Transient shear and elongational behavior of blends of PET with a LCP

Blends of polyethylene terephthalate (PET) with a liquid crystalline polymer (LCP) and a compatibilizer were produced by twin screw extrusion and injection molding. Transesterification and compatibilization studies were made in a torque rheometer. The morphology of the injection-molded plaques was studied by scanning electron microscopy. The blends shear growth function was measured in a cone and plate rheometer. The elongational growth function was measured in a modified rotational rheometer. Transesterification was observed in the PET/LCP/compatibilizer 95/5/0 blend. The injection-molded plaques displayed the usual “skin-core” morphology. All the blends were highly shear-thinning, even at low shear rates; thus, a zero-shear viscosity could not be calculated. The compatibilized blend had the highest shear viscosity of all the blends, confirming the strong PET/LCP interphase and the effectiveness of the compatibilizing agent. On the other hand, the 90/10/0 blend had the lowest shear viscosity. All the blends showed strain softening behavior, similar to the PET. The 90/10/0 blend had the highest elongational growth function, while the 95/5/0 had the lowest. The compatibilized blend had an intermediate behavior between both blends.     

Morphology development in polystyrene/polyethylene blends during uniaxial elongational flow

The deformation of linear low-density and low-density polyethylene particles dispersed in a polystyrene matrix was studied during defined uniaxial elongational flow conditions for different capillarity numbers and different temperatures. The morphology of the elongated samples was analysed by quenching the specimens in liquid nitrogen directly after the deformation. Furthermore, morphology development after recovery was investigated. By measuring the transient elongational viscosity of the blend matrix the true hydrodynamic stress during the flow process was calculated. Using a modified critical capillarity number, the fibril formation of the dispersed phase could be described at all test conditions. Virtually no break-up processes were observed. This finding could be explained by calculating the characteristic time of fibril break-up due to Rayleigh instabilities. By annealing the elongated samples a spherical shape of the dispersed droplets was regained. Compared with the initial sample morphology a pronounced increase of the particle sizes due to coalescence processes during elongation was observed.     

Shear and elongational flow behavior of acrylic thickener solutions

We investigate the effect of hydrophobic aggregation in alkali-swellable acrylic thickener solutions on shear and extensional flow properties at technically relevant polymer concentrations using the commercial thickener Sterocoll FD as model system. Apparent molecular weight of aggregates in water is M _w  ≈ 10⁸ g/mol and decreases by more than an order of magnitude in ethanol. Zero shear viscosity η ₀ is low and shear thinning is weak compared to the high molecular weight of the aggregates. Linear viscoelastic relaxation is described by the Zimm theory up to frequencies of 10⁴ rad/s, demonstrating that no entanglements are present in these solutions. This is further supported by the concentration dependence of η ₀ and is attributed to strong association within the aggregates. Extensional flow behavior is characterized using the capillary break-up extensional rheometry technique including high-speed imaging. Solutions with ϕ ≥ 1% undergo uniform deformation and show pronounced strain hardening up to large Hencky strains. Elongational relaxation times are more than one order of magnitude lower than the longest shear relaxation times, suggesting that aggregates cannot withstand strong flows and do not contribute to the elongational viscosity.

Numerical simulation of elongational flow behaviour in the cross cell experiments

In this work, numerical simulation of an elongational flow of polymer solutions is tried. The flow field is computed in a cell of simple geometry for newtonian, non-newtonian inelastic and non-newtonian elastic fluids. For the latter, an Oldroyd four-constant-model was adopted. The results are qualitatively in good agreement with the experimental results.     

Extensional flow of HDPE/LDPE blends

Elongational viscosity data, obtained through the converging flow analysis by Cogswell, are presented for two types of HDPE/LDPE blends at various compositions and different temperatures. The results relative to the homopolymer parents compare favourably with literature data obtained also with different and more sophisticated techniques. Those relative to blends show peculiar features for the two cases: when the newtonian viscosity of the LDPE is higher all the blends show a behaviour typical of the LDPE with a maximum in _el / ₀ enhanced at small percentage of HDPE; when the newtonian viscosity of the LDPE is similar to that of the HDPE there is only a gradual change in the properties.     

