Miscibility studies of polymer blends by viscometry methods

The intrinsic viscosities of blends of poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) (PVC/EVA), poly(vinyl chloride)/poly(styrene-co-acrylonitrile) (PVC/SAN), and poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile) (EVA/SAN) have been studied in cyclohexanone as a function of blend composition. In order to predict the compatibility of polymer pairs in solution, the interaction parameter term, Δb, obtained from the modified Krigbaum and Wall theory, and the difference in the intrinsic viscosities of the polymer mixtures and the weight average intrinsic viscosities of the two polymer solutions taken separately are used. © 1994 John Wiley & Sons, Inc.     

Studies on polymer blends with moderate specific interactions. 2. phase structure of blends SAN/TPU and SAN/TPU/EVA

This paper deals with morphological studies of binary and ternary blends composed of poly(styrene-co-acrylonitrile) (SAN), polyurethane elastomer (TPU) and poly(ethylene-co-vinyl acetate) (EVA). Selective etching was found necessary to expose the morphologies of the blends. Chloroform or hot acetone, hexane/toluene (2/1v/v) and NaOH/CH₃OH (1wt%) were found to be selective etching agents for SAN, EVA and TPU, respectively. SAN and TPU form blends with fine dispersion structure, while SAN and EVA lead to rough phase structure with poor phase adhesion. These results are in accordance with the difference in the mechanical properties of SAN/TPU and SAN/EVA. In addition, for SAN/TPU/EVA blends, if TPU is only a minor component, it is preferentially located at the interphase, playing the role of a compatibilizer. As the amount of TPU increases, the compatibility is gradually improved. ©1997 SCI     

Rheological studies of the poly(styrene-co-acrylonitrile) and poly(vinyl chloride-co-vinyl acetate) blends

The rheological studies of the poly(vinyl chloride-co-vinyl acetate) and poly(styrene-co-vinyl acetate) and poly(styrene-co-acrylonitrile) blends were performed by a Brabender Rheotron at three different temperatures and also at different shear rates. Flow curves of the blends at different temperatures were drawn. The flow behavior index and, also, zero-shear viscosity of the blends at different temperatures were determined. From the flow curves, it has been found that as shear stress increases, melt viscosity decreases at all temperatures, indicating that pseudoplastic behavior and experimental values lies above the line of the log-additivity value and below the line of the additivity rule of mixture. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2577–2583, 1998     

Fourier transform infrared spectroscopic studies of the poly(styrene-co-acrylonitrile) and poly (vinyl chloride-co-vinyl acetate) blends

The Fourier transform infrared (FTIR) spectroscopic studies of the poly-(styrene-co-acrylonitrile) (SAN) and poly(vinyl chloride-co-vinyl acetate) (VYHH) blends produced by different blending techniques, viz., solution blending, melt-blending, and also the co-precipitation methods of blending, were performed. In the case of miscible blend systems, substantial band shiftings took place, whereas immiscible blend systems showed slight or no band shifting. The miscible blends showed a substantial residual spectrum which was absent in the case of the immiscible system when a similar subtraction process was carried out. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 991–1000, 1997     

Compatibility enhancement of ABS/PVC blends

The compatibilizing effect of poly(styrene-co-acrylonitrile) (SAN) whose acrylonitrile (AN) content is 25 wt % (SAN 25) in poly(acrylonitrile-co-butadiene-co-styrene) (ABS)/poly(vinyl chloride) (PVC) blend was studied when the AN content of the matrix SAN in ABS was 35 wt % (SAN 35). When some amount of matrix SAN 35 was replaced by SAN 25 in a ABS/PVC (50/50 by weight) blend, the mixed phase of SAN and PVC at the interface was thickened, and about a twofold increase of impact strength was observed. The changes in morphology, dynamic mechanical properties, and rheological properties by the compatibilizing effect of SAN 25 were observed. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 705–709, 1998     

Synthesis of poly[(2‐oxo‐1,3‐dioxolan‐4‐yl)methyl vinyl ether‐co‐N‐phenylmaleimide] and its miscibility in blends with styrene‐acrylonitrile or poly(vinyl chloride)

