Linear and non-linear rheology of linear polydisperse polyethylene

Rheological techniques, size-exclusion chromatography, and molecular spectroscopy are the most widely used tools for describing polymer molecular structure in polyolefins. The detection of long-chain branching, and to some extent, its quantification, have been based on quantifying the deviation of polyethylene??s (PE) rheological behavior from that of a linear reference. Although metallocene-based PE has been extensively studied, linear polydisperse originating from Ziegler or Chromium-based catalysts are not often thoroughly considered, despite their high industrial importance. Within this work, we study the linear and non-linear rheology of a set of polydisperse PEs, for which the topological linearity is confirmed by GPC-MALLS measurements. Thus, we can safely quantify the effect of broad molecular weight distribution, high and ultra-high molecular weight fractions on rheological quantities and model parameters. Specifically, the zero-shear viscosity, ?? ₀ vs. M _w, relaxation spectra, phase lag vs. the complex modulus plot (van Gurp?CPalmen method) were applied and significant deviations from the ??rheologically linear?? behavior were observed, attributed only to M _w, M _z and polydispersity. Since the elongational viscosity was typical of linear PE, large-amplitude oscillatory shear and FT-Rheology were applied to quantify the non-linear rheological behavior. The latter was described by a single parameter, $Q=I_{3/1}/\gamma_0^2$ , which for linear polydisperse PE was correlated to the high molecular weight fraction and was constant over a broad range of applied Deborah numbers for the respective excitation frequencies. Since we need to correlate structural features such as broad MWD and HMW to polymer performance under processing conditions, we have to extend the analysis of linear rheological parameters, such as zero-shear viscosity, to non-linear parameters, e.g., the Q parameter quantified and used here.     

Predicting the rheology of linear with branched polyethylene blends

A series of melt blended commercial linear and branched polyethylenes are used to explore the generality of blending laws. The measured relaxation modulus G(t), and zero shear viscosity ₀ for each blend and blend fraction, have been compared with prediction for miscible blends, particularly using equations derived by Tsenoglou (1987). Plus or minus deviation between theory and measurement is dependent on the relative molecular weights of the blend components. We have found empirically that a generalised form of the blending law for G(t) and for ₀, with a floating index C, provides an improved prediction of the blend fraction data. In particular the function defining C is non-symmetrical, from which we infer the significance of branching as well as molecular weight. The optimum value of the index differs for each of our blends, in the range 1.25 to 4, the variability being accounted for by the different degrees to which branched and linear polymers relax co-operatively in the melt. Blends of two near linear polymers do not fit the floating index prediction and conform more closely, though not precisely, to the original Tsenoglou rule.     

Sharkskin instabilities and the effect of slip from gas-assisted extrusion

This paper is concerned with a polymer extrusion instability and the effect of introducing slip by means of a thin lubricating gas layer between the extrusion die wall and the flowing polymer melt. Gas-assisted extrusion (GAE) experiments were carried out using high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE) for a number of different gas injection die geometries. The stress distributions within the polymer melt were monitored during extrusion using flow birefringence. Polyflow numerical simulations were used to calculate the local stress concentrations in the melt at the die exit, as these were believed to be related to the occurrence of sharkskin. Simulations were also used to observe the effect of a full slip boundary condition as imparted by GAE. A key finding of the paper is that GAE in the parallel section of the die wall simply moved the local exit stress concentration upstream to the point of gas injection, and therefore did not reduce sharkskin. Simulations indicated that for correctly designed dies, the local surface stress concentration would be reduced. However, it was found experimentally that it was not possible to obtain a stable gas layer for this die design with upstream gas injection. A numerical investigation, involving simulations of varying levels of partial slip along the die wall, indicated an optimum level of slip where the stress concentrations were reduced. It is speculated that this is the reason that coatings such as PTFE, which impart a partial slip, can reduce sharkskin while GAE does not. The findings show that a controlled level of partial slip lowers the overall stress concentrations.     

The rheology of bread dough made from four commercial flours

 A selection of four commercial flours has been subjected to extensive rheological measurements as part of a comprehensive program of wheat improvement. The results have been used to determine which of the many types of rheological measurements provide significant discrimination between various types of modern baker's flours (including biscuit flours) and to procure data suitable for use in mathematical models describing the dough rheology. The rheological measurements undertaken include oscillatory shear at low amplitude, steady shear at a low shear rate, stress relaxation and extensional viscosity testing. Although oscillatory shear data show minor differences between these flours, the other tests show significant variations and these provide very good discrimination between the different flour types in comparison with conventional dough testing (e.g. by the extensograph). The current dough rheological measurements provide further insight into molecular structure. In the future, mathematical (constitutive) models are expected to provide a means of predicting processing and baking behaviour of bread dough. Received: 27 June 2001 Accepted: 28 August 2001     

Stretching flow instabilities at the exits of extrusion dies

As liquid leaves an extrusion die, the surface layers are rapidly stretched. Stretching flows may become unstable in two ways: by breaking, or in a ductile manner producing an uneven “necked” sample which, in continuous extrusion and drawing, is sometimes called “draw resonance”. There is a quantitative correlation between the extrusion defect known as “sharkskin” and the cohesive failure of polymer melts. By extruding under closely defined conditions, it is possible to introduce a transitory “structure” into the surface layer of the extrudate greatly enhancing its cohesive strength and eliminating this defect. A similar quantitative correlation is established between the uneven coating thickness sometimes obtained during coextrusion of a high viscosity melt on the surface of a low viscosity melt and the tensile drawing instability known as “draw resonance”. Simple criteria are established to avoid this problem in practical flow engineering.     

