Shear dependence of thermal conductivity in polyethylene melts

Thermal conductivity measurements with a modified Couette flow cell were obtained as a function of shear rate for two linear polyethylene melts of weight-average molecular weights 27,300 and 56,700, respectively. The lower-molecular-weight polyethylene revealed a maximum decrease in thermal conductivity of 55 percent at 150 s^?1. After shearing at 400 s^?1, approximately 90 minutes was required to recover the value corresponding to the zero shear condition. This was considered consistent with molecular orientation into the flow direction during shear with a subsequent relaxation upon the removal of stress. The higher-molecular-weight polyethylene gave a similar decrease in thermal conductivity at 50 s^?1. Unlike the lower-molecular-weight melt, an increase was observed at higher shear rates. Enhancement of energy transport via cluster flow mechanism was presented as a possible interpretation of these results. A theory of molecular orientation of liquid poly(dimethylsiloxane) (PDMS) under shear flow was previously developed from thermal conductivity and birefringence data of this material. An attempt to clarify the difference in behavior between the two melts examined in this work, and between the polyethylene melts and the PDMS previously studied is presented.     

Rheology of PVC. Part 5: Melt elasticity

The behavior of PVC changes drastically with the temperature and the method of sample preparation. In the steady-state shear mode, upon a decrease of the rate of deformation, the data may show either a steady increase of the shear viscosity or a leveling off to a Newtonian plateau. In the dynamic test mode, both the storage modulus, G′, and the loss modulus, G″, show an effect of the yield stress. Only at temperatures above 210°C are flow curves normal for polymer melts obtained. Rigid and nonrigid PVC formulations have been tested in Weissenberg Rheogoniometer, using steady-state or dynamic test modes at temperatures from 140 to 220°C. It was observed that yield affects elasticity more (measured by the first normal stress difference or the storage modulus) than viscosity (expressed by the shear stress or the loss modulus). The corrected for yield plots of elastic vs. viscous parameter can be easily interpreted in terms of a composite flow.     

Jetting phenomena in injection mold filling mold filling

Experimental studies of injection molding of polymer melts have classified two regimes of mold filling–simple filling and jetting. In this paper we have examined a wide range of polymer melts and mold designs in an attempt to devise a criterion for the transition between these regimes. This criterion is found to be related to the extrudate swell d, gate diameter D, and small cavity dimension at the gate h. For isothermal mold filling, if d/h exceeds 1.0, the-melt will contact the mold, stick to it, and induce a simple mold filling regime. The variation in behavior in vertical and horizontal mold filling is considered, as is the influence of barriers near the gate. For the non-isothermal mold case, the manner of filling is similar, and the criterion for jetting remains the same, The die swell behavior in the non-isothermal case is complex.     

The macroscopic volume changes of selected polymers subjected to uniform tensile deformation

High density polyethylene (PE), polycarbonate (PC), and polymethylmethacrylate (PMMA) were subjected to uniaxial tensile deformation up to the onset of instability or necking. Simultaneous readings of longitudinal extension and transverse contraction (width and thickness) were obtained continuously during the loading period. From these data, plots of longitudinal versus “average” transverse strain were produced and it was found that the trends were neither constant nor linear over the full strain range employed. Additional plots of per cent volume change versus longitudinal strain indicate that the PMMA and PC show a maximum volume increase of about 0.6% while PE shows a maximum volume decrease on the order of 2.5%. Similar volume decreases have been noted by others and it would appear that structural changes are the most likely cause of this behavior.     

Elastic behavior of LDPE/HEPE blend melts in capillary extrusion

The studies of the elastic behavior in the capillary flow of LDPE/HDPE blend melts were carried out at a test temperature range from 180 to 200°C and at an apparent shear rate of about 25–120 s⁻¹. The end‐pressure drop (ΔP_end) increased nonlinearly with increasing wall shear stress (τ_w) and achieved a minimum value at a weight fraction (ϕ_HD) of HDPE of 50%. The die‐swell ratio (B) increased basically linearly with increasing τ_w or ΔP_end and achieved a maximum value at ϕ_HD of 50%. With the addition of the die length–diameter ratio, the values of B were decreased linearly. At a low shear rate, the temperature sensitivity of the melt die‐swell was more significant than at a high shear rate. With increasing ϕ_HD, B increased when ϕ_HD < 50%, then decreased. B reached a maximum value at ϕ_HD of 50% and a fixed apparent shear rate. This phenomenon may be explained by using the theory of viscoelastic competition between components of polymer blend melts. Furthermore, the first normal stress difference (N₁) of the sample melts was estimated by using an equation published in a previous work. The results showed that B increased linearly with increasing N₁. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 759–765, 2000     