The aim of the study was to investigate the synthesis of a copolymer bearing cyclic carbonate and its miscibility with styrene/acrylonitrile copolymer (SAN) or poly(vinyl chloride) (PVC). (2‐Oxo‐1,3‐dioxolan‐4‐yl)methyl vinyl ether (OVE) as a monomer was synthesized from glycidyl vinyl ether and CO₂ using quaternary ammonium chloride salts as catalysts. The highest reaction rate was observed when tetraoctylammonium chloride (TOAC) was used as a catalyst. Even at the atmospheric pressure of CO₂, the yield of OVE using TOAC was above 80% after 6 h of reaction at 80°C. The copolymer of OVE and N‐phenylmaleimide (NPM) was prepared by radical copolymerization and was characterized by FTIR and ¹H‐NMR spectroscopies and differential scanning calorimetry (DSC). The monomer reactivity ratios were given as r₁ (OVE) = 0.53–0.57 and r₂ (NPM) = 2.23–2.24 in the copolymerization of OVE and NPM. The films of poly(OVE‐co‐NPM)/SAN and poly(OVE‐co‐NPM)/PVC blends were cast from N‐dimethylformamide. An optical clarity test and DSC analysis showed that poly(OVE‐co‐NPM)/SAN and poly(OVE‐co‐NPM)/PVC blends were both miscible over the whole composition range. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1809–1815, 2000     

Spherical nanoparticle effects on the lower critical solution temperature phase behavior of poly(ε-caprolactone)/poly(styrene-co-acrylonitrile) blends: Separation of thermodynamic aspects from kinetics

The effects of spherical nanosilica particles on the lower critical solution temperature (LCST) phase diagram of poly(ε-caprolactone) (PCL)/poly(styrene-co-acrylonitrile) (SAN) blends are investigated by using isochronal dynamic temperature sweep tests at different cooling rates. A stronger dependency of the rheologically determined phase-transition points on the cooling rate is observed in the presence of nanoparticles, which results from the large contribution of entropic surface tension of chains in the Gibbs free energy of mixing and much slower rate of PCL/SAN phase dissolution. By alleviating the effects of kinetic factors, it is found that the drop in the LCST-type phase boundary of PCL/SAN blends by adding nanofiller is more apparent than real. However, the closest LCST phase diagram to the real steady-state thermodynamic diagram shows an unexpected shift to lower temperatures by adding nanosilica. The migration of nanosilica particles to the SAN domains especially at lower cooling rates in the dynamic measurements is the most likely explanation of these observations. The findings that prove the profound impact of kinetic factors in dynamic temperature measurements are reached in a hybrid system, wherein the SAN chains are preferentially absorbed on the surface of a nanofiller having very small primary particle size. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48679.     

Processability enhancement of poly(lactic acid-co-ethylene terephthalate) by blending with poly(ethylene-co-vinyl acetate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(butylene succinate)

Processability enhancement feasibility of an in-house synthesized poly(lactic acid-co-ethylene terephthalate), PLET, is investigated by blending with commercial poly(ethylene-co-vinyl acetate), EVA, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), PHBV, and poly(butylene succinate), PBS. The three blend systems are prepared by varying PLET contents, and their properties are characterized. DSC, SEM, and FTIR results indicate that PLET/EVA blends are immiscible, while the corresponding PLET/PBS and PLET/PHBV blends are miscible and partially miscible, respectively. DMA results show that the three blend systems have storage modulus comparable to those of commercial EVA, PHBV, and PBS, when PLET content is kept lower than 50, 25, and 25 wt%, respectively. PLET/EVA blends show higher thermal stability, compared to those of the other two blend systems. Results on degradability tests indicate that PLET/PBS blends show highest hydrolytic degradability, compared to the other two blends, as both blend constituents are associated in the hydrolytic degradation.     

Free volume as an internal material parameter to probe interfaces in ternary polymer blends: A positron lifetime study

A new method to characterize individual interfaces in ternary polymer blends from experimentally measured fractional free volume from Positron Annihilation Lifetime Spectroscopy (PALS) has been developed. By this, we derive the composition dependent miscibility level in ternary polymer blends. This method has its genesis in KRZ (Kirkwood–Risemann–Zimm) theory which introduces hydrodynamic interaction parameter as a measure of excess friction generated at the interface between dissimilar polymer chains resulting in energy dissipation. The method successfully applied for binary blends has been theoretically modified to suit ternary blends in the present work. The efficacy of this method has been tested for two ternary blends namely polycaprolactone/poly(styrene‐co‐acrylonitrile)/poly(vinyl chloride) (PCL/SAN/PVC) and polycaprolactone/poly(vinyl chloride)/poly(vinyl acetate) (PCL/PVC/PVAc) in different compositions. We obtained a maximum effective hydrodynamic interaction (α_eff) of ?12.60 at composition 80/10/10 of PCL/PVC/PVAc while PCL/SAN/PVC showed ?1.60 at 68/16/16 composition. These results suggest that these compositions produce high miscibility level as compared to other compositions. DSC measurements have also been used to supplement positron results. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3335–3344, 2013     

A Viscometric Study of the Miscibility Behaviour of Poly(N-Vinyl Pyrrolidone) Blends

The miscibility behaviour of blends of poly(N-vinyl pyrrolidone) (PVP) with poly(vinyl chloride) (PVC), poly(vinyl acetate) (PVAc) and vinyl chloride–vinyl acetate (VCVAc) copolymer has been investigated on the basis of a viscometric approach. PVP is found to be miscible with PVC over the entire composition range, as is evident from the high values observed for the intrinsic viscosity of transfer. This is further supported by the single glass transition temperature observed in differential scanning calorimetry studies of the blend films. Blends of PVP with VCVAc copolymer exhibit microphase separation which is shown clearly in the scanning electron micrographs of the films. PVAc/PVP blends show interaction only at low PVAc contents, but in general are immiscible. © of SCI.     

Plastification of poly(vinyl chloride) by polymer blending

Blends of poly(vinyl chloride) (PVC) with different copolymers have been studied to obtain a plasticized PVC with improved properties and the absence of plasticizer migration. The copolymers used as plasticizers in the blends were acrylonitrile butadiene rubber, ethylene vinyl acetate (EVA), and ethylene-acrylic copolymer (E-Acry). Blends were studied with regard to their processing, miscibility, and mechanical properties, as a function of blend and copolymer composition. The results obtained were compared with those of equivalent compositions in the PVC/dioctyl phthalate (DOP) system. Better results than PVC/DOP were obtained for PVC/acrylonitrile butadiene rubber blends. The plasticizing effect on PVC of EVA and E-Acry copolymers was similar to that of DOP. It is shown that crosslinking PVC/E-Acry blends or increasing the vinyl acetate content in PVC/EVA blends, are alternatives that can increase the compatibility and mechanical properties of these blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1303–1312, 2000     

Role of methods of blending on polymer–polymer compatibility

The role of methods of blend preparation on polymer-polymer compatibility was investigated. Three different types of methods of blending, such as solution-casting, melt-mixing, and coprecipitation, were applied for three types of blend systems, viz., poly(vinyl chloride-co-vinyl acetate) (VYHH)/polystyrene (PS), VYHH/poly(styrene-co-acrylonitrile) (SAN), and VYHH/poly(methyl methacrylate) (PMMA) by measuring their glass transition temperatures (T_g) by a differential scanning calorimeter (DSC). It has been found that compatibility of the polymers depends on the method of blending and compatibility also varies from one blend system to another. Among the various types of blending methods, the coprecipitation method of blending gives the best compatibility result. © 1996 John Wiley & Sons, Inc.     

Impact-modified poly(styrene-co-acrylonitrile) blends containing both oxazoline-functionalized poly(ethene-co-1-octene) elastomers and poly(styrene-co-maleic anhydride) as compatibilizer

Blends of a poly(styrene-co-acrylonitrile) (SAN) with poly(ethene-co-1-octene) rubber (EOR) were investigated. An improved toughness–stiffness balance was obtained when adding as a compatibilizer a blend consisting of oxazoline-functionalized EOR, prepared by grafting EOR with oxazoline-functional maleinate, and poly(styrene-co-maleic anhydride) (SMA), which is miscible with SAN. Enhanced interfacial adhesion was evidenced by the improved dispersion of the EOR in the SAN matrix and the reduced glass transition temperature of the dispersed EOR phase. Morphology studies using transmission electron microscopy revealed formation of an interphase between the matrix and the rubber particles. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1685–1695, 1999     

Miscibility of copolycarbonate blends with poly(styrene-co-acrylonitrile) copolymer and their interaction energies

The phase behavior of dimethyl polycarbonate-tetramethyl polycarbonate (DMPC-TMPC) blends with poly(styrene-co-acrylonitrile) copolymers (SAN) and the interaction energies of binary pairs involved in blend has been explored. DMPC-TMPC copolycarbonates containing 60 wt% TMPC or more were formed miscible blends with SAN containing limited amounts of AN. The miscibility of copolycarbonate with SAN decreases as the DMPC content increases. The miscible blends showed the LCST-type phase behavior or did not phase separate until thermal degradation. The binary interaction energies involved in the miscible blends were calculated from the phase boundaries using the lattice-fluid theory combined with binary interaction model. The phenyl ring substitution with methyl groups did not lead to interactions that are favorable for miscibility with polyacrylonitrile (PAN). The interaction energies of the polycarbonates blends with SAN copolymers as a function of AN content were obtained. It was revealed that the incline of the number of methyl groups on the phenyl rings of bisphenol-A unit acts favorably for the miscibility with SAN copolymer when SAN contains less than about 30 wt% AN and shifts the most favorable interaction to the low AN content.     

Thermodynamics of mixing of poly(vinyl chloride) and poly(ethylene-co-vinyl acetate)

The miscibility of poly(vinyl chloride) (PVC) and an ethylene-vinyl acetate copolymer with 85 wt[percnt] of vinyl acetate units (EVA85) has been studied by measuring the glass transition temperature and the enthalpy of mixing of several mixtures covering the whole composition range. An accurate thermal characterization as regards the specific heat of the two polymers and their blends has also been obtained. The enthalpy of mixing has been found negative for all the mixtures, indicating that specific interactions are involved between the polar groups of the two components. Particular attention has been paid also to the excess specific heat, which comes out positive for the PVC-rich blends and with a small negative value in a narrow region at high contents of EVA85. This finding is in agreement with negative and positive deviations that are observed for the glass transition temperature. Modelistic considerations about the type of interactions and the organization between PVC and EVA85 in the blends are proposed.     

Compatibility behavior in thermoplastic polymer blends containing poly(t-butylstyrene-co-acrylonitrile)

The phase behavior of a series of binary component polymer blends of poly(ε-caprolactone) (PCL) and poly(t-butylstyrene-co-acrylonitrile) (TBSAN) containing varying contents of acrylonitrile (AN) was examined to determine the influence of copolymer composition and PCL content on blend miscibility or immiscibility. Thermal measurements were extensively used to determine phase behavior, i.e., a single compositionally dependent glass transition temperature implies blend miscibility. Otherwise, immiscibility is assumed to dominant blend behavior. It was determined that TBSAN and PCL form miscible blends over a broad range of AN content, i.e., spanning from below 43.2 mol % (19.8 wt %) to about 66.4 mol % (39.6 wt %), a range considerably different from that found in poly(styrene-co-acrylonitrile) copolymers. TBSAN-containing blends were found to be immiscible when the AN content is less than about 43 mol % or greater than about 67 mol %. Small-angle light-scattering and polarized light microscopy was used to probe the substantial morphological changes in the miscible blends. Little change was observed in the immiscible blends. These results clarify the phase separation observed in these blend systems. © 1993 John Wiley & Sons, Inc.     

Styrene-co-acrylonitrile resin modifications of PVC/CPE blends

The effects of styrene-co-acrylonitrile resin (AS) on the mechanical properties, morphology, and plasticizing and rheological behaviors of poly(vinyl chloride)/chlorinated polyethylene(PVC/CPE) blends are studied. The results show that the impact strength and the tensile strength are all increased and the plasticizing and rheological behaviors are also improved when a certain amount of AS is added into PVC/CPE blends, which are different in characteristics and regularity from plastics toughened with elastomers. It is blends of brittle—ductile transition regions (i.e., PVC/CPE = 100/10, 100/15) that can obviously be toughened by AS. The analysis of the morphological structure shows that AS promotes the formation of a CPE network that embeds the primary particles of PVC. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1455–1460, 1997     

Miscibility of poly(vinyl chloride) with ethylene-ethyl acrylate-carbon monoxide terpolyrners

Ethylene/ethyl acrylate/carbon monoxide ter polymers (E/ EA/CO) can exhibit a very high degree of miscibility with poly(vinyl chloride) as determined from dynamic mechanical measurements. The blends yield transparent films and show a large amorphous phase which exhibits only one major glass transition. However, some crystallinity can be detected and has been measured by differential, scanning calorimetry. Residual crystallinity is at least partially due to the somewhat non-uniform nature of the terpolymerization. The acrylate monomer exhibits faster polymerization rates than the other two constituents. By contrast, ethylene/ethyl acrylat copolymers are not miscible with poly(vinyl chloride). The addition of carbon monoxide to the termpolymer structure is believed to yield miscibility with poly(vinyl chloride) via specific interaction of the ketone carbonyl of the terpolymer (proton acceptor) and the tertiary hydrogen of poly(vinyl chloride) (proton donor). This specific interaction allows for a broad range of terpolymer compositions which retain miscibility with polyvinyl chloride. Similar results are also observed with ethylene/vinyl acetate/carbon monoxide (E/VA/CO) as well as ethylene/2-ethylhexyl acrylate/carbon monoxide termpojymers. The vinyl acetate terpolymers (and their blends) display a lower degree of crystallinity than the E/EA/ CO. This is consistent with the more uniform nature of the E/VAJCO terpolymerization.     

Reactive extrusion of poly(vinyl chloride) compounds with polyethylene and with ethylene-vinyl acetate copolymers

The mechanical properties of poly(vinyl chloride)/polyethylene blends can be improved by a reactive extrusion process in the presence of an organic peroxide and a coupling agent. With a judicious loading of dibenzoyl peroxide and triallyl isocyanurate coupling agent, such blends generally exhibit significantly greater ultimate tensile strengths and dynamic moduli. The nature of the sample posttreatment after compression molding is shown to have a major impact upon the relative magnitude of these differences. Evidence is also presented to suggest that such improvements result from a superior physical interlocking between blend components, rather than through the formation of co-crosslinked graft segments (which would, presumably, impart a compatibilization effect). Similar extrusion trials with a poly(vinyl chloride)/poly(ethylene-stat-vinyl acetate) mixture revealed a general worsening of material properties with increasing dibenzoyl peroxide levels. These observations can be rationalized by examination of the degradation reactions that likely occur in these reacting systems.     

Mechanochemical synthesis and characterization of poly(vinyl chloride)-block-poly(ethylene-co-propylene) copolymers by ultrasonic irradiation

Mechanical degradation and mechanochemical reaction in heterogeneous and homogeneous systems of poly(vinyl chloride) and poly(ethylene-co-propylene) polymer have been studied by ultrasonic irradiation at 30 °C. The rates of decrease in the number-average molecular weights of the degraded poly(vinyl chloride) and poly(ethylene-co-propylene) polymer were much faster in order of the solid poly(vinyl chloride)—poly(ethylene-co-propylene) polymer solution, the swelled poly(vinyl chloride)—poly(ethylene-co-propylene) polymer solution, and the homogeneous solution systems. On the other hand, mechanochemical reaction occurred by free radicals produced from the chain scissions of both polymers by ultrasonic waves. The changes in the composition of the total block copolymer, the unreacted poly(vinyl chloride), and the unreacted poly(ethylene-co-propylene) polymer in individual reaction systems were obtained. In addition, the microscopic observation of the surfaces of the polymers on before and after mechanochemical reaction is carried out. Received: 10 May 2000/Revised version: 1 August 2000/Accepted: 3 August 2000