The effect of die exit curvature,die surface roughness and a fluoropolymer additive on sharkskin extrusion instabilities in polyethylene processing

This paper reports experimental observations and numerical simulations relating to sharkskin extrusion instabilities for two different types of polyethylene, a metallocene high-density polyethylene (HDPE) and a linear low-density polyethylene (LLDPE). Experimental results are presented for both the effect of die exit curvature and die surface roughness for slit die geometry. Matching polyflow numerical simulations are also reported and are shown to be qualitatively consistent with experimental observations. The onset of the sharkskin instability is correlated with the magnitude of the stress concentration at the die exit, and is found to be sensitive to both the melt/wall separation point for a curved exit die, and the level of partial slip at the die wall. Additional observations on the effect of a fluoropolymer additive also support the sensitivity of the sharkskin instability to partial slip at the wall.     

Inlet instabilities in the capillary flow of polyethylene melts

Inlet instabilities in the capillary flow of polyethylene melts were studied in this work. Extrudate distortions in branched polyethylenes, produced by unstable upstream flow, were found to be accompanied by pressure oscillations that do not have their origin in the slip phenomenon, but on polymer compressibility. The absence of slip was clearly evidenced in the experiments, and the differences between pressure oscillations occurring in linear and branched polymers are shown.Pressure oscillations in the capillary flow of branched polyethylenes were found to be made up of at least two components of different frequency and amplitude. These two components were identified with different bulk defects appearing in the extrudates. Information about the dynamics of vortices upstream of the contraction and extrudate distortions is obtained from the analysis of pressure oscillations.The influence of capillary entrance angle on flow curves was also investigated. From the results, it is concluded that the extensional component of the flow in the contraction is the main factor responsible for the slope change usually found in the log-log flow curves of both linear and branched polyethylenes.     

Linear and non-linear viscoelastic rheology of hybrid nanostructured materials from block copolymers with gold nanoparticles

A polystyrene-b-poly-4-vinypyridine (PS-b-P4VP) diblock copolymer is modified with a gold precursor to obtain an organic–inorganic (hybrid) block copolymer in bulk with gold nanoparticles selectively incorporated in the P4VP block. In the linear viscoelastic regime, temperature sweep tests over a series of these hybrid block copolymer systems revealed consistent shifts (ΔT) in the glass transition temperatures (both T _g\text-PS_{\rm g\text{-}PS} and T _g\text-P4VP_{\rm g\text{-}P4VP}) of the hybrid materials in comparison to the pristine polymers. Studying different volume fractions of the pyridine block, a level-off point was found for block copolymers with f _P4VP > 0.26, where the shifts in T _g\text-P4VP_{\rm g\text{-}P4VP} consistently increased up to ΔT = 25°C. By artificially increasing the volume fraction of the pyridine block, the nanoparticles reduce the transition regime determined in master curves. At higher volume fractions of the pyridine block, crossover frequencies were not detected after the entanglement regime, indicating that the material does not relax from topological constraints (entanglements and nanoparticles) into the terminal regime. Above a specific volume fraction of nanoparticles (Φ _P = 0.05), the flow behaviour of the hybrid materials becomes increasingly elastic, exhibiting wall-slip from the geometry at lower strain values in comparison to the pristine material. In the non-linear viscoelastic regime, Fourier-transformed rheology was used to analyse the raw signals from strain sweep experiments. It was clearly demonstrated the nanoparticle effect by following the second and third harmonic (I _2/1, I _3/1) of the stress response. Comparing the behaviour of the third and second harmonics provided an unambiguous fingerprint for the effect of the nanoparticles.     

A new look at extensional rheology of low-density polyethylene

The nonlinear rheology of three selected commercial low-density polyethylenes (LDPE) is measured in uniaxial extensional flow. The measurements are performed using three different devices including an extensional viscosity fixture (EVF), a homemade filament stretching rheometer (DTU-FSR) and a commercial filament stretching rheometer (VADER-1000). We show that the measurements from the EVF are limited by a maximum Hencky strain of 4, while the two filament stretching rheometers are able to probe the nonlinear behavior at larger Hencky strain values where the steady state is reached. With the capability of the filament stretching rheometers, we show that LDPEs with quite different linear viscoelastic properties can have very similar steady extensional viscosity. This points to the potential for independently controlling shear and extensional rheology in certain rate ranges.     

