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.     

Rheotens-mastercurves and elongational viscosity of polymer melts

In a Rheotens experiment, the tensile force needed for elongation of an extruded filament is measured as a function of the draw ratio. For thermo-rheologically simple polymer melts, the existence of Rheotens-mastercurves was proved by Wagner, Schulze, and Göttfert (1995). Rheotens-mastercurves are invariant with respect to changes in melt temperature and changes in the average molar mass. By use of purely viscous models, we convert Rheotens-mastercurves of a branched and a linear polyethylene melt to elongational viscosity as a function of strain rate. The resulting elongational viscosity from constant force extension experiments is found to be in general agreement with what is expected as steady-state viscosity of polyethylene melts measured in either constant strain-rate or constant stress mode.Dedicated to Prof. Dr. J. Meissner on the occasion of his retirement from the chair of Polymer Physics at the Eidgenössische Technische Hochschule (ETH) Zürich, Switzerland     

The role of elongational viscosity in the mechanism of drag reduction by polymer additives

The role of elongational viscosity in the mechanism of drag reduction by polymer additives is investigated qualitatively by means of direct numerical simulations of a turbulent pipe flow. For the polymer solution, a generalised Newtonian constitutive model is utilised in which the viscosity depends on the second and third invariant of the rate-of-strain tensor via an elongation parameter. This elongation parameter is capable of identifying elongational type of regions within the flow. The simulations show that complementary to stretching of the polymers, also compression must be incorporated to have drag reduction, contrary to many suggestions done in the literature on the mechanism which assume that stretching of the polymers is most important.     

The effect of 1,3:2,4-<Emphasis Type="Italic">bis</Emphasis>-<Emphasis Type="Italic">O</Emphasis>-(<Emphasis Type="Italic">p</Emphasis>-methylbenzylidene)-<Emphasis Type="SmallCaps">d</Emphasis>-sorbitol (PDTS) on uniaxial elongational viscosity of polypropylene

We investigated the dynamic viscoelasticity and elongational viscosity of polypropylene (PP) containing 0.5 wt% of 1,3:2,4-bis-O-(p-methylbenzylidene)-d-sorbitol (PDTS). The PP/PDTS system exhibited a sol–gel transition (T _gel) at 193 °C. The critical exponent n was nearly equal to 2/3, in agreement with the value predicted by a percolation theory. This critical gel is due to a three-dimensional network structure of PDTS crystals. The elongational viscosity behavior of neat PP followed the linear viscosity growth function 3η ⁺ (t), where η ⁺ (t) is the shear stress growth function in the linear viscoelastic region. The elongational viscosity of the PP/PDTS system also followed the 3η ⁺ (t) above T _gel but did not follow the 3η ⁺ (t) and exhibited strong strain-softening behavior below T _gel. This strain softening can be attributed to breakage of the network structure of PDTS with a critical stress (σ _c) of about 10⁴ Pa.     

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.     

The shear viscosity dependence on concentration,molecular weight,and shear rate of polystyrene solutions

The solution viscosity of narrow molecular weight distribution polystyrene samples dissolved in toluene and trans-decalin was investigated. The effect of polymer concentration, molecular weight and shear rate on viscosity was determined. The molecular weights lay between 5 10⁴ and 24 10⁶ and the concentrations covered a range of values below and above the critical valuec ^*, at which the macromolecular coils begin to overlap. Flow curves were generated for the solutions studied by plotting log versus log . Different molecular weights were found to have the same viscosity in the non-Newtonian region of the flow curves and follow a straight line with a slope of – 0.83. A plot of log ₀ versus logM _w for 3 wt-% polystyrene in toluene showed a slope of approximately 3.4 in the high molecular weight regime. Increasing the shear rate resulted in a viscosity that was independent of molecular weight. The sloped (log)/d (logM _w ) was found to be zero for molecular weights at which the corresponding viscosities lay on the straight line in the power-law region.On the basis of a relation between _sp and the dimensionless productc · [], simple three-term equations were developed for polystyrene in toluene andt-decalin to correlate the zero-shear viscosity with the concentration and molecular weight. These are valid over a wide concentration range, but they are restricted to molar masses greater than approximately 20000. In the limit of high molecular weights the exponent ofM _w in the dominant term in the equations for both solvents is close to the value 3.4. That is, the correlation between _sp andc · [] results in a sloped(log _sp)/d(logc · []) of approximately 3.4/a at high values ofc · [] wherea is the Mark-Houwink constant. This slope of 3.4/a is also the power ofc in the plot of ₀ versusc at high concentrations. a Mark-Houwink constant - B ₁,B ₂,B _n constants - c concentration (g · cm^–3) - c ^* critical concentration (g · cm^–3) - K, K constants - K _H Huggins constant - M molecular weight - M _c critical molecular weight - M _n number-average molecular weight - M _w weight-average molecular weight - n sloped(log _sp)/d (logc · []) at highc · [] - PS polystyrene - T temperature (K) - shear rate (s^–1) - critical shear rate (s^–1) - viscosity (Pa · s) - ₀ zero-shear viscosity (Pa · s) - _s solvent viscosity (Pa · s) - _sp specific viscosity - [] intrinsic viscosity (cm³ · g^–1) - dynamic viscosity (Pa · s) - | ^*| complex dynamic viscosity (Pa · s) - angular frequency (rad/s) - density of polymer solution (g · cm^–3) - ₁₂ shear stress (Pa) Dedicated to Prof. Dr. J. Schurz on the occasion of his 60^th birthday.Excerpt from the dissertation of Reinhard Kniewske: Bedeutung der molekularen Parameter von Polymeren auf die viskoelastischen Eigenschaften in wäßrigen und nichtwäßrigen Medien, Technische Universität Braunschweig 1983.     

Stress relaxation behavior of PMMA/PS polymer blends

In this work, the stress relaxation behavior of PMMA/PS blends, with or without random copolymer addition, submitted to step shear strain experiments in the linear and nonlinear regime was studied. The effect of blend composition (ranging from 10 to 30 wt.% of dispersed phase), viscosity ratio (ranging from 0.1 to 7.5), and random copolymer addition (for concentrations up to 8 wt.% with respect to the dispersed phase) was evaluated and correlated to the evolution of the morphology of the blends. All blends presented three relaxation stages: a first fast relaxation which was attributed to the relaxation of the pure phases, a second one which was characterized by the presence of a plateau, and a third fast one. The relaxation was shown to be faster for less extended and smaller droplets and to be influenced by coalescence for blends with a dispersed phase concentration larger than 20 wt.%. The relaxation of the blend was strongly influenced by the matrix viscosity. The addition of random copolymer resulted in a slower relaxation of the droplets.     

Rheological study of heterogeneities in melt blends of ZN-LLDPE and LDPE: Influence of M<Subscript>w</Subscript> and comonomer type,and implications for miscibility

The influences of molecular weight and LLDPE comonomer type on the heterogeneity (immiscibility) of Ziegler-Natta LLDPE and LDPE blends are investigated with rheological methods. Dynamic and steady shear measurements were carried out in a Rheometrics Mechanical Spectrometer 800.Blends of low-M_w (<10⁵)LLDPE (butene) and LDPE are likely homogeneous and miscible as revealed by the dependence of their on blend composition at 140 °C. Blends of high-M_w (10⁵)LLDPE (butene) and LDPE mixed and tested at 190 °C were only partially miscible; heterogeneity and immiscibility was likely to occur around the 50/50 composition and in the LDPE-rich blends. Blends were likely miscible in the LLDPE-rich range. Increasing the LLDPE branch length (comonomer) from butene to octene slightly increased the miscibility of LLDPE/LDPE blends. It is suggested that the molecular order in polyethylenes (see Hussein and Williams (1999) J Non-Newtonian Fluid Mech 86:105–118; (1998) Macromol Rapid Commun 19:323–325) and mismatch of the molecular conformations of different polyethylene structures provide explanations for the immiscibility of polyethylenes. Agreement was observed between the measured G() and G() and theoretical predictions of Palierne and Bousmina-Kerner models, which are based on two-phase emulsion behavior.     

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.     

Shear viscosity of polybutyleneterephthalate/liquid crystal polymer blends

Viscosity measurements have been carried out on blends of polybuty-leneterephthalate (PBT) and a liquid crystalline copolyesteramide (LCP). The flow curves of the blends with LCP content larger than 20%, show a behavior similar to that of the pure LCP, with a rapid rise of the viscosity at low shear rates. The viscosity-composition curves exhibit a deep minimum at low LCP content which may be mainly attributed to the lack of interactions between the two phases.     

Comparison of a new internal viscosity model with other constrained-connector theories of dilute polymer solution rheology

Complex viscosity ^* = -i predictions of the Dasbach-Manke-Williams (DMW) internal viscosity (IV) model for dilute polymer solutions, which employs a mathematically rigorous formulation of the IV forces, are examined in the limit of infinite IV over the full range of frequency number of submolecules N, and hydrodynamic interaction h ^*. Although the DMW model employs linear entropic spring forces, infinite IV makes the submolecules rigid by suppressing spring deformations, thereby emulating the dynamics of a freely jointed chain of rigid links. The DMW () and () predictions are in close agreement with results for true freely jointed chain models obtained by Hassager (1974) and Fixman and Kovac (1974 a, b) with far more complicated formalisms. The infinite-frequency dynamic viscosity predicted by the DMW infinite-IV model is also found to be in remarkable agreement with the calculations of Doi et al. (1975). In contrast to the other freely jointed chain models cited above, however, the DMW model yields a simple closed-form solution for complex viscosity expressed in terms of Rouse-Zimm relaxation times.     

The imbedded disk retraction method for measurement of interfacial tension between polymer melts

A method for measuring interfacial tension of high viscosity polymer melts at elevated temperatures is described. The method involves the tracking of the shape evolution of a disk of one material imbedded in a second one. This makes it possible to determine the interfacial tension over a relatively short time period. The technique of preparing the samples makes it possible to measure on practically any combination of polymer melts without restrictions on viscosities and melting temperature, as long as one of the materials is transparent in the molten state.The retraction of the disk is observed by using a microscope with a high resolution video camera. The camera is connected to a video frame grabber in a personal computer which is programmed to collect images with preselected time intervals. Data of the retraction is acquired by using an image analysis software, measuring the average radius of the disk.The driving force for the shape evolution is interfacial tension and it is balanced by viscous forces. The analysis of the retraction process is done analytically with a simplified one-dimensional model. The model has been compared to experiments with the system PS/PMMA at 210 °C, covering viscosity ratios over a range of six decades and five different molecular weight values of PS. It is shown that interfacial tension can be determined over the whole range and a value of 1.1±0.2 mN/m was obtained for all samples.     

Rheological characterization of well-defined tetrafluoroethylene/hexafluoropropylene copolymers

The rheology of tetrafluoroethylene/hexafluoropropylene (TFE/HFP) copolymers, also known as Teflon FEP polymers, having different molecular weight and composition (HFP content) was studied by means of a parallel-plate rheometer. Two groups of polymers having different molecular weights with nearly constant polydispersity (around 2.5) were considered; namely, one group having a relatively low melting temperature (amorphous with a high content of HFP) and a second group having a higher melting point (semi-crystalline with a lower content of HFP). The relaxation time spectrum, H(λ), calculated by use of the BSW model (developed for monodisperse linear polymers) followed a scaling relationship in the terminal zone with scaling exponent of 0.13. However, at higher frequencies the model fails to predict adequately the experimental data. The longest relaxation time calculated from both the BSW model and discrete relaxation spectra (λ _i ,g _i ), which was determined by use of a parsimonious fitting software, depends on the molecular weight in a similar way as the zero-shear viscosity does with the well-established scaling factor of 3.4. The critical molecular weight for the onset of entanglements, M _c , was found to be about 100000, a value much higher than those previously reported in literature for other polymers. The rheology of resins in the second group (higher melting point) was found to exhibit a strong dependence on thermal history during oscillatory-shear measurements. The data obtained in experiments at different temperatures without a preheating to a certain value (330°C) exhibited a violation of the time-temperature superposition principle and no well-defined values of the zero-shear viscosity. This is attributed to residual crystallinity even at temperatures well above their melting point (260°C). However, the same experiments with preheating and subsequent cooling to desired temperature resulted into a very good time-temperature scaling. Received: 13 January 1998 Accepted: 6 April 1998     

Solidification behavior of the theta system 2-propanol/poly(n-butyl methacrylate) I. Influences of thermoreversible gelation on stationary flow

Zero shear viscosities, ₀, were determined by means of a magnetoviscometer for melts of poly(n-butyl methacrylate) (M = 8.7 to 450 kg/mol, T =53.5 to 200°C) and for concentrated solutions of the highest molecular weight sample in isopropanol (T = 34.8 to 131.5 °C). Master curves can be constructed in both cases if the reference temperature is set proportional to the gelation temperature of the particular fluid. Special intersegmental interactions (eventually leading to thermoreversible gelation) can above all be felt in ₀ (T) and in M _c , the critical molecular weight determined in plots of log ₀ vs. log M. As the temperature is lowered, the behavior changes from WLF to Arrhenius, and M _c declines considerably. The former observation is explained by analogy to the transition from fragile to hard glasses resulting from increased crosslinking. The latter effect can also be rationalized in terms of a physical network reducing the molecular weight that is required for the formation of entanglements.     

Transient behavior of Boger fluids under extended shear flow in a cone-and-plate rheometer

Three different dilute solutions of high molecular weight polymers in viscous, binary solvents were used in experiments performed in a cone-and-plate rheometer. The solutions all fall into the class of fluids referred to as Boger fluids and were previously used in studies of viscoelastic Taylor-Couette instabilities. Under prolonged shearing in the cone-and-plate geometry, these fluids all exhibited a decrease of the first normal stress growth function N₁⁺(t) from an initial plateau value to a second, lower plateau value. This behavior has been previously observed, but is here reported for widely used polyisobutylene-based Boger fluids for the first time. As in earlier studies (Magda JJ, Lee C-S, Muller SJ, Larson RG (1993) Macromolecules 26:1696–1706; MacDonald M, Muller SJ (1997) J Rheol Acta 36:97–109), the time at which this decrease occurs (the decay time) is much longer than the polymer molecules relaxation time. Here, we focus on three issues: 1) the time-temperature superposition of the first normal stress growth function N₁⁺(t), including the decay time and the value of the second plateau, 2) the sample recovery time required to reproduce the initial plateau value of N₁⁺ and the decay time, and 3) the relationship between the time scales for this decay of normal stresses and the onset of viscous heating induced instabilities in the Taylor-Couette geometry. Our results suggest that shear-induced conformational changes, possibly coupled to viscous heating of the sample, may be responsible for the decrease in the first normal stress growth function during prolonged shearing.