Viscoelastic and thermal behaviour of partially compatible polymer blends polycarbonate/tetramethylpolycarbonate

Differential scanning calorimetry (DSC) and thermomechanical analysis (TMA) measurements show that, in the case of polycarbonate (PC) with tetramethylpolycarbonate (MPC), the homopolymers are miscible up to 70% PC weight fraction; at higher PC content, an additional PC phase appears. The partial miscibility of PC and MPC has been confirmed by ultrasonic attenuation measurements and scanning electron microscopy. The viscoelastic behaviour of these blends has been correlated with the blend composition and compatibility. The free volume contraction, found to explain the variations of glass transition temperature and viscosity with concentration, suggests strong intermolecular interaction in the compatible range.     

Viscoelastic and thermal behaviour of ternary blends polystyrene/polycarbonate/tetramethylpolycarbonate

The thermal analysis characteristics of ternary blends polystyrene(PS)/polycarbonate(PC)/tetramethylpolycarbonate (MPC) show that the PS forms mostly a pure PS phase, whereas the PC and MPC go into a second phase very close to a binary blend of the same PC/MPC weight composition. However, an additional broad glass transition is observed for most blends within the same temperature range (129–133°). On the other hand, the viscoelastic properties of the ternary blends containing 75% PC/MPC weight fraction exhibit an additional low frequency (large relaxation times) relaxation domain. This relaxation domain might be attributed either to a PS/MPC interphase or to PS “trapped” at the PS-PC/MPC interphase.     

Viscoelastic behaviour of non-compatible polymer blends: Polystyrene-polycarbonate

The linear and non-linear viscoelastic properties of a series of non-compatible polymer blends (polystyrene-bisphenol A polycarbonate) have been studied in the temperature range 180–250°. Glass transition temperature measurements show a small degree of compatibility at low PS contents. Variations of zero-shear viscosities as a function of blend composition have been related to the glass transitions and to the values of the thermodynamic interaction parameter λ₂₃ reported by Lipatov. An attempt was made to derive the linear viscoelastic properties of the blends as a function of the composition of the dispersed phase, given the viscoelastic behaviour of the pure components, using phenomenological models. Morphology of the dispersed phase has also been studied using scanning electron microscopy.     

Photon correlation spectroscopy of compatible polymer blends

The dynamics of concentration fluctuations in compatible polymer mixtures can be investigated by dynamic light scattering. The experiment yields both the dynamic and static structure factors from which the mutual diffusion coefficient and the segment-segment interaction parameter can be obtained. Examples of applications are the unentangled blends poly(ethylene oxide/poly(propylene oxide) and polystyrene/poly(phenylmethylsiloxane) in the one phase region.     

Phase behaviour and morphology of polymer/liquid crystal blends

Abstract

The phase behaviour of blends of poly(ethylene oxide) (PEO) with the liquid crystal p-azoxyanisole (PAA) has been studied by differential scanning calorimetry and optical microscopy. This system exhibits partial miscibility of the components in the molten state (at temperatures above 337 K). The melting temperature and enthalpy of the PAA phase has been found to depend on the blend composition, whereas the melting behaviour of the polymer phase remains quite unaltered. The occurrence of the PAA nematic phase, dispersed within an isotropic liquid phase, has been observed at high concentrations of liquid crystal. The morphology of the blends in the solid state changes largely with the PAA content, depending on the solubility of the components in the liquid phase.     

Polystyrene/thermoplastic starch blends with different plasticizers

Conventional plastics has a large impact in increasing the environment’s pollution. That’s why the interest has turned towards novel partially and completely biodegradable polymers. In this work, blends of polystyrene and thermoplastic starch with glycerol and Buriti (Mauritia flexuosa L.) oil as plasticizers were prepared. Samples were analyzed using TG/DTG and DSC techniques. The TG results indicated that the blends with Buriti oil are thermally more stable than those with glycerol. The DSC analysis that Buriti oil provides a higher degree of plasticization of PS, compared to the blends plasticized using glycerol under the studied conditions.     