Effects of non-linear rheology on electrospinning process: A model study

We develop an analytical bead-spring model to investigate the role of non-linear rheology on the dynamics of electrified jets in the early stage of the electrospinning process. Qualitative arguments, parameter studies as well as numerical simulations, show that the elongation of the charged jet filament is significantly reduced in the presence of a non-zero yield stress. This may have beneficial implications for the optimal design of future electrospinning experiments.     

Determination of mechanical properties of non-linear coatings from measurements with coated beams

Coatings are applied to structural components for several various reasons, such to protect against erosion or corrosion, as thermal barrier coatings, or to increase the energy dissipation. As determining the material properties of such coatings from homogeneous specimens is often difficult, it is sometimes necessary to conduct testing on coated specimens, with the properties of the coating then to be extracted from the results of testing. A methodology for doing this is given here. While applicable to other materials, the properties of such coatings as ceramics, metallics, or compounds to be applied to rotating and static components of gas turbines are of special interest. Such materials present a special challenge as the mechanical properties have generally been found to display a strong dependence on the amplitude of cyclic strain. Application of the methodology requires careful measurement of specimen dimensions, weights, natural frequencies, and system loss factors before and after coating. From these, the storage (Young’s) modulus, the loss modulus, and the loss factor can be extracted. The methodology is demonstrated through the use of data taken on flat specimens of titanium with plasma-sprayed coatings of NiCrAlY and a titania–alumina blend ceramic, vibrating in a cantilever mode.     

Elongational rheology of polyethylene melts — temporary network constitutive laws

The uniaxial elongational properties of various polyethylenes have been evaluated using an elongational rheometer and a melt-strength apparatus. It is possible to derive the data obtained in elongation from the distribution of relaxation times obtained from oscillatory shearing measurements (linear viscoelasticity), using a Wagner constitutive equation. The effects of the molecular parameters of the samples have been studied, in particular the effect of polydispersity on the shape of the damping function.     

Analysis of flow instabilities at the natural circulation loop DANTON with regard to non-linear effects

The natural circulation loop DANTON at the Dresden University of Technology was designed to investigate the thermohydraulic properties of integrated reactor concepts with a natural circulation driven primary loop. It is not possible to reach a stable two-phase flow in the loop without passing flow instabilities. At an equilibrium of heating and cooling power the flow oscillations can exist at nearly constant frequencies and amplitudes. The oscillating mass flow signal had been investigated by various methods: (a) autocorrelation function, (b) Fast Fourier transformation, (c) estimation of a temporal Liapunov-exponent and (d) reconstruction of the system attractor in a three-dimensional phase space. The selected time-series express a non-linear behaviour, however, they are not chaotic. In comparison to the usual methods the applied analysing methods yield additional information about system frequencies, sensitiveness to disturbances and properties due to non-linear and chaotic behaviour in a natural circulation loop. Received on 17 January 2000     

Pressure effects on viscosity and flow stability of polyethylene melts during extrusion

In the present work, the effects of pressure on the viscosity and flow stability of four commercial grade polyethylenes (PEs) have been studied: linear-low-density polyethylene copolymer, high-density polyethylene, metallocene polyethylenes with short-chain branches (mPE-SCB), and metallocene polyethylenes with long chain branching (mPE-LCB). The range of shear rates considered covers both stable and unstable flow regimes. “Enhanced exit-pressure” experiments have been performed attaining pressures of the order of 500×10⁵ Pa at the die exit. The necessary experimental conditions have been clearly defined so that dissipative heating can be neglected and pressure effects isolated. The results obtained show an exponential increase in both shear and entrance-flow pressure drop with mean pressure when shear rate is fixed and as long as flow is stable. These pressure effects are described by two pressure coefficients, β_S under shear and, β_E under elongation, that are calculated using time–pressure superposition and that are independent of mean pressure and flow rate. For three out of four PE, pressure coefficient values can be considered equal under shear and under elongation. However, for the mPE-LCB, the pressure coefficient under elongation is found to be about 30% lower than under shear. Flow instabilities in the form of oscillating flows or of upstream instabilities appear at lower shear rates as mean pressure increases. Nevertheless, the critical shear stress at which they are triggered remains independent of mean pressure. Moreover, it is found that the β_S values obtained for stable flows do not differ much from the values obtained during upstream instability regimes, and differ really from pressure effects observed under oscillating flow and slip conditions.     

High-resolution measurements of two-dimensional instabilities and turbulence transition in plane mixing layers

 High-resolution two-dimensional (2D) measurements on a large plane mixing layer provide new quantitative information of its spatial and temporal evolution to turbulence. Periodic acoustic excitation with three frequencies was used to stabilize the fundamental instability of the mixing layer (roll-up) and its first and second subharmonics (vortex pairings). Phase-locked velocity measurements of the time evolution in 2D space (x, y, t) reveal accurate spatially resolved primary (2D) instabilities of the mixing layer and turbulence transition. The measurements unