Shear-induced anisotropy in thermal conductivity of a polyethylene melt

A rotating concentric-cylinder thermal conductivity cell for polymer liquids is described. Thermal conductivity can be measured at temperatures approaching 200°C and at strain rates up to 400 s^?1, The transient heat flux probe (with inner cylinder as heat source and temperature probe) method is used to permit the separation of the viscous heating effect from the probe heating effect. A polyethylene melt was studied and showed that at 50 s^?1, a 2 percent increase in thermal conductivity occurs, followed by a gradual decrease until a value 10 percent less than the no-shear thermal conductivity was found at 400 s^?1. This effect is due to molecular orientation.     

Rheology of polymer melts in high shear rate

Little is known of the rheology of polymer melts in the high shear rate up to 10⁶ s^?1 or more. A specially designed high-shear-rate rheometer was developed, by which the rheology of polymer melts for shear rates up to 10⁸ s^?1 can be investigated. Two non-Newtonian regions and a transition or the second Newtonian region were observed in the wide range of shear rates up to 10⁷ s^?1. The observed flow curves for various polymer melts are classified into three typical patterns. One is the flow curve typically shown of high-density polyethylene in which a clear second Newtonian region appears after the first non-Newtonian region. The second is the typical flow curve of polystyrene in which a “transition region” appears instead of the second non-Newtonian region. The third is the flow curve shown of acrylonitrile-styrene copolymer, which exhibits behavior between the two types. A generalized flow curve is proposed to explain the observed flow behaviors of various polymers over a wide range of shear rates. The flow behavior in high shear rate results from high orientation and scission of polymer molecules.     

Comparison of superimposed effects in high‐shear‐rate capillary rheology of polystyrene,polypropylene, and linear low‐density polyethylene melts

Polymer melts exhibit unique rheological behaviors at high shear rate up to 10⁶ s^?1, which is a common phenomenon in micro‐injection molding. Both online and commercial capillary rheometers, which were modified to allow regulation of back pressure, were used for measuring the melt shear viscosities of polystyrene (PS), polypropylene (PP), and linear low‐density polyethylene (LLDPE) under high shear rates. The rheological characteristics of the three melts were compared through the systematical analyses for three significant effects, namely the end pressure loss, pressure dependence, and dissipative heating in capillary flow. Pronounced end effect begins to appear at the shear rates of 1.6 × 10⁵, 8.0 × 10⁵, and 2.8 × 10⁶ s^?1 for the PS, PP, and LLDPE melts, respectively. The significance of the end effect can be ordered as PS > PP > LLDPE. It seems that the polymers with more complex molecular structures exhibit a higher degree of divergence between the comprehensively corrected and uncorrected melt viscosity curves. Moreover, the dissipation effect begins to predominate over the pressure effect under the lowest shear rate of 10⁵ s^?1 for the PS melt among the three melts. POLYM. ENG. SCI., 55:506–512, 2015. © 2014 Society of Plastics Engineers     

High shear strain rate rheometry of polymer melts

The rheology of a range of polymer melts has been measured at strain rates above those attained during conventional rheometry using an instrumented injection molding machine. Deviations from shear thinning behavior were observed at high rates, and previously unreported shear thickening behavior occurred for some of the polymers examined. Measured pressure and volumetric throughputs were used to calculate shear and extensional viscosity at wall shear strain rates up to 10⁷ s^?1. Parallel plate rheometry and twin bore capillary rheometry were used to provide comparative rheological data at low and medium shear strain rates, respectively. Commercial grades of polyethylene, polypropylene, polystyrene, and PMMA were studied. Measured shear viscosity was found to follow Newtonian behavior at low rates and shear thinning power law behavior at intermediate strain rates. At shear strain rates approaching or above 10⁶ s^?1, shear viscosity reached a rate‐independent plateau, and in some cases shear thickened with further increase in strain rate. A relationship between the measured high strain rate rheological behavior and molecular structure was noted, with polymers containing larger side groups reaching the rate‐independent plateau at lower strain rates than those with simpler structures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Shear and extensional flow of a thermotropic liquid crystalline polymer

