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.

Theoretical calculation of Flory-Huggins and scattering interaction parameters by means of the lattice fluid theory for PVME/PSD blends

By fitting the spinodals of poly(vinyl methyl ether)/deuterated polystyrene (PVME/PSD) systems, the adjustable parameters epsilon (12)* and delta epsilon* in the Sanchez-Balasz lattice fluid (SBLF) theory could be determined for different molecular weights. According to these parameters, Flory-Huggins and scattering interaction parameters were calculated for PVME/PSD with different molecular weights by means of the SELF theory. From our calculation, Flory-Huggins and scattering interaction parameters are both Linearly dependent on the reciprocal of the temperature, and almost linearly on the concentration of PSD. Compared with the scattering interaction parameters, the Flory-Huggins interaction parameters decreased more slowly with an increase in the concentration for all three series of blends.

Study of elastic modulus and yield strength of polymer thin films using atomic force microscopy

Nanometer-scale elastic moduli and yield strengths of polycarbonate (PC) and polystyrene (PS) thin films were measured with atomic force microscopy (AFM) indentation measurements. By analysis of the AFM indentation force curves with the method by Oliver and Pharr, Young's moduli of PC and PS thin films could be obtained as 2.2 +/- 0.1 and 2.6 +/- 0.1 GPa, respectively, which agree well with the literature values. By fitting Johnson's conical spherical cavity model to the measured plastic zone sizes, we obtained yield strengths of 141.2 MPa for PC thin films and 178.7 MPa for PS thin films, which are similar to2 times the values expected from the literature. We propose that it is due to the AFM indentation being asymmetric, which was not accounted for in Johnson's model. A correction factor, epsilon, of similar to0.72 was introduced to rescale the plastic zone size, whereupon good agreement between theory and experiment was achieved.

Mixing enthalpy and phase behavior of PEO/PVAc blends

Phase behaviors and heats of mixing of the miscible blends of poly(ethylene oxide) (PEO) and poly(vinyl acetate) (PVAc) with different molecular weights were investigated by DSC. A method proposed by Natasohn and Ebert et al. was adopted to estimate the binodal temperatures and the enthalpies of mixing from onset temperatures and values of areas of a series of endothermic peaks (corresponding to heats of demixing), respectively, in their heating scanning thermograms obtained with different heating rates. Phase diagrams and heats of mixing of this blending system were also predicted by using Sanchez-Lacombe lattice fluid theory. A very good agreement was obtained for both. phase behaviors and heats of mixing obtained with two different methods.

Studies on blends of LLDPE and polar polymers compatibilized by a random copolymer

Compatibilization of blends of Linear low-density polyethylene (LLDPE)-poly(methyl methacrylate) (PMMA) and LLDPE-copolymer of methyl methacrylate (MMA) and 4-vinylpyridine (poly(MMA-co-4VP) with poly(ethylene-co-methacrylic acid) (EMAA) have been studied. Mechanical properties of the LLDPE-PMMA blends increase upon addition of EMAA. In order to further improve interfacial adhesion of LLDPE and PMMA, 4-vinyl pyridine units are introduced into PMMA chains, or poly(MMA-co-4VP) is used as the polar polymer. In LLDPE-poly(MMA-co-4VP)-EMAA blends, interaction of MAA in EMAA with 4VP of poly(MMA-co-4VP) causes a band shift in the infrared (IR) spectra. Chemical shifts of N-1s binding energy in X-ray photoelectronic spectroscopy (XPS) experiments indicate a transfer of proton from MAA to 4VP. Scanning electron microscopy (SEM) pictures show that the morphology of the blends were improved upon addition of EMAA. Nonradiative energy transfer (NRET) fluorescence results attest that there exists interdiffusion of chromophore-labeled LLDPE chains and chromophore-labeled poly(MMA-co-4VP) chains in the interface. Based on experimental results, the mechanism of compatibilization is studied in detail. Compatibilization is realized through the interaction between MAA in EMAA with 4VP in poly(MMA-co-4VP). (C) 1999 John Wiley & Sons, Inc.

Effect of the core-shell latex polymer content on the compatibility, morphology and mechanical properties of PC/PBA-cs-PMMA blends

The toughening effect of the content of a core-shell poly(butyl acrylate)/poly(methyl methacrylate) latex polymer (PBA-cs-PMMA) on the mechanical properties, morphology and compatibility of its blends with polycarbonate(PC), i.e., PC/PBA-cs-PMMa, was studied. The mechanical properties of the blends are strongly affected by varying the content of PBA-cs-PMMA in the blend. When the PBA-cs-PMMA content is only 5 wt.-%, the impact strength of PC/PBA-cs-PMMA is almost 19 times as high as that of pure PC, indicating that PBA-cs-PMMA is a very good impact modifier for PC. With increasing interphacial layer thickness and decreasing interphacial tension, the interphacial activity becomes more and more effective and, at the same time, miscibility increases too.

The miscibility of homopolymer random copolymer blends .3. Blends of SAA with polymethacrylates and polyesters

The miscibility of blends of poly(styrene-co-allyl alcohol) (SAA) with poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), poly(n-butyl methacrylate) (PnBMA), poly-epsilon-caprolactone (PCL) or polycarbonate (PC) has been studied by means of NMR, FT-IR and DSC techniques. It was found that SAA and PMMA, PEMA or PCL form miscible blends and SAA is only partially miscible with PC or PnBMA. Both phenyl groups and hydroxyl groups in SAA are involved in the intermolecular interactions between SAA and PMMA, PEMA or PCL. Also the hydroxyl-carbonyl hydrogen bonds existing in all the miscible blends studied are formed partially at the expense of the disruption of self-association of hydroxyl groups in pure SAA. (C) 1997 Elsevier Science Ltd. All rights reserved.