Uniaxial deformation and relaxation of polymer blends: relationship between flow and morphology development

Uniaxial elongational flow followed by stress relaxation of a dilute mixture of polystyrene/polymethylmethacrylate) PS/PMMA with PS (5 wt%) as a dispersed phase was investigated. The behavior of the blend was found to be dominated by the PMMA matrix during elongation and by the interface during the relaxation at long time. Such a behavior was related to drop deformation and shape recovery during the relaxation process as was confirmed by morphological analyses on samples quenched within the rheometer just after elongation and at various times during the relaxation process. The morphology and the rheological material functions variation were compared to the Yu model (Yu W, Bousmina M, Grmela M, Palierne JF, Zhou C (2002) Quantitative relationship between rheology and morphology in emulsions. J Rheol 46(6):1381–1399).     

Uniaxial extensional flow behavior of immiscible and compatibilized polypropylene/liquid crystalline polymer blends

In this work liquid crystalline polymer (LCP) and thermoplastic (TP) blends with and without compatibilizer were studied with respect to their elongational flow behavior, under uniaxial extensional flow. This knowledge is important because in processes involving dominantly extensional deformations, like the case of the formation of the LCP fibrillation, transient extensional flow properties become more important than transient or steady-shear properties. In systems characterized by disperse phase morphologies (10 and 20 wt%) the LCP acts as a plasticizer, decreasing the viscosity of the system and increasing its durability with respect to that of the matrix. On the other hand, for a system in which a co-continuous morphology is present (40 wt% LCP) fibrils and droplets deformation occurs simultaneously, leading to a much higher strain hardening and durability. Moreover, the addition of compatibilizers to the blends gives rise to an increase of the strain hardening and to a decrease of the durability, which is in accordance with the mechanical properties, namely a higher Young’s modulus and lower elongation at break, in comparison with noncompatibilized systems.     

Rheological properties of carbon black-filled blends of liquid-crystalline copolyester with thermoplastic polysulfone

Rheological properties of a two-phase polymeric blend containing LCCPE of poly(ethylene terephthalate) and p-hydroxybenzoic acid and thermoplastic polysulfone with varying concentrations of polymeric components and particulate filler have been studied. The theological behavior of such blends at different temperatures is governed by variation of the degree of ordering of LC-CPE macromolecules associated with the phase transition in the CPE at 260°C. Experimental results are discussed on the basis of concepts of compatibility of polymeric components in the melt or, if the system is incompatible, of the degree of interphase interaction between the components, as well as the impact of the filler and of the shear straining conditions on structurization in the system and compatibility. The filler exerts a compatibilizing effect on blend components, while the shear stress encourages the phase separation in the system. An extremal variation of viscosity of the LC-CPE/carbon black, silica and talk blends with the filler concentration on both at the flow in a uniform shear stress field and at the capillary flow has been found. Normalization of the filler concentration with respect to its specific surface yields a unified concentration dependence of the relative viscosity of LC-CPE filled with solid particles of various natures and specific surfaces.     

Dynamic rheology of the immiscible blends of liquid crystalline polymers and flexible chain polymers

Immiscible blends containing liquid crystalline polymers (LCP) as dispersed phases show different dynamic rheological properties than those composed of flexible polymers. The widely used Palierne’s model was shown by many authors to be insufficient to describe the frequency dependence of dynamic modulus of such blends. A new model was presented to describe the dynamic rheology of the immiscible blend containing LCP as a dispersed phase. The flexible chain polymer matrix was assumed to be a linear viscoelastic material under small amplitude oscillatory shear flow, and the LCP was assumed to be an Ericksen’s transversely isotropic fluid. The Rapini-Papoular equation of anisotropic interfacial energy was used to account for the effect of nematic orientation on the interfacial tension. It was found that the orientation of the director and the anchoring energy greatly influenced the storage modulus at the “shoulder” regime. The overall dynamic modulus of the blend can be well described by the model with suitable choice of the orientation of the director and anchoring energy of LCP.     