Prediction of the glass transition temperature for compatible polymer blends of varying compositions

Compatible polymer blends have been found to have widespread commercial applications. The simplest criterion for judging polymer—polymer miscibility in the solid state is the glass transition temperature (T_g), which can vary widely according to blend composition for a compatible system.Recently, an equation which predicts the T_g of intimate mixtures of compatible polymers has been derived, based on classical thermodynamics. Only a knowledge of the T_g and heat capacity increment (ΔC_p) of each pure component is required to predict the T_g at any composition.In this paper, the validity of this entropy-based relationship is investigated for a variety of commercial compatible polymer blends, including some based on poly(vinyl chloride), polystyrene, and poly(2,6-dimethyl-,4-phenylene oxide). The T_g and ΔC_p of each pure component are measured with a Perkin-Elmer DSC-2 differential scanning calorimeter, are predicted glass transition temperatures are compared with those observed experimentally.     

Viscoelastic effects on early stage of spinodal decomposition in dynamically asymmetric polymer blends

Spinodal decomposition induced by a rapid pressure change was investigated for a dynamically asymmetric polymer blend [deuterated polybutadiene (DPB)/polyisoprene (PI)] with a composition of 50/50 wt/wt by using time-resolved small angle neutron scattering. The time change in the scattered intensity distribution with wave number (q) during the spinodal decomposition was found to be approximated by the Doi-Onuki theory [M. Doi and A. Onuki, J. Phys. II 2, 1631 (1992)]. The theoretical analysis yielded the q dependence of the Onsager kinetic coefficient which is characterized by the q(-2) dependence at qxive > 1 with the characteristic length xive being much larger than the radius of gyration of DPB or PI. The estimated xive agrees well with that obtained previously in the relaxation processes induced by pressure change within the one phase region for the same blend.     

Entanglement,friction, and free volume between dissimilar chains in compatible polymer blends

Dynamic oscillation, shear creep, and time-temperature superposition are used to study the entanglement, friction, and free volume between dissimilar chains in compatible polymer blends: PMMA/PEO, PMMA/PVF2, PMMA/SAN, and PS/PPO. It is found that interchain specific interactions, responsible for the compatibility, tend to reduce the entanglement but increase the friction between dissimilar chains. The former appears to arise from local reduction of chain convolution due to segmental alignment and the latter from increased interchain attraction. The entanglement probability and the friction coefficient between dissimilar chains correlate with the strength of specific interactions. On the other hand, the free volume tends to be linearly additive but may deviate either positively or negatively, apparently influenced by segmental conformation and packing rather than specific interactions. The reduced entanglement and the free volume additivity tend to reduced the melt viscosity, while the increased friction tends to increase it. The former two effects are often stronger than the latter, resulting in a net reduction of melt viscosity in many cases.     

Pressure dependence of the demixing behaviour in polymer blends: I. Experimental procedure

The most common way to influence the liquid-liquid phase behaviour in partially miscible (co-)polymer blends is changing the blending temperature. Since most extruders can handle pressures, up to 300 bar, pressure may also be used to influence the miscibility of polymers during blending. We have developed equipment and an experimental procedure to study the pressure dependence of the liquid-liquid demixing behaviour of high-viscous polymer blends under equilibrium conditions. Small amounts (1–4 grams) of specially made polymers are blended in the ‘DSM MINI EXTRUDER’. After a chosen mixing time, a small portion of the blend is injected into a small capillary tube and kept at the blending temperature. The phase behaviour of the blends as a function of temperature and pressure is studied via laser light scattering (at a scattering angle of 90°) in a specially made 400 bar/250°C window autoclave, where the capillary cell is placed in a high temperature grade silicon oil.     

PC/ABS blends: Compatibilization and mechanical behaviour

PC/ABS(M) blends, encompassing the whole composition range between pure PC and ABS(M), were prepared by melt-mixing in a Brabender-like apparatus. Thermal, mechanical and impact tests were performed on compression moulded specimens. Inward Tg shifts were detected for PC and ABS(M) in the blends with respect to pure PC and ABS(M) values, indicating an interaction between the component domains. This finding was confirmed by the comparison of the experimental tensile moduli with the Kernels model predictions, showing an evidence of a good adhesion between the phases. A synergistic effect was observed for the impact strength as well as for the maximum stress at an ABS(M) blend content of about 25 weight %. All the results are interpreted on the basis of an interlayer existing at the boundary between the PC and ABS phases. A preliminary investigation on the influence of the ABS internal composition, keeping constant all the other conditions (mixing, processing, specimen preparation), was carried out as well. Differences in the properties of PC/ABS(M) and PC/ABS(B) blends are thoroughly discussed. The compatibility between PC and ABS domains seems to be scarcely influenced by such a parameter in these blends.     