Correlation between viscoelasticity,microstructure, and molecular properties of zein and pennisetin melts

Cereals are a large source of biopolymers, where mainly the starch is used for food and feed. A rapidly growing cereal application is the production of biofuel, mainly produced from corn in the US. The starch is fermented to ethanol leaving spent grain rich in cereal proteins as a by-product. The corn protein zein is currently extracted on a large scale and used in, for example, material applications. Similarly, pennisetin can be extracted from pearl millet, a crop critical for food security in sub-Saharan Africa. The formation of viscoelastic melts is crucial for (bio)plastics production and the viscoelasticity, microstructure, and molecular properties of zein and pennisetin melts were determined here. The proteins were mixed with plasticizers (polyethyleneglycol or glycerol/citric acid) to form melts. The melts displayed a phase separated microstructure with protein-rich and plasticizer-rich regions with distinctly separate T_gs. The pennisetin melts formed cross-links at temperatures above 60°C, which could be related to the high content of cysteine and methionine, as compared to zein. As a consequence, pennisetin melts showed a more thermocomplex behavior than zein melts. For zein melts, the mixture of glycerol and citric acid interacted with protein in addition to being a plasticizer causing a high-molecular weight shoulder in the molecular weight distribution. The study showed that, although both zein and pennisetin form viscoelastic melts, the choice of plasticizer strongly affects both melt structure and physical properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Extrudate swell behavior of polypropylene composites filled with microencapsulated red phosphorus

The microencapsulated red phosphorus (MRP) filled polypropylene (PP) composites were prepared using a twin‐screw extruder. The effects of load and temperature on the extrudate swell behavior of the PP/MRP composite melts were investigated by means of a melt flow indexer. The test temperatures and loads were varied from 180 to 205°C and from 2.16 to 12.5 kg, respectively. The results showed that the die‐swell ratio (B) of the composite melts increased roughly linearly with increasing load while decreased slightly with a rise of test temperature. The sensitivity of the die‐swell ratio of the composite melts to load was significant. When the test temperature or load was constant, the values of the B of the composite melts decreased slightly with increasing MRP weight fraction. The findings can provide useful information for processing of these composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Experimental study of elongational flow and failure of polymer melts

A new and simple instrument for measurement of elongational flow response of polymer melts in constant uniaxial extension rate experiments is described. Quantitative stress development data are presented for a series of low-density polyethylene (LDPE), high-density polyethylene (HDPE), polystyrene (PS), polypropylene (PP), and poly(methyl methacrylate) (PMMA) melts. For small elongation rate E, linear viscoelastic behavior was observed; while for large E, LDPE and PS showed exponential stress growth, while HDPE and PP showed only linear stress growth. Stress relaxation experiments were carried out for several of the same melts in the instrument. Elongation to break and mechanisms of filament failure were studied. HDPE and PP have a tendency to neck and exhibit ductile failure, while at high E, LDPE and PS seem to show cohesive fracture. The elongational flow stress response data were compared to predictions of nonlinear viscoelastic fluid theory, specifically the Bogue-White formulation. The qualitative differences in responses of the melts studied were explained in terms of different dependences of the effective relaxation times on deformation rate and, more specifically, on values of the a parameter in the theory.     

Dynamic rheological behavior and mechanical properties of PVC/CPE/MAP–POSS nanocomposites

Poly(vinyl chloride)/chlorinated polyethylene (PVC/CPE)/methylacryloylpropyl‐containing polyhedral oligomeric silsesquioxane (MAP–POSS) nanocomposites are prepared. The plastic behavior and dynamic rheological behavior of PVC/CPE/MAP–POSS are investigated. The influences of composition on dynamic storage modulus G′, loss modulus G″, and complex viscosity η* of PVC/CPE/MAP–POSS melts are discussed. The dynamic mechanical properties, mechanical properties, and morphology are determined. The results show that both plastic time and balance torque of the nanocomposites decrease, but the G′, G″, and η* all increase with increasing MAP–POSS content. The maximum value of the dynamic mechanical loss tan δ decreases and elasticity increases when MAP–POSS is added. The impact strength of the nanocomposites increases with increasing MAP–POSS content and has the best value at 10% content of MAP–POSS, which is 5.38 kJ/m² higher than that of the blend without MAP–POSS. The MAP–POSS can be used as an efficient process aid and impact aid for the PVC/CPE blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Rheological effects of polyethylenes in film blowing

The aim of this work is to correlate the rheological properties and processability of various polyethylenes during the film‐blowing process. The effect of rheology on the kinematics and dynamics of film blowing for five different polyethylene resins has been extensively studied using a fully instrumented laboratory unit. The complex viscosity, shear viscosity, uniaxial elongational viscosity, and non‐uniform biaxial elongational viscosity, as well as the strain rates and stresses during film blowing, have been determined and correlated to the bubble stability. G′ versus G″ plots were found to be virtually independent of temperature for all polymers investigated. The more elastic polymers (larger G′ values) were found to be more stable in film blowing. Also, the more stable polymer melts were found to be those possessing larger elongational properties.     

