PC-SAFT Equation: A Predictive Tool to Determine Experimental Conditions for Polymer Blend Demixing

Abstract

The perturbed-chain statistical associating fluid theory equation of state (PC-SAFT) was applied to predict the phase behavior of polymer solutions in order to determine the pressure – temperature region for the high molecular weight polymer blend separation by using n-alkanes at high pressure and high temperature. The polymer blends selected were physical blends of polyethylene (PE)/polystyrene (PS), and polypropylene (PP)/PS. The miscibility and immiscibility region of each polymer in different alkanes (n-pentane, n-hexane, and n-heptane) was studied and from this analysis, the experimental conditions of the polymer blend demixing were predetermined. The results obtained were validated with experimental data indicating that the PC-SAFT equation is a good tool to predict experimental conditions for the processing windows of polymer blend separation.     

Preparation of polypropylene and polystyrene with NCO and NH2 functional groups and their applications in polypropylene/polystyrene blends

Isocyanate‐ and amine‐functionalized polypropylene (PP) and polystyrene (PS) were prepared through grafting and copolymerization method. These compounds are used as precursors for PP‐graft‐PS (PP‐g‐PS) copolymers and reacted at the matrix interface of PP/PS blends. Functionalized polymer structures were characterized by ¹H NMR and FTIR spectroscopy. The effects of the synthesized compatibilizer on the rheological and morphological behavior of PP/PS blends were investigated systematically. Results showed that the functional polymer was successfully synthesized, and the additional two different compatibilizer systems dramatically decreased the size of the dispersed phase domains in PP/PS blends. Compared with the uncompatibilized blends, compatibilized blends exhibited a slightly higher crystallization temperature because the melting points of the blend components were not evidently affected by the addition of compatibilizer, as revealed by differential scanning calorimetry. The compatibilizer effect on the PP/PS blends was reflected through rheological property and dynamic mechanical analysis. POLYM. ENG. SCI., 55:614–623, 2015. © 2014 Society of Plastics Engineers     

Synthesis of polypropylene‐grafted graphene and its compatibilization effect on polypropylene/polystyrene blends

Polypropylene‐graft‐reduced graphene oxide (PP‐g‐rGO) was synthesized and used as a novel compatibilizer for PP/polystyrene (PP/PS) immiscible polymer blends. SEM observation revealed an obvious reduction of the average diameter for the dispersed PS phase with the addition of PP‐g‐rGO into a PP/PS (70/30, w/w) blend. The compatibilization effect of PP‐g‐rGO will subsequently lead to the enhancement of the tensile strength and elongation at break of the PP/PS blends. The compatibilizing mechanism should be ascribed to the fact that PP‐g‐rGO can not only adsorb PS chains on their basal planes through π‐π stacking but also exhibit intermolecular interactions with PP through the grafted PP chains. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40455.     

Sorption,diffusion, and pervaporation separation of water–acetic acid mixtures through the blend membranes of sodium alginate and guar gum‐grafted‐polyacrylamide

Nonporous homogeneous dense membranes were prepared from the blends of sodium alginate (Na–Alg) with guar gum‐grafted polyacrylamide (GG‐g‐PAAm) in the ratios of 3 : 1 and 1 : 1 and these were tested for the pervaporation separation of water–acetic acid mixtures at 30°C. Blend compatibility was studied in solution by measuring the viscosity and the speed of sound. Membranes were crosslinked by glutaraldehyde. The GG‐g‐PAAm polymer and the crosslinked blend membranes were characterized by Fourier transform infrared spectra. High separation selectivity was exhibited by the pure Na–Alg membrane for water–acetic acid (HAc) mixtures containing 20 mass % of water. The permeation flux increased with increasing mass percent of water in the feed as well as with an increase in the amount of GG‐g‐PAAm in the blend, but separation selectivity decreased. Sorption selectivity was higher for the Na–Alg membrane than for the blend membranes, but it decreased with increasing mass percent of GG‐g‐PAAm in the blends. Diffusion selectivity values vary systematically with the blend composition, but not with the amount of water in the feed. Diffusion coefficients of the water–HAc mixtures were calculated from Fick's equation using sorption data and compared with those calculated from flux values obtained in pervaporation experiments. The Arrhenius activation parameters were calculated for the 20 mass % of water in the feed using flux and diffusion data obtained at 30, 40, and 50°C. The diffusion and pervaporation results are explained in terms of solution–diffusion concepts. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 259–272, 2002     

Studies on molecular transport of n‐alkanes through poly(tetrafluoroethylene‐co‐propylene) elastomeric membrane

Molecular transport of a series of n‐alkanes through commercial TFE elastomer (FA 150L) has been studied in the temperature range 30–50 °C using sorption‐gravimetric method. The Fickian diffusion equation was used to calculate the diffusion coefficients, which were dependent on the size of the alkanes and temperature. The diffusion coefficients at 30°C varied from 4.53 × 10^?8 cm²/s (n‐heptane) to 0.18 × 10^?8 cm²/s (n‐hexadecane). The liquid concentration profiles have also been computed using analytical solution of Fick's equation with the appropriate initial and boundary conditions and these were presented as a function of penetration depth of molecular migration and time of immersion. These results have been discussed in terms of molecular size of alkanes as well as temperature. In all the liquid penetrants, the transport phenomenon was found to follow the anomalous behavior. From the temperature dependence of diffusion and permeation coefficients, the Arrhenius activation parameters have been estimated. These parameters do not exhibit any systematic variation with the size of the penetrants. The resulting low diffusion coefficients, contribute to the superior barrier performance of the membrane, is due, in part, to the high glass transition temperature of Aflas? TFE elastomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2228–2235, 2006     

Polypropylene‐dispersed domain as potential nucleating agent in PS and PMMA solid‐state foaming

The potential of using dispersive domains in a polymer blend as a bubble nucleating agent was investigated by exploiting its high dispersibility in a matrix polymer in the molten state and its immiscibility in the solid state. In this experiments, polypropylene (PP) was used as the nucleating agent in polystyrene (PS) and poly(methyl methacrylate) (PMMA) foams at the weight fraction of 10, 20, and 30 wt %. PP creates highly dispersed domains in PS and PMMA matrices during the extrusion processing. The high diffusivity of the physical foaming agent, i.e., CO₂ in PP, and the high interfacial tension of PP with PS and PMMA could be beneficial for providing preferential bubble nucleation sites. The experimental results of the pressure quench solid‐state foaming of PS/PP and PMMA/PP blends verified that the dispersed PP could successfully increase the cell density over 10⁶ cells/cm³ for PS/PP and 10⁷ cells/cm³ for PMMA/PP blend and reduce the cell size to 24 μm for PS/PP and 9 μm for PMMA/PP blends foams. The higher interfacial tension between PP and the matrix polymer created a unique cell morphology where dispersed PP particles were trapped inside cells in the foam. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study of the nonlinear phase‐separation behavior of a polystyrene/poly(vinyl methyl ether) blend using small‐angle light scattering

The thermally induced phase‐separation behavior of a polystyrene/poly(vinyl methyl ether) (PS/PVME) blend was studied mainly using time‐resolved small‐angle light scattering, as a function of temperature and heating rate. Under a non‐isothermal field, the dependence of the critical temperature on heating rate deviated obviously from linearity, even at very low heating rates. Such a nonlinear dependence was consistent with the deviation from linearity of the temperature dependence of the isothermal phase‐separation behavior in a wider temperature range from 100 to 140 °C. It was also found that a Williams–Landel–Ferry (WLF)‐like equation could be employed to describe the temperature dependence of the apparent diffusion coefficient (D_app) and the relaxation time (τ) of normalized scattering intensity at the early stage of spinodal decomposition (SD), as well as τ of phase behavior at the late stage of SD for the PS/PVME blend. The equilibrium phase‐separation temperature could hardly be established through the conventional linear extrapolation of heating rate or D_app to zero at the early stage of SD. The successful use of the WLF‐like function for PS/PVME blends extends the applicability of the time–temperature superposition principle for describing the phase‐separation behavior of binary polymer mixtures over a relatively large temperature range. Copyright © 2010 Society of Chemical Industry     

Time‐temperature superposition principle applicability for blends formed of immiscible polymers

In this work, the linear viscoelastic behavior of PP/PS and PP/HDPE blends modified with SEBS and EPDM, respectively, was studied. Small amplitude oscillatory shear measurements were carried out at different temperatures, ranging from 190°C to 240°C. The storage (G') and loss (G") moduli curves obtained were horizontally shifted and curves of angle delta (δ) (δ = atan (G"/G')) as a function of complex shear modulus (G*), known as van Gurp plots, were obtained at several temperatures, to test the applicability of time‐temperature superposition principle (TTS) to these blends. The results showed that successful application of TTS depends on the flow energy of activation and horizontal shift factors of the individual components of the blend, on the interfacial properties of the blend and on the concentration of compatibilizer added to the blend. TTS application failed for PP/PS blend, but held for PP/HDPE blend. Addition of SEBS to PP/PS blends promoted successful TTS application at specific concentrations that corresponded to interfacial saturation of the dispersed phase. Addition of EPDM did not imply sensitive change on TTS application for the PP/HDPE blends.     