Study of the blends containing core-shell latex polymer

Polycarbonate (PC) and a core-shell latex polymer composed of poly(butyl acrylate) and poly(methyl methacrylate) (PBA-cs-PMMA) as core and shell, respectively, were mixed using a Brabender-like apparatus under different conditions. The mechanical properties, the morphology and the processability of the blends were investigated. Because of the good compatibility of PC and PMMA, even dispersion of PBA-cs-PMMA in PC matrix and good adhesion between the components have been achieved. PBA-cs-PMMA is thus a very good impact modifier for PC. The toughening mechanism is both cavitation and shear yielding, as indicated by SEM observation. (C) 1997 Elsevier Science Ltd.

Dynamic mechanical properties of interpenetrating polymer networks based on polyacrylates and epoxy

Interpenetrating polymer networks (IPNs) based on polyacrylate (poly(polyethylene glycol diacrylate), PEGDA) and epoxy(diglycidyl ether of bisphenol A, DGEBA) were prepared simultaneously Dynamic mechanical properties of the SINs (simultaneous interpenetrating networks) with various compositions were studied. Enhanced mechanical properties were found in this case. From the point of view of pre-swollen networks, all of the PEGDA/DGEBA IPNs were composed of the individual pre-swollen networks. A micro-phase segregation system was produced in the SIN. Glass transition temperatures shifted inward, which was attributed to molecular packing effects or mutual-entanglements of molecular segments among the individual pre-swollen networks. In accordance with the additivity of properties, namely the parallel model, the entanglement density between the two polymer networks reached its maximum at 50/50 PEGDA/DGEBA IPN.

Synthesis and characterization of interpenetrating polymer networks based on polyacrylate and epoxy

The synthesis and properties of simultaneously interpenetrating networks (SINs) based on poly(polyethylene glycol diacrylate) (PEGDA) and epoxy (diglycidyl ether of bisphenol A, DGEBA) were studied. The effect of compositional variation on the morphology and properties of products was investigated. The swelling coefficient, densities, glass transition behavior, and thermal stability of these interpenetrating networks (IPNs) are discussed. Microphase separation morphological structures were found in all PEGDA/DGEBA IPNs. Decreased swelling ratios compared to the calculated swelling coefficients based on the weight additivity of the components were obtained after the formation of IPNs. Increased density and thermal stability were also obtained in these IPNs, implying the existence of interpenetration (topological entanglements) among the component networks.

Plastic zone in front of mode I crack in phenolphthalein polyether ketone

The plastic zone size and crack opening displacement of phenolphthalein polyether ketone (PEK-C) at various conditions were investigated. Both of them increase with increasing temperature (decreasing strain rate), i.e. yield stress steadily falls. Thus, the mechanism increasing the yield stress leads to increased constraint in the crack tip and a corresponding reduction in the crack opening displacement and the plastic deformation zone. The effect of the plastic deformation on the fracture toughness is also discussed.

TEMPERATURE AND STRAIN-RATE DEPENDENCE OF FRACTURE-TOUGHNESS OF PHENOLPHTHALEIN POLYETHER KETONE

A strong strain-rate and temperature dependence was observed for the fracture toughness of phenolphthalein polyether ketone (PEK-C). Two separate crack-blunting mechanisms have been proposed to account for the fracture-toughness data. The first mechanism involves thermal blunting due to adiabatic heating at the crack tip for the high temperatures studied. In the high-temperature range, thermal blunting increases the fracture toughness corresponding to an effectively higher test temperature. However, in the low-temperature range, the adiabatic temperature rise is insufficient to cause softening and Jic increases with increasing temperature owing to viscoelastic losses associated with the p-relaxation there. The second mechanism involves plastic blunting due to shear yield/flow processes at the crack tip and this takes place at slow strain testing of the single-edge notched bending (SENB) samples. The temperature and strain-rate dependence of the plastic zone size may also be responsible for the temperature and strain-rate dependence of fracture toughness.

A DIFFERENTIAL SCANNING CALORIMETRY STUDY OF PLASMA IRRADIATION GRAFTING OF NASCENT POLYETHYLENE REACTOR POWDER

The melting behavior of poly(methyl methacrylate)-grafted nascent polyethylene reactor powder by plasma irradiation was studied by differential scanning calorimetry (DSC). The grafting yield ranged hom 11 to 190%. Grafting was found to lower both melting point and heat of fusion during the first run of DSC determination. The heat of fusion was used to calculate the apparent grafting yield of the samples. There was little strain induced by plasma-irradiated grafting on the surface of the polyethylene crystals. A method to determine the covalent grafting yield in the graft copolymer systems was developed. (C) 1995 John Wiley & Sons, Inc.

A STUDY ON POLYMER-POLYMER INTERACTIONS THROUGH MIXING CALORIMETRY

The aim of this work is to describe the most recent achievements in the field of the physical chemistry of mixing. The systems studied have been classified according to the amount of thermic effect due to the blending and its interpretation. When polystyrene (PS) and poly(alpha-methylstyrene) (P alpha MS) are blended, the interaction is weak and Delta(mix)H is close to zero. The presence of polar atoms and/or groups increases the stability of the blend and, therefore, Delta(mix)H becomes more negative. Poly(ethylene oxide) (PEO), poly(methyl acrylate) (PMA), poly(methyl methacrylate) (PMMA) and poly(vinylacetate) (PVAc), when mixed to form binary systems, show large differences from their properties when pure. If hydrogen bonding takes place, the interactions are readily detected and a large effect is calorimetrically determined. Cellulose diacetate (CDA) and poly(vinylpyrrolidone) (PVP) have been studied as an example of a strongly interacting system.

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.