Rheological behaviors of glass bead‐ and wollastonite‐filled polypropylene composites modified with thermoplastic elastomers

Steady‐ and oscillatory‐shear rheological behaviors of polypropylene/glass bead (PP/GB) and PP/wollastonite (PP/W) melts modified with thermoplastic elastomers, poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) copolymer (SEBS) and the corresponding block copolymer grafted with maleic anhydride (SEBS‐g‐MA), were examined by means of a parallel‐plate rheometer. With adding the elastomers (SEBS and SEBS‐g‐MA) and fillers (spherical GB and acicular W) to PP, viscosity especially at low shear rates and shear‐thinning flow behavior at high shear rates were pronounced as evidenced quantitatively by Carreau–Yasuda (CY) parameters, but Cox–Merz analogy became weakened. Besides, melt‐elasticity in terminal region and relaxation time (t_c) in crossing point increased, indicating an enhancement in quasi‐solid behavior of molten PP. Comparing with the elastomers, rheological behaviors of molten PP were more influenced with adding the rigid fillers, especially with W due to distinct acicular shape of W particles. SEBS‐g‐MA elastomer more affected rheological behaviors of the ternary composites than SEBS elastomer, implying that SEBS elastomer and the filler particles behaved individually (i.e., development of separate microstructure) in (PP/GB)/SEBS and (PP/W)/SEBS ternary composites, but core‐shell microstructure developed with strong interfacial adhesion by adding SEBS‐g‐MA elastomer, and the filler particles encapsulated with the thick SEBS‐g‐MA elastomer interlayer (i.e., core‐shell particles) acted like neither big elastomer particles nor like individual rigid particles in melt‐state. Moreover, effects of SEBS‐g‐MA elastomer reached a maximum on rheological behaviors of (PP/W)/SEBS‐g‐MA ternary composite, indicating a synergy between core‐shell microstructure and acicular W particles. Correlations between oscillatory‐shear flow properties and microstructures of the blends and composites were evaluated using Cole–Cole (CC), Han–Chuang (HC), and van Gurp–Palmen (vGP) plots. COMPOS., 2012. © 2012 Society of Plastics     

Deformation and energy absorption characteristics of microcellular ethylene‐octene copolymer vulcanizates

Compressive stress‐strain properties of unfilled, CaCO₃, silica and aluminum silicate filled closed‐cell microcellular ethylene‐octene co‐polymer vulcanizates were studied with variation of blowing agent loading (density). With decrease in density, the compressive stress‐strain curves for microcellular vulcanizates behave differently from those of the solid vulcanizates. The stress‐strain properties are found to be strain rate dependent. The log‐log plots of relative compressive moduli versus relative density of the microcellular vulcanizates show a fairly linear correlation. The energy absorption behavior was also studied from the stress‐strain properties. The efficiency, E, and Ideality parameter, I, were evaluated. These parameters were plotted against stress to find the maximum efficiency and maximum ideality region, which will make these materials suitable for cushioning and packaging applications. The cushioning factor, C, for microcellular vulcanizates has also been evaluated for various systems.     

Studies of thermal transition behavior in plasticized poly(vinyl butyral-co-vinyl alcohol) with solid-state NMR and thermal analysis techniques

Samples of plasticized poly(vinyl butyral-co-vinyl alcohol) (PVB) are found to exhibit multiple thermal transitions as observed by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). Arrhenius plots using DSC and DMA data suggest that two of the transitions are glass-type ones. Variable temperature solid-state ¹³C-NMR experiments show a temperature-dependent line-broadening pattern for all PVB backbone carbons with maximum broadening at 55°C or at about 50°C above the second-order-type transitions α₁ and α₂ as measured by DSC. Using Arrhenius plots, the NMR transition is found to best correlate with α₁, which is consistent with glass transition behavior. The solid-state NMR spectra also show that vinyl alcohol tacticity remains unresolved up to a temperature of about 95°C, beyond which line narrowing begins to occur. High-temperature thermal transitions are also observed by DSC and DMA, which suggest that the onset of motion involving vinyl alcohol sequences may be responsible for these transitions.     