Relationship between branch length and the compatibilizing effect of polypropylene‐g‐polystyrene graft copolymer on polypropylene/polystyrene blends

Three polypropylene‐g‐polystyrene (PP‐g‐PS) graft copolymers with the same branch density but different branch lengths were evaluated as compatibilizing agents for PP/PS blends. The morphological and rheological results revealed that the addition of PP‐g‐PS graft copolymers significantly reduced the PS particle size and enhanced the interfacial adhesion between PP and PS phases. Furthermore, it is verified that the branch length of PP‐g‐PS graft copolymer had opposite effects on its compatibilizing effect: on one hand, increasing the branch length could improve the compatibilizing effect of graft copolymer on PP/PS blends, demonstrated by the reduction of PS particle size and the enhancement of interfacial adhesion; on the other hand, increasing the branch length would increase the melt viscosity of PP‐g‐PS graft copolymer, which prevented it from migrating effectively to the interface of blend components. Additionally, the crystallization and melting behaviors of PP and PP/PS blends were compared. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40126.     

Thermal degradation and combustion of polymeric blends

The thermal stability of polymer blends was investigated by means of gas chromatography–mass spectroscopy (GC/MS) and thermal analysis. Evaluated changes in thermal stability can be attributed to blending. On the other hand, we were interested in whether blending may provide a method to control thermal stability and combustibility of polymeric materials. A new scheme of thermal degradation for polystyrene‐polydimethylsiloxane (PDMS) blend was suggested. In the case of polystyrene (PS) as a part of the blend, the products of degradation of PS diffuse through the phase boundary, which cause interaction with PDMS polymers. Apparently, PDMS acts as an inert component, slowing down the termination reaction by dilution of macroradicals formed in random scission degradation process of the PS component. On the other hand, it stabilizes the PS by means of interpolymer recombination, which leads to cross products of thermal degradation. Two of the degradation products: 2‐phenyl‐4(1′,3′,3′,5′,5′‐pentamethylcyclotrisiloxane)‐butane and 2‐phenyl‐4(1′,3′,3′,5′,5′,7′,7′‐heptamethylcyclotrisiloxane)‐butane were assigned to the products of cross‐interpolymer recombination which can accelerate the process of PDMS depolymerization by means of radical initiation of PS* fragments. The connection between a polymer thermal oxidative degradation and its combustion under diffusion flames condition was shown by using composition of polypropylene‐polypropylene‐co‐polyethylene (PP/PP‐co‐PE). In general, the solid‐phase polymer reaction can play a very important role in the reduction of polymer combustibility. It was shown that the composition of PP/PP‐co‐PE (62 : 38) has the highest induction period of autooxidation, which correlates with its combustibility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3300–3311, 2002     

Rheology,morphology, and mechanical properties of reactive compatibilized polypropylene/polystyrene blends via Friedel–Crafts alkylation reaction in the presence of clay

Attempts were made to study the effect of reactive compatibilization via Friedel–Crafts alkylation reaction, using AlCl₃ as a catalyst, on rheology, morphology, and mechanical properties of polypropylene/polystyrene ( PP/PS) blends in the presence of an organoclay (Cloisite 15A). During the reactive compatibilization process, PS showed much more degradation than that of PP in the presence of AlCl₃. It was found that the effect of generation of PP‐g‐PS copolymer at the interface of the PP/PS blend dominates the effects of degradation of PS and PP phases, which manifested itself by increased toughness as well as uniform dispersion of the dispersed PS particles in the PP matrix. Generation of PP‐g‐PS copolymer was confirmed by using Fourier‐transform infrared analysis. By using rheological and X‐ray diffraction analyses, it was shown that the clay had higher affinity to PS than that of PP. It was also shown that the clay located at the interface of PP and PS phases, leading to increased relaxation time of the deformed PS dispersed particles, exhibited higher dispersion in PP/PS blend, which resulted in higher ductility of the blend. By using the results of rheological studies, it was concluded that during reactive compatibilization of the blend nanocomposite, the clay migrated into the dispersed PS phase, which was confirmed by scanning electron microscopy analysis. It was demonstrated that the rheological studies have a reliable sensitivity to the clay partitioning and phase morphology of the studied blends and blend nanocomposites . J. VINYL ADDIT. TECHNOL., 24:18–26, 2018. © 2015 Society of Plastics Engineers     