Viscometric behaviour of polymer blends based on poly (vinylidene fluoride)

The viscosity behaviour of dilute dimethylformamide solutions of poly(vinylidene fluoride)-poly (methyl methacrylate) and poly(vinylidene fluoride)-polystyrene has been studied at 25°C. The polymer concentration ranges are such that neither phase separation nor microgel formation occurs, although we are very close to theta conditions. The intrinsic viscosity and viscosity interaction parameter of the ternary mixtures have been calculated. The estimation of the compatibility of the above polymer pairs has been studied based on: a) specific viscosities; b) viscosity interaction parameters, according to Krigbaum and Wall formalism, and c) viscosity interaction parameters of a system formed by a dilute probe polymer in the presence of a matrix polymer and a small molecule solvent.     

Processing/morphology/rheology relationships in polymer blends

In this paper certain aspects concerning the influence of rheological parameters on the morphology of immiscible polymer blends are considered. The author reviews his own work with reference to other key studies carried out in the field. The influence of the viscosity ratio on morphology for compatibilized and non-compatibilized systems are treated, as well as the influence of shear stress. The role of viscosity and viscosity ratio in controlling co-continuous and complex composite droplet morphologies are also discussed.     

Photooxidative behaviour of polyethylene/polyamide-6 blends

The photochemical behaviour of several polyethylene/polyamide-6 blends was studied under conditions of artificial accelerated weathering. Particular attention was paid to five different compositions ranging from pure polyethylene to pure polyamide with blends of PE/PA-6 of various compositions: 75/25, 50/50 and 25/75 wt/wt%. Analysis by infrared spectroscopy of the chemical modifications caused by photooxidation showed that exposing the polyethylene/polyamide-6 blends to UV-light irradiation led to the formation of oxidation photoproducts in both polymer phases. In agreement with both the mechanical and spectroscopic analyses, the photooxidation rate of the blends was observed to be much higher than that of the homopolymers. The results given in this paper suggest that photooxidation of the PE/PA blends starts in the polyamide phase and that the subsequent photooxidation of the polyethylene phase may be initiated by the radicals coming from the oxidation of PA.     

Orientation and relaxation study of polystyrene: Polystyrene/poly(phenylene oxide) blends

Polarization modulation infrared linear dichroism has been used to study the molecular orientation and relaxation of polystyrene/poly(2,6‐dimethyl 1,4‐phenylene oxide) (PS/PPO) miscible blends, containing up to 20% PPO, during and after a rapid uniaxial deformation above T_g. In general, it is found that both the PS and PPO chain orientation functions increase with stretching rate and PPO content, and decrease with temperature. For all blends investigated, between T_g + 5 and T_g + 13 °C, the relaxation occurs at the same rate for PS and PPO and, therefore, the relaxation times calculated are similar indicating, under those conditions, a strong relaxation coupling between the two polymers at both short and long times. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1405–1415, 2000     

Phase behavior of tetramethylpolycarbonate blends with styrene‐based methacrylate copolymers and their interaction energies

The miscibility of tetramethylpolycarbonate (TMPC) blends with styrenic copolymers containing various methacrylates was examined, and the interaction energies between TMPC and methacrylate were evaluated from the phase‐separation temperatures of TMPC/copolymer blends with lattice‐fluid theory combined with a binary interaction model. TMPC formed miscible blends with styrenic copolymers containing less than a certain amount of methacrylate, and these miscible blends always exhibited lower critical solution temperature (LCST)‐type phase behavior. The phase‐separation temperatures of TMPC blends with copolymers such as poly(styrene‐co‐methyl methacrylate), poly(styrene‐co‐ethyl methacrylate), poly(styrene‐co‐n‐propyl methacrylate), and poly(styrene‐co‐phenyl methacrylate) increase with methacrylate content, go through a maximum, and decrease, whereas those of TMPC blends with poly(styrene‐co‐n‐butyl methacrylate) and poly(styrene‐co‐cyclohexyl methacrylate) always decrease. The calculated interaction energy for a copolymer–TMPC pair is negative and increases with the methacrylate content in the copolymer. This would seem to contradict the prediction of the binary interaction model, that systems with more favorable energetic interactions have higher LCSTs. A detailed inspection of lattice‐fluid theory was performed to explain such phase behavior. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1288–1297, 2002     