Junction properties of Schottky diode based on composite organic semiconductors: Polyaniline-polystyrene system

Schottky barrier diode based on composite of polyaniline with polystyrene has been fabricated and characterized using aluminium as Schottky contact and platinum as an ohmic contact. The observed current-voltage characteristics can be satisfactorily fitted using the modified Schottky equation. Current-voltage (I-V) plots were non-linear and capacitance-voltage (C-V) plots were almost linear in reverse bias indicating rectification behavior. Various junction parameters were calculated from the temperature dependent I-V and C-V data and discussed. These results indicate that the composite materials have better mechanical strength and diode quality compared to the pure semiconducting polymer.     

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.     

Comparison of the behaviour of glassy carbon and some metals for use as nonconsumable anodes in alumina-cryolite melts

Current interest exists in development of nonconsumable anodes for the Hall-Heroult process of aluminium production and also in situ analytical probes for determination of Al₂O₃ content in the cryolite melts used in this process. A comparison of the behaviour of glassy carbon and metals such as tungsten, tungsten carbide, nickel and stainless steel (SS-316) used as anodes in alumina-cryolite melts is investigated by means of electrochemical transient techniques (cyclic voltammetry and chronoamperometry) and Tafel anodic polarization experiments. The results show that only glassy carbon could be used as a successful sensor electrode for an in situ determination of Al₂0₃ in alumina-cryolite melts and that the metals investigated are unresistant to anodic attack in such melts. Consequently, the metals investigated cannot be used as sensor electrodes for in situ electro-analytical determination of alumina in alumina-cryolite melts, nor as anodes in the production of aluminium by the Hall-Heroult process.     

Rheological and thermal properties of blends of low-density polyethylene and its ionomers

Melt rheology and DSC studies of blends of two ionomers′ ethylene-acrylic acid copolymers are reported, EAA (4.6 mole % AA) and EAA (6.5), as a function of their concentration and counter ion types with their precursor, a low-density polyethylene. Various isothermal dynamic measurements in the frequency range of 0.01 to 10 rad/sec, from 120 to 200°C, were made; and partial master curves of G′ and G″ were generated. Although the melts appeared to follow the conventional superposition principle, the Cole-Cole plots were found to be unsatisfactory in describing the miscibility of such blends. The analysis based on the calculations of activation energies and other supporting measurements such as Vicat softening and DSC thermal analysis indicate that such blends are immiscible and perhaps do not have LCST. The blends failed to follow the additivity rule. The Vicat softening measurements indicated variations in the morphology of blends. The DSC studies performed on various 50/50 blends clearly demonstrated phase immiscibility.     

Influence of shearing history on the rheological properties and processability of branched polymers. IV. Capillary flow and die swell of low-density polyethylene

Low-density polyethylene (LDPE) melts show anomalous rheological behavior; their viscoelastic properties vary with their shearing histories although their molecular structural parameters do not change. Capillary flow and die swell behavior were dependent not only on the experimental conditions such as temperature or shear stress but also on the processing index (PI), which was introduced in a preceding article in order to quantify the anomalous rheological behavior of LDPE melts. In addition, it was found that the flow activation energy at constant shear stress also varied with the shearing histories. The experimental findings are discussed in terms of the rheological flow units of LDPE melts.     

Correlations of the first normal stress difference with shear stress and of the storage modulus with loss modulus for homopolymers

The effects of temperature, molecular weight and its distribution, side chain branching, and the structure of polymers on the elastic behavior of bulk homopolymers were investigated, by using logarithmic plots of first normal stress difference (N₁) against shear stress (σ₁₂) and logarithmic plots of storage modulus (G′) against loss modulus (G″). For the investigation, we have used data from the literature as well as our recent experimental results, covering a very wide range of temperature and shear stress or loss modulus. It has been found that such plots are very weakly sensitive to (or virtually independent of) temperature and to the molecular weight of high molecular weight polymers, but strongly dependent upon the molecular weight distribution and the degree of side chain branching. A theoretical interpretation of the observed correlations is presented, using molecular theories.     

Flow behavior of polypropylenes with different molecular structures in a coat‐hanger die

An experimental investigation of the flow behavior of three polypropylene melts with different molecular structures during extrusion through a coat‐hanger die is presented. Two linear and one long‐chain branched material, rheologically characterized in shear and elongation, were investigated. Using laser–Doppler velocimeter measurements of the velocity profiles across the gap height were performed at five various locations along the die. The uniformity of the velocity distribution along the die has been assessed using the maximum velocities v₀ of the corresponding velocity profiles across the gap. The velocity distribution along the die changes with throughput and temperature. Regarding the rheological properties, it was found that the power‐law index of the viscosity as a function of shear rate has a decisive influence on the uniformity of flow but that the pronounced strain hardening in elongation typical of the long‐chain branched polypropylene is not reflected by the velocity distribution along the die. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers