane

With the aid of Sanchez-Lacombe lattice fluid theory (SLLFT), the phase diagrams were calculated for the system cyclohexane (CH)/polystyrene (PS) with different molecular weights at different pressures. The experimental data is in reasonable agreement with SLLFT calculations. The total Gibbs interaction energy, g*(12) for different molecular weights PS at different pressures was expressed, by means of a universal relationship, as g(12)* =f(12)* + (P - P-0) nu*(12) demixing curves were then calculated at fixed (near critical) compositions of CH and PS systems for different molecular weights. The pressures of optimum miscibility obtained from the Gibbs interaction energy are close to those measured by Wolf and coworkers. Furthermore, a reasonable explanation was given for the earlier observation of Saeki et al., i.e., the phase separation temperatures of the present system increase with the increase of pressure for the low molecular weight of the polymer whereas they decrease for the higher molecular weight polymers. The effects of molecular weight, pressure, temperature and composition on the Flory Huggins interaction parameter can be described by a general equation resulting from fitting the interaction parameters by means of Sanchez-Lacombe lattice fluid theory.

Thermodynamics of PMMA/SAN blends: Application of the Sanchez-Lacombe lattice fluid theory

Polymer blends of poly(methyl methacrylate) (PMMA) and poly(styrene-co-acrylonitrile) (SAN) with an acrylonitrile content of about 30 wt % were prepared by means of solution-casting and characterized by virtue of pressure-volume-temperature (PVT) dilatometry. The Sanchez-Lacombe (SL) lattice fluid theory was used to calculate the spinodals, the binodals, the Flory-Huggins (FH) interaction parameter, the enthalpy of the mixing, the volume change of the mixing, and the combinatorial and vacancy entropies of the mixing for the PMMA/SAN system. A new volume-combining rule was used to evaluate the close-packed volume per mer, upsilon*, of the PMMA/SAN blends. The calculated results showed that the new and the original volume-combining rules had a slight influence on the FH interaction parameter, the enthalpy of the mixing, and the combinatorial entropy of the mixing. Moreover, the spinodals and the binodals calculated with the SL theory by means of the new volume-combining rule could coincide with the measured data for the PMMA/SAN system with a lower critical solution temperature, whereas those obtained by means of the original one could not.

Properties of ethylene-propylene copolymer/PA-1010 blends using ethylene-propylene copolymer-graft-acrylic acid as a compatibilizing agent

The modification of ethylene-propylene copolymer (EP) has been accomplished by radical EP-graft-acrylic acid (EP-g-AA) has been used to obtain ternary PA/EP/EP-g-AA blends by melt mixing. Different blend morphologies were observed by scanning electron microscopy; the domain size of the EP-dispersed phase in the polyamide 1010 matrix of compatibilized blends decreased compared with that of uncompatibilized blends. It is found that EP-g-AA used as the third component has a profound effect on the mechanical properties of the resulting blends. This behavior has been attributed to serious chemical interactions taking place between the two components. Thermal analysis shows that some thermal properties of PA in compatibilized PA/EP/EP-g-AA changed because of chemical reactions taken place during the blending process. Wide angle x-ray diffraction measurements also confirmed this result. (C) 1996 John Wiley & Sons, Inc.

Phase behavior in mixtures of a homopolymer and a block copolymer .4. SALS and SAXS studies

Phase behavior of blends of poly(vinyl methyl ether) (PVME) with four styrene-butadienestyrene (SBS) triblock copolymers, being of various molecular weights, architecture, and compositions, was investigated by small-angle light scattering. Small-angle X-ray scattering investigation was accomplished for one blend. Low critical solution temperature (LCST) and a unique phase behavior, resembling upper critical solution temperature (UCST), were observed. It was found that the architecture of the copolymer greatly influenced the phase behavior of the blends. Random phase approximation theory was used to calculate the spinodal phase transition curves of the ABA/C and BAB/C systems; LCST and resembling UCST phase behavior were observed as the parameters of the system changed. Qualitatively, the experimental and the theoretical results are consistent with each other. (C) 1996 John Wiley & Sons, Inc.

INFLUENCE OF ESTER GROUP-SIZE IN PMAS ON BETA-PHASE CRYSTALLIZATION OF PVF2 IN HIGHLY ORIENTED FILMS OF PVF2/PMAS BLENDS

Influence of ester group size in polymethacrylates (PMAs) , including PMMA, PEMA and PBMA, on beta phase crystallization of poly(vinylidene fluoride) (PVF2) in highly oriented films of PVF2/PMAs=80/20 blends has been investigated by FTIR and TEM. The melt-drawn films of pure PVF2 consist of highly oriented lamellae, in which the alpha phase is predominant. Adding a given amount of PMAs (20 wt%) into PVF2 results in formation of fibrillar crystals and increase of relative amount of the beta phase. The influence extent is in order of PMMA > PEMA > PBMA, regarding the ester group size in the PMAs.