Viscoelastic behaviour of rubberwood-polymer composites

The dynamic storage modulus E' of rubberwood (Hevea braziliensis) increased after the in situ polymerization of methylmethacrylate in the wood cellular structure. A significant linear relationship existed between the percentage increase in E' and polymer loading. A thermal scan of tan δ values between -120° and 200°C revealed that the damping pattern of rubberwood was affected to different extents by three different polymeric systems. Poly(styrene-co-acrylonitrile) caused the greatest change in the damping pattern, followed by polymethylmethacrylate-dioxane, and polymethylmethacrylate. This observed trend was attributed to the relative extent of monomer penetration and interaction with the wood cell-wall components.     

Entanglement between dissimilar chains in compatible polymer blends: poly(methyl methacrylate) and poly(vinylidene fluoride)

The plateau modulus and zero-shear melt viscosity of binary compatible blends of poly(methyl methacrylate) and poly(vinylidene fluoride) were measured by dynamic oscillation and shear creep, and used to analyze the entanglement between dissimilar chains and its effect on melt viscosity. It is found that dissimilar chains are less likely to entangle with each other than similar chains, resulting in a large reduction of zero-shear melt viscosity in this system.     

Entanglement and phase separation in hyperbranched polymer/linear polymer/solvent ternary blends

Hyperbranched polyethylene (HBPE)/linear polystyrene (PS)/chloroform (CF) solution was selected as a model system to investigate the effect of branching structure on entanglement and phase separation behavior in semi-dilute ternary polymer solutions. All the HBPE materials in this work were found to have similar chain architectures and the critical molecular weight was estimated to be 81.2 kDa. The results obtained by elastic light scattering and intrinsic fluorescence methods suggested that all ternary solutions exhibited UCST transition behavior upon cooling. Also, it was found that the increase in the molecular weight of PS led to increase in the phase separation rate, consistent with de Gennes prediction. However, the increase of molecular weight of HBPE did not monotonously reduce the compatibility of polymer components and the phase separation rate in ternary blends is as follows: medium molecular weight HBPE (HBPE-M) > high molecular weight HBPE (HBPE-H) > low molecular weight HBPE (HBPE-L). This abnormal behavior can be explained by the fact that, (i) for HBPE-L, no entanglements between HBPE chains occurred and the branching effect can be ignored, and (ii) for HBPE-M and HBPE-H, entanglement of HBPE chains can be formed, and the dilution of branches on entanglement of backbones should be taken into consideration, that is, the shorter the branches of HBPE, the higher the possibility of interpenetration of HBPE backbones between neighboring molecules and, consequently, the faster aggregation of HBPE during phase separation. Furthermore, a simple model based on decomposition reaction was proposed to quantitatively describe the phase separation kinetics and the apparent activation energies of phase separation were calculated to be −150.3 and −52.3 kJ/mol for HBPE-M/PS/CF and HBPE-H/PS/CF systems, respectively.     

Thermodynamics of polymer blends

The general principles of thermodynamic equilibrium in binary liquid systems are reviewed briefly, and extended to quasi-binary mixtures of polydisperse polymers. Molecular models allowing actual phase behaviour to be discussed in terms of molecular parameters are exposed to data on the system polystyrene/polyvinylmethylether. Disparity in size and share between the repeating units must be introduced to obtain reasonable agreement between theory and experiment. The neccessary introduction of the molar-mass distribution detracts from this agreement which makes clear that other aspects exist that must be taken into account. For example, cross association between repeating units has a marked effect on phase behaviour. Blends are subject to two kinds of thermodynamic aging which lead either to considerable mutual solubility in supposedly immiscible blends, or to metastable equilibria transforming into states of lower Gibbs energy. In both cases physical proerties of the blend will change with time.