Phase diagrams of thermally stable,polymer‐dispersed liquid crystals: Exploring the impact of chain length and chemical structure

Polymer‐dispersed liquid crystals (PDLCs) have garnered significant interest and motivated the investigation of the phase behavior of thermally stable smectic liquid crystals (LCs) via thermally induced phase separation (TIPS). In this study, we examined a series of two, biphenyl‐based smectic LCs suitable for high temperature polymer blend processing. Phase diagrams for LC/polystyrene (PS) blends at various compositions (0–60 wt%) were constructed. Less than 15 wt% of 8B8 (1,1′‐biphenyl‐4,4′‐diyl dioctanoate) LC in PS led to good polymer miscibility, while phase separation was induced at concentrations higher than 15 wt%. The LC concentration at saturation decreased with increasing aliphatic chain length. We also investigated the chain length (C6‐C16) effect on the PS glass transition temperature (T_g) at the LC saturation point. The T_g increased with increasing chain length due to reduced plasticization. We further examined the role of chemical structure (relatively less polar ether vs. more polar ester) on the phase diagram regions and the T_g of the nonpolar PS matrix, respectively. It is anticipated that these LC/PS phase diagrams will benefit elevated temperature processing for TIPS by highlighting the role of LC chemical structure and chain length on blend morphology. POLYM. ENG. SCI., 56:388–393, 2016. © 2016 Society of Plastics Engineers     

Compatibilization of poly(vinyl chloride) and polystyrene blends with poly(styrene‐co‐n‐methylolacrylamide)

In this work, the compatibilization of blends of plasticized polyvinyl chloride (PVC) and polystyrene (PS) with poly(styrene‐co‐n‐methylolacrylamide) (PSnMA) was investigated. The PSnMA was synthesized by emulsion polymerization with different amounts of n‐methylolacrylamide (nMA). Particle size and phase behavior was determined by scanning electron microscopy, and mechanical properties were determined in an Universal Testing Machine. Micrographs revealed that an appreciable size reduction of the dispersed phase was achieved when small amounts of PSnMA were added to the blend, and as the amount of nMA was increased, particle size decreased. When the (PVC/PS/PSnMA) blend was subjected to solvent extraction to remove PS and unreacted PVC, the residue showed a single T_g. Tensile modulus and the ultimate strength of the blends increased with PSnMA content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of additives on the composition dependent glass transition variation in PS/PP blends

The effect of additives on glass transition behavior in melt processed blends of polystyrene (PS) and polypropylene (PP) was studied. Blends of additive‐free polystyrene and additive‐free polypropylene revealed the known effect of the PS T_g increase in blend compositions where PP surrounds PS. Glass transition behavior in these blends was compared to blends prepared from additive‐free PP and commercial grade PS, which contained lubricant additives. The thermal transitions of PS and PP were measured using modulated DSC. Although the behavior of low PS concentration blends was similar in both systems, the characteristics of the high PS blends differed substantially. These differences and the contrast in the PP T_g behaviors were attributed to the migration of additives from the PS phase across the immiscible interface into the PP phase. Similar T_g variations were observed in blends of commercial grade PS and commercial grade PP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polyamide/Polystyrene Blend Compatibilisation by Montmorillonite Nanoclay and its Effect on Macroporosity of Gas Diffusion Layers for Proton Exchange Membrane Fuel Cells

This work deals with a new route to modify polymer blend morphology in order to improve the porosity of gas diffusion layers (GDLs) for proton exchange membrane fuel cells (PEMFCs). First, electrically conductive polymer‐based blends were carefully formulated using a twin‐screw extrusion process. Blend electrical conductivity was ensured by the addition of high specific surface area carbon black and synthetic graphite flakes. Final GDL porosity, in particular its macroporosity, was generated by melt blending polyamide 11 (PA11) matrix with polystyrene (PS) followed by PS extraction with tetrahydrofuran (THF) solvent at room temperature. In order to improve GDL porosity by the optimisation of PS dispersion in the PA11 matrix, PA11/PS blends were compatibilised by the addition of 2 wt.‐% of clay. It was observed that both macroporosity and pore size distribution were beneficially modified after blend compatibilisation. Final GDL conductivity of about 1.25 S cm^–1, a porosity of 53% and a specific pore surface area of 75 m² g^–1 were achieved.     