A NEW ISOTHERMAL EQUATION OF STATE FOR POLYMERS

A new isothermal equation of state for polymers in the solid and the liquid is given by P = B(T, 0)/(n - m){[V(T, 0)/V(T, P)]n + 1 - [V(T, 0)/V(T, P)]m + 1} where n = 6.14 and m = 1.16 are general constant's for polymer systems. Comparison of the equation with experimental data is made for six polymers at different temperatures and pressures. The results predict that the equation of state describes the isothermal compression behaviour of polymers in the glass and the melt states, except at the transition temperature.

COMPATIBILIZING EFFECT OF POLY(ETHYLENE OXIDE)-B-POLYSTYRENE-B-POLY(ETHYLENE OXIDE) IN PHENOLPHTHALEIN POLY(ETHER ETHER KETONE) POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

The morphology and mechanical behaviour of phenolphthalein poly(ether ether ketone) (PEK-C)/poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) blends has been investigated. A poly(ethylene oxide)-b-polystyrene-b-poly(ethylene oxide) (PEO-PS-PEO) triblock copolymer was used as compatibilizer. It was found that PEO-PS-PEO has a compatibilizing effect on the PEK-C/PPO blends. The addition of PEO-PS-PEO to the blends greatly improves phase dispersion and interfacial interfacial adhesion and also enhances the ultimate tensile strength and Young's modulus at compositions ranging from 30 to 70% PEK-C. However, all the values of the ultimate tensile strength within the whole composition range are lower than those expected by simple additivity, probably owing to the poor mechanical properties of PEO-PS-PEO copolymer.

Solvent and polymer concentration effects on the surface morphology evolution of immiscible polystyrene/poly(methyl methacrylate) blends

The effects of solvent nature on the surface topographies of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend films spin-coated onto the silicon wafer were investigated. Four different solvents, such as ethylbenzene, toluene, tetrahydrofuran and dichloromethane, were chosen. They are better solvents for PS than that for PMMA. When dichloromethane, tetrahydrofuran and toluene were used, PMMA-rich phase domains protruded from the background of PS. When ethylbenzene was used, PS-rich phase domains elevated on the average height of PMMA-rich phase domains. In addition, continuous pits, networks and isolated droplets consisted of PS formed on the blend film surfaces with the decrease of polymer concentrations. The mechanism of the surface morphology evolution was discussed in detail.

Autophobic Dewetting of a Poly(methyl methacrylate) Thin Film on a Silicon Wafer Treated in Good Solvent Vapor

The wettability of thin poly(methyl methacrylate) (PMMA) films on a silicon wafer with a native oxide layer exposed to solvent vapors is dependent on the solvent properties. In the nonsolvent vapor, the film spread on the substrate with some protrusions generated on the film surface. In the good solvent vapor, dewetting happened. A new interface formed between the anchored PMMA chains and the swollen upper part of the film. Entropy effects caused the upper movable chains to dewet on the anchored chains. The rim instability depended on the surface tension of solvent (i.e., the finger was generated in acetone vapor (gamma(acetone) = 24 mN/m), not in dioxane vapor (gamma(dioxane) = 33 mN/m)). The spacing (lambda) that grew as an exponential function of film thickness h scaled as similar to h(1.31) whereas the mean size (D) of the resulting droplets grew linearly with h.

Monte Carlo simulation of miscibility of polymer blends with repulsive interactions: effect of chain structure

The effects of the chain structure and the intramolecular interaction energy of an A/B copolymer on the miscibility of the binary blends of the copolymer and homopolymer C have been studied by means of a Monte Carlo simulation. In the system, the interactions between segments A, B and C are more repulsive than those between themselves. In order to study the effect of the chain structure of the A/B copolymer on the miscibility, the alternating, random and block copolymers were introduced in the simulations, respectively. The simulation results show that the miscibility of the binary blends strongly depends on the intramolecular interaction energy ((ε) over bar (AB)) between segments A and B within the A/B copolymers. The higher the repulsive interaction energy, the more miscible the A/B copolymer and homopolymer C are. For the diblock copolymer/homopolymer blends, they tend to form micro phase domains. However, the phase domains become so small that the blend can be considered as a homogeneous phase for the alternating copolymer/ homopolymer blends. Furthermore, the investigation of the average end-to-end distance ((h) over bar) in different systems indicates that the copolymer chains tend to coil with the decrease Of (ε) over bar (AB) whereas the (h) over bar of the homopolymer chains depends on the chain structure of the copolymers.