The flow of a thermotropic liquid crystalline polymer (unfilled and glass fiber filled) was studied using a capillary rheometer and an instrumented injection molding machine. Despite different thermal histories, the techniques gave similar results. From 330 to 350°C, viscosity was independent of temperature. At 340°C, where most measurements were carried out, pronounced shear-thinning occurred and the shear flow curves were nonlinear, the power law exponent decreasing from 0.51 at a shear rate of 10 s⁻¹ to 0.35 at 10⁴ s⁻¹. A previously reported model was used to derive elongational flow curves from die entry pressure data. Because of the nonlinearity of the flow curves, quadratic log-stress vs. log-strain rate plots were needed to model behavior over the strain rate region studied. The elongational flow curves were similar in shape to the shear flow curves, with an effective Trouton ratio of 30. Despite orientation and structure present in the melt, the extensional viscosities and Trouton ratios were within the range found with normal thermoplastic melts. The results suggest that extensional flow may be inhomogeneous, the flowing units possibly being partially ordered domains.     

Molecular orientation of polydimethylsiloxane induced by elongational and shearing strains

A study examining the molecular orientation of poly(dimethylsiloxane) for different combinations of elongational and shear strains is presented. Three different cases were studied: (1) pure elongational strain; (2) increasing shear and decreasing elongational strains; (3) increasing shear and increasing elongational strains. The experiments were performed in a converging flow cell (at room temperature), where elongational and shearing strain rates achieved values of 370 s^?1 and 640 s^?1 respectively. Values of the Hermans orientation function were obtained from measurements of birefringence and polarization angles while strain rates were estimated from laser Doppler anemometry velocity measurements. Prospects for predicting molecular orientation from the stress-optical laws and rheological flow models are outlined and commented on.     

Viscosity of polydimethylsiloxane gum: Shear and temperature dependence from dynamic and capillary rheometry

The rheology of Dow Corning polydimethylsiloxane gum (PDMS/silicone gum) was studied over a time range of 10^?2 to 10⁵ s^?1 and a temperature range of 23–150°C using both capillary and dynamic rheometry. A low shear Newtonian region is observed at room temperature below 0.01 rad/s (increasing to 0.1 rad/s at 150°C) for which an Arrhenius activation energy for a viscous flow of 13.3 kJ/mol was determined. The Cox–Merz rule for merging of shear and complex viscosities is found to be valid up to 10 s^?1. Viscosity is found to be independent of temperature above 100 s^?1, where terminal power‐law flow is encountered. This is exhibited in the dynamic data as equal plateau moduli for the various temperature curves. Gross wall slippage is seen in capillary flows above approximately 100 s^?1, corresponding to a stress value of 70–100 kPa. Slip‐stick (spurt) flow is not observed. The viscosity data are best fitted by the Carreau–Yasuda model with a fitting parameter a of 0.7, a power‐law index n of 0.05 (low because of slip effect), and a zero shear viscosity of 32 kPa s at 23°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2533–2540, 2002     

Chemorheological study of compatibilized blends of low‐density polyethylene and polydimethyl siloxane rubber

Compatibilization of the blends of polydimethyl siloxane (PDMS) rubber and low‐density polyethylene (LDPE) was achieved through reactive processing during extrusion in a Monsanto Processability Tester (MPT). The chemorheological characteristics of 50 : 50 LDPE : PDMS blends with varying proportions (0–8 wt %) of ethylene comethyl acrylate (EMA) were investigated at three different temperatures (170, 190, and 210°C) and four different shear rates (61.3, 122.6, 306.6, and 613.1 s^?1). It was found that EMA reacts with vinyl groups of PDMS rubber at a temperature of 190°C during extrusion through the capillary of MPT, forming EMA‐grafted‐PDMS rubber (EMA‐g‐PDMS), which acts as the compatibilizer for the blend systems. The results are based on IR spectroscopy, melt rheology, and phase morphology of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2810–2817, 2003     