Shear and elongational flow behavior of acrylic thickener solutions. Part II: effect of gel content

We have investigated the effect of crosslink density on shear and elongational flow properties of alkali-swellable acrylic thickener solutions using a mixing series of the two commercial thickeners Sterocoll FD and Sterocoll D as model system. Linear viscoelastic moduli show a smooth transition from weakly elastic to gel-like behavior. Steady shear data are very well described by a single mode Giesekus model at all mixing ratios. Extensional flow behavior has been characterized using the CaBER technique. Corresponding decay of filament diameter is also well fitted by the Giesekus model, except for the highest crosslink densities, when filament deformation is highly non-uniform, but the non-linearity parameter α, which is independent of the mixing ratio, is two orders of magnitude higher in shear compared to elongational flow. Shear relaxation times increase by orders of magnitude, but the characteristic elongational relaxation time decreases weakly, as gel content increases. Accordingly, variation of gel content is a valuable tool to adjust the low shear viscosity in a wide range while keeping extensional flow resistance essentially constant.     

Linear stability of homogeneous elongational flow of the upper convected Maxwell fluid

We prove that planar elongational flow of the upper convected Maxwell fluid is linearly stable and analyze the associated spectral problem.     

液晶高分子取向特征及其流变性质研究

研究液晶高分子取向特征及其流变性质,在向矢输运方程基础上,研究了管内Posieulle流动和纺丝拉伸流动中一维向矢部分,应用偏光显微镜研究了热致性和溶致性液晶高分子织构,显示出液晶态的各向异性特征,测定了溶致性液晶高分子羟基丙基纤维素（HPC）的流变特性。     

Diffusion effects on the interfacial tension of immiscible polymer blends

Most methods of measuring the interfacial tension between two immiscible polymers are based on the analysis of the shape that a drop of one polymer immersed in the other one exhibits under the action of flow or gravity. In such a situation, the small, yet nonzero mutual solubility between the two polymers acts toward mass transfer between the drop and the surrounding fluid. In this work, diffusion effects on the interfacial tension of the pair polyisobutylene/polydimethylsiloxane have been investigated by drop deformation under shear flow. When the drop was made of polyisobutylene, drop size decreased with time due to diffusion. Drop shrinkage was associated with a significant increase in interfacial tension, until an apparent plateau value was reached. The effect was attributed to a selective migration of molecular weights, which would act to enrich the drop with higher molar mass material. To support such an interpretation, drop viscosity was evaluated by drop shape analysis and it was actually found to increase with time. In some cases, the ratio between drop and continuous phase viscosity became higher than the critical value for drop breakup in shear flow. Upon inverting the phases (i.e., when the drop was made of polydimethylsiloxane), no significant transient effects were observed. In the light of these results, the problem of what are the correct values of interfacial tension and viscosity ratio for a polymer blend of a certain composition will also be discussed. Received: 25 January 1999 Accepted: 24 May 1999     

Design and operation of the free jet elongational rheometer

The controlled free jet instability is used for elongational rheometry of polymer solutions. The instantaneous elongational viscosity represents a convenient comparative parameter. Its dependence on the operating parameters and the conditions of operation will be discussed.     

Rheology and morphology of starch/synthetic polymer blends

Corn starch and maleic anhydride functionalized synthetic polymers were melt blended in a Haake twin-screw extruder. The amount of starch in the blends was 60 and 70% by weight. The synthetic polymer used was either styrene maleic anhydride (SMA) or ethylene propylene maleic anhydride copolymer (EPMA). The blends did not exhibit normal thermoplastic behavior; and hence, rheological data was obtained by extrusion feeding the material through a slit die or cylindrical tube viscometer. The starch/SMA blends were extruded through a slit viscometer with a 45% half entry angle, while the starch/EPMA blends were extruded through a cylindrical tube viscometer with a half entry angle of 37.5°. For the blends, data could be obtained at low to moderate shear rates (10< _app<200s^–1). At higher shear rates, blends exhibited slip and/or degradation of starch. The viscosity of the blends exhibited shear-thinning properties. Regrinding and re-extruding through the viscometer a second time showed a significant reduction in shear viscosity for starch/SMA blends. Gel permeation chromatography data indicated that starch macromolecules degraded upon successive extrusion. Extensional viscosity, as estimated from entrance pressure drop method for starch/EPMA blends showed stretch thinning properties. Regrinding and re-extruding showed that the samples were more sensitive to changes in extensional viscosity as observed from the Trouton ratio versus extension rate plot. Optical microscopy showed the presence of starch granules after melt blending, the size of which was related to the torque (or stress) generated during extrusion. The higher the torque, the smaller the size of the starch granules. Successive extrusion runs reduced the number of unmelted granules.Nomenclature A,B Constants associated with power law fluids (Pa s^{m or n}) - e Entrance correction - H Height of slit die (m) - m, n Flow behavior index in shear and extension flow respectively - P _s Shear component of the entrance pressure drop (Pa) - P _e Extensional component of the entrance pressure drop (Pa) - Q volumetric flow rate (m³S^–1) - R _o radius of barrel exit (m) - R ₁ radius of cylindrical die (m) - T _r Trouton ratio - w width of slit die (m) - pressure gradient (Pam^–1) - half die entry angle - P _en Entrance Pressure Drop (Pa) - apparent extension rate (s^–1) - apparent shear rate (s^–1) - _w wall shear stress (Pa) - first normal stress difference in uniaxial extension (Pa)     

Viscoelasticity and diffusion in miscible blends of saturated hydrocarbon polymers

Linear viscoelasticity and tracer diffusion were investigated as functions of temperature, component molecular weight and blend composition for entangled, single-phase blends of nearly monodisperse poly(ethylene-alt-propylene) (PEP) and head-to-head polypropylene (HHPP). Both components are non-polar and, despite evidence for slight differences of component glass temperatures in their blends, the viscoelastic data obey time-temperature superposition rather well. The properties of the blends were compared at constant T-T _g (blend) with predictions of the tube-model theories. The composition dependence of viscosity agrees best with the double-reptation prediction, as had been found earlier for molecular weight blends. The variation in plateau modulus with composition is consistent with reptation, but the changes are too small to provide a definitive test. The tracer diffusion coefficients, D ^* _PEP and D ^* _HHPP are nearly independent of composition, consistent with the reptation prediction and in sharp contrast with tracer diffusion for blends with specific associations. Results for the recoverable compliance depart from this pattern, varying differently and much less strongly with composition than the predictions of either single or double reptation. It thus seems that microstructural blends may behave in significantly more complex ways than molecular weight blends even for components with only weak dispersive interactions and rather modest differences in glass temperature and plateau modulus.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.     

Capillary flow behavior of bicomponent polymer blends

The flow behavior of bicomponent polymer blends of four types of polymers (polypropylene, polystyrene, high-density polyethylene and polymethyl-methacrylate) was examined using a capillary extrusion rheometer. The viscosity of the blend was generally less than the value calculated by the theoretical or empirical additivity rules proposed in previous reports, whereas the entrance pressure loss, which is considered to be an effect of elasticity, was larger than the estimated value. Thus the variation of the viscosity with blending ratio was inversely proportional to the variation in the elastic property. The cross-section of the material extruded in a roughly dispersed state showed an annularly stratified flow pattern in which the lower viscosity component polymer appeared to form the outer skin layer. However, the observation that the viscosity of the properly blended material at certain blending ratios was sometimes lower than that of either homopolymer could not be explained.     

Determination of the elongational viscosity of polymer melts by melt spinning experiments. A comparison with different experimental techniques

In this work, melt spinning experiments were tentatively used for the determination of the elongational viscosity of polymer melts at different levels of tensile strain and strain rate. The materials examined were two high-density polyethylene grades for blow moulding with similar number-average molecular mass but different polydispersity index. The data from melt spinning tests were compared with transient extensional viscosity data obtained by uniform isothermal tensile tests, performed by means of an extensional rheometer, as well as with those produced by converging flow tests (Cogswell model). The results showed that for high strain and strain rate levels, the melt spinning experiments provide elongational viscosity data quite close to the transient extensional viscosity values obtained from the tensile tests.