Comparison of olefin copolymers as compatibilizers for polypropylene and high‐density polyethylene

Some polyolefin elastomers were compared as compatibilizers for blends of polypropylene (PP) with 30 wt % high‐density polyethylene (HDPE). The compatibilizers included a multiblock ethylene–octene copolymer (OBC), two statistical ethylene–octene copolymers (EO), two propylene–ethylene copolymers (P/E), and a styrenic block copolymer (SBC). Examination of the blend morphology by AFM showed that the compatibilizer was preferentially located at the interface between the PP matrix and the dispersed HDPE particles. The brittle‐to‐ductile (BD) transition was determined from the temperature dependence of the blend toughness, which was taken as the area under the stress–strain curve. All the compatibilized blends had lower BD temperature than PP. However, the blend compatibilized with OBC had the best combination of low BD temperature and high toughness. Examination of the deformed blends by scanning electron microscopy revealed that in the best blends, the compatibilizer provided sufficient interfacial adhesion so that the HDPE domains were able to yield and draw along with the PP matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Determination of the phase diagram of HBA‐HNA liquid crystalline polymer/polycarbonate blends

The phase diagram of blends of liquid crystalline polymer (LCP) and polycarbonate (PC) was constructed. The effect of temperature on morphological development in melt‐blended samples was examined with a polarized light microscope, in conjunction with a heating stage. Phase separation in the blend was observed as the temperature was increased. For a particular LCP/PC blend composition, two‐phase separation temperatures (T_sp1 and T_sp2) were determined. Consequently, the corresponding phase diagram relating to phase separation was constructed. It was divided into three regions. No phase separation occurred when the blend was below T_sp1. However, a slight phase separation was detected when the temperature was between T_sp1 and T_sp2. Moreover, pronounced phase separation was observed when the blend was at a temperature above T_sp2. The phase‐separated structure varied according to the initial composition of the blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Fine disperse dyeable polypropylene fiber from polypropylene/polystyrene nano‐ceria blends

The blend of polypropylene (PP) and atactic polystyrene (PS) hybrid with nano‐ceria (CeO₂) was prepared for fine dyeable fiber. Nano‐CeO₂ modified with stearic acid was in situ added to PS by radical suspension polymerization. The dispersion of hy‐PS with nano‐CeO₂ in the PP crystals was investigated. The rheological behavior of the blend was similar to that of PP under the testing conditions, and the blend had stable spinning and drawing processability. The fine modified PP filaments were processed from the blend and had practical mechanical properties. The dyeability of the knitting fabrics from these filaments was studied. The increased amorphous content and the interface between PP and hy‐PS allowed the dye to penetrate the fiber, and the modified PP fiber had strong affinity to dye because of the complexation between cerium and dye. These effects resulted in improving K/S value and color fastness to soaping. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Molecular Weight Polydispersity Effects on Diffusion at Polymer/Polymer Interfaces

The effect of molecular weight distribution (MWD) on diffusion at symmetric polymer/polymer interfaces is investigated by rheological tools. A new model allowing the determination of a self‐diffusion coefficient of polydisperse polymer systems is presented. The model is based on the double reptation theory and Doi and Edwards' molecular dynamics applied to A/A polymers brought into intimate contact in the molten state. The material parameters for the model are obtained from linear oscillatory shear experiments, in which the dynamic shear modulus is measured in parallel plate geometry under a small amplitude of deformation as a function of time and frequency for a sandwich‐like assembly. The experiments were conducted on polystyrene (PS) blends with constant weight average molecular weight (M_w) but with variable number average molecular weights (M_n). The measured self‐diffusion coefficients showed that the presence of short molecules in the blend increases the mean value of the self‐diffusion coefficient and the magnitude of such increase can be quantitatively evaluated by the proposed model.     

Nonisothermal crystallization kinetics of polypropylene/polypropylene‐g‐polystyrene/polystyrene blends

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