An empirical model relating the molecular weight distribution of high-density polyethylene to the shear dependence of the steady shear melt viscosity

An empirical model has been developed to relate molecular weight distribution to the shear dependence of the steady shear viscosity in high-density polyethylene melts. It uses a molecular weight, M_c, which partitions molecular weights into two classes; those below M_c contribute to the viscosity as they do at zero shear, and those above M_c contribute to the viscosity as though they were of molecular weight M_c at zero shear. Each individual molecular weight species contributes on the basis of its weight fraction. M_c is proposed to be a unique function of the shear rate. Using this method of treating the molecular weight distribution, and the zero shear relation for relating η0 to molecular weight, the calculated steady shear viscosities at various shear rates for polyethylene samples of widely varying polydispersities agree well with experimental results. The model makes no judgment on the existence or importance of entanglements in non-Newtonian behavior since it has no specific parameters involving an entanglement concept. Use of the model suggests that for the samples studied, only the upper portion of the molecular weight distribution contributes toward the experimentally observed decrease of steady shear viscosity with shear rate for shear rates of up to 10,000 sec^?1. The lower molecular weight species are assumed to behave in a Newtonian manner.     

The rheology of filled polymers

The flow properties of polymer melts containing fillers of various shapes and sizes have been examined. If there is no failure of either the filler or polymer in the solid state, then the modulus enhancement for randomly distributed filler is equal to the melt viscosity enhancement under medium shear stress conditions (10⁴ Nm^?2) in simple shear flow or in oscillatory shear flow. Submicron-size fillers, in particular, can form weak structures in the melt that greatly increase the low shear rate viscosity without changing the modulus of the solid proportionately. The highly pseudo-plastic nature of polymer melts at shear stresses of 10⁶ Nm^?2 means that, even without orientation of filler particles toward the flow direction, the viscosity enhancement is less than at lower shear stresses.     

Interrelationship of strength and flow characteristics of polystyrene

This study investigated the interrelationship between strength and flow characteristics of general-purpose polystyrene (GPPS) used in injection molding applications. The ease of flow was chosen as a measure of processability and was evaluated using the melt flow rate and capillary rheometer techniques. Of the different strength tests that were examined, flexural and notched tensile strength tests were most effective in differentiating between commercial grades of high and low molecular weight GPPS. While characterizing strength of injection molded specimens, the degree of molecular orientation was taken into consideration. For unplasticized resins, increasing the weight average molecular weight by about 100,000 enhanced the flexural strength by 10%, but also increased the viscosity at low shear rates (10 to 100 s^?1). The increase in molecular weight had virtually no effect on viscosity at the highest shear rates (up to 10,000 s^?1). Plasticized resins displayed a 6% loss in flexural strength as well as a significant reduction in viscosity (throughout the shear rate range) as compared with the unplasticized resins. As expected, the improvement in strength achieved by increasing molecular weight leads to a simultaneous increase in the viscosity, i.e., a deterioration of processability. In addition, our study indicates that for samples without preferential molecular orientation, narrowing the molecular weight distribution significantly improves the balance of strength and melt flow rate properties.     

Assessment of development and relaxation of orientation in a sheared thermotropic liquid crystalline copolyester

Shear-induced chain orientation and relaxation of chain orientation in a thermotropic liquid-crystalline poly(4-hydroxybenzoic acid (73mol%)-co-2-hydroxy-6-naphthoic acid (27 mol%)) (Vectra A950) were studied by means of transmitted light intensity through crossed polarizers in a shear cell. Shear rates ranged between 4 and 1000 s^?1 and the level of chain orientation increased with increasing shear rate and increasing temperature. Overall, the times for relaxation were very short. The longest relaxation times (?21s) were obtained at the lowest shear temperatures and at intermediate shear rates. At high shear rates, the relaxation times were generally short (?2s) and independent of temperature. The rapid relaxation of orientation after high rate shearing (100–1000 s^?1) indicates that shear-induced crystallization is inhibited under these conditions. A certain degree of chain orientation was still present although the relaxation as judged by the transmitted light intensity was complete. Signs of recrystallization were observed if the samples were not preheated to 320°C prior to shearing. By simultanecous shearing and cooling, high degrees of orientation were achieved (f ? 0.7) as revealed by X-ray diffraction and infrared dichroism. Infrared spectroscopy showed that annealing of oriented samples at 250°C led to an increase in thermal stability of the orientation with annealing time.     

Molecular orientation effects on thermal conductivity of polydimethylsiloxane under shearing strain

Experimental results for thermal conductivity and flow birefringence on liquid poly (dimethyl siloxane), PDMS, under a shearing strain are discussed. An increase in thermal conductivity with increasing shear rate is attributed to an increased degree of orientation in a direction at 45° to the flow direction for simple shear. A mathematical model is set up. It is based on the assumption that the macromolecules do not change their time-average shape and otherwise behave as rigid, thin cylinders which can be influenced by convection and external fields and are endowed with rotational Brownian motion. The model predicts that thermal conductivity will reach a maximum value at moderate rates of strain and begin to decrease eventually reaching a minimum value (the transverse thermal conductivity of the basic element) at very high rates of strain when the molecules are completely aligned in the flow direction. Liquids studied were a 12,500 centipoise PDMS in the pure state and in solution in methyl ethyl ketone, MEK, as well as a 65,000 centipoise solution in MEK.     

Equibiaxial elongational viscosity measurements of commercial polymer melts

The equibiaxial elongational viscosity of six commercially available polymer melts is measured using a novel technique known as continuous lubricated squeezing flow. This technique is a modification of simple lubricated squeezing flow. The systems were chosen in order to investigate the dependence of equibiaxial elongational viscosity on molecular structure. Three of the melts are polyethylene with long chain branching, two are polyethylene with short chain branching, and one is polyisobutylene with linear chains. Each polymer was subjected to strain rates ranging from 0.003 to 0.1 s^?1 and compared to the linear viscoelastic prediction so that the degree of strain hardening could be determined. For a modestly branched polymer, comparison of rheological behavior in both uniaxial and equibiaxial deformations was possible. POLYM. ENG. SCI., 55:1012–1017, 2015. © 2014 Society of Plastics Engineers     

Effects of ?CH2CH2CF3 on properties of RTV polysiloxane rubber: Processability,thermal stability,and oil/solvent resistance

Room temperature vulcanizing fluorosilicone rubbers (FSRs) were prepared from polydimethylsiloxane (PDMS), vinyl fluorosilicone‐oil (VFS‐oil), and precipitated silica (PDMS/VFS/SiO₂). Rheological tests showed appropriate processing condition could be obtained when shear rate > 10 s^?1. Mechanical tests indicated that tensile strength and elongation at break were not much affected by VFS‐oil and no decline was observed after being aged in 70 °C ASTM 1# oil. The ? CF₃ group could not only increase oil‐resistance, but also decrease surface energy, which were proved by ATR‐FTIR and contact angle tests. The PDMS oil immersion tests showed that the higher the content of VFS‐oil, the better oil resistance can be obtained. The solvent‐resistance tests indicated that the VFS‐oil improved resistance to nonpolar/low‐polar solvent. TGA results showed that the increasing content of VFS‐oil could slightly decrease FSRs' thermal stability but increase FSRs' residual mass ratio at 790°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39708.     

Effects of CH2CH2CF3 on properties of RTV polysiloxane rubber: Processability,thermal stability,and oil/solvent resistance

Room temperature vulcanizing fluorosilicone rubbers (FSRs) were prepared from polydimethylsiloxane (PDMS), vinyl fluorosilicone‐oil (VFS‐oil), and precipitated silica (PDMS/VFS/SiO₂). Rheological tests showed appropriate processing condition could be obtained when shear rate > 10 s^?1. Mechanical tests indicated that tensile strength and elongation at break were not much affected by VFS‐oil and no decline was observed after being aged in 70 °C ASTM 1# oil. The ?CF₃ group could not only increase oil‐resistance, but also decrease surface energy, which were proved by ATR‐FTIR and contact angle tests. The PDMS oil immersion tests showed that the higher the content of VFS‐oil, the better oil resistance can be obtained. The solvent‐resistance tests indicated that the VFS‐oil improved resistance to nonpolar/low‐polar solvent. TGA results showed that the increasing content of VFS‐oil could slightly decrease FSRs' thermal stability but increase FSRs' residual mass ratio at 790°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39708.     

Rheological properties of poly(trimethylene terephthalate) in capillary flow

The shear viscosity, extensional viscosity, and die swell of the PTT melt were investigated using a capillary rheometer. The results showed that the PTT melt was a typical pseudoplastic fluid exhibiting shear thinning and extensional thinning phenomena in capillary flow. There existed no melt fracture phenomenon in the PTT melt through a capillary die even though the shear rate was 20,000 s^?1. Increasing the shear rate would decrease the flow activation energy and decline the sensitivity of the shear viscosity to the melt temperature. The molecular weight had a significant influence on the flow curve. The flow behavior of the PTT melt approached that of Newtonian fluid even though the weight‐molecular weight was below 43,000 s^?1 at 260°C. The extensional viscosity decreased with the increase of the extensional stress, which became more obvious with increasing the molecular weight. The sensitiveness of the extensional viscosity to the melt temperature decreased promptly along with increasing the extensional strain rate. The die swell ratio and end effect would increase along with increasing the shear rate and with decreasing the temperature, which represented that the increase of the shear rate and the decrease of temperature would increase the extruding elasticity of the PTT melt in the capillary die. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 705–709, 2005     

The viscosity of monomolecular melts of poly(vinyl chloride)

PVC melts are predicted to be homogeneous with single molecules as the stable flow units (monomolecular melts) at corresponding values of high temperatures and/or high shear stresses. Under these conditions, it is found that the zero shear viscosity in simple shearing flow of rigid compounds depends on the average molecular weight by weight to the 3.5 power for molecular weights between 24,000 and 100,000. All data measured under conditions where monomolecular melts are predicted fall on a master curve of reduced viscosity versus reduced shear rate when a relaxation time proportional to η0/c²T is used. It is, therefore, concluded that monomolecular melts of PVC compounds follow the same structure–viscosity relations as found for other linear melts in viscometric flow.     

A study of low shear viscosity of polymer melts

An inexpensive, accurate falling coaxial cylinder viscometer is described. Viscosities can be measured at shear stresses at least as low as 10³ dynes per cm² and flow curves can be obtained with shear thinning fluids. Data for a polystyrene and a polyethylene polymer coincide with those from other techniques and with corresponding literature values. The lower Newtonian viscosities pf both polymers were experimentally accessible, and it is shown that estimation of η_o by extrapolation from viscosities in the non-Newtonian region may be subject to errors of uncertain magnitude. Shear history of the sample affects the Newtonian and low shear viscosities of high molecular weight polymer melts.     

A rheo-optical study on the reformation of structure in racemic poly(γ-benzyl glutamate) liquid crystals

Transmitted light intensities were measured by means of the polarized light technique for the nematic liquid crystal phase of racemic poly(γ-benzyl glutamate) (PBG) in m-cresol at 25°C after cessation of steady flow at shear rates ranging from 0.2 to 110 s^?1. Weight-average molecular weights of PBG used were 1.5, 2.1, and 2.6 × 10⁵, while the concentrations varied between 20, 30, and 40 wt percent. Transmitted light intensities with crossed and parallel polarizers, I_x and I_|, show wavy changes with time after cessation of steady flow, indicating the retardation decreases with time. An attempt was made to explain experimental results on the basis of a simple model, in which not only relaxation of molecular orientation but also effects of the wall and disclination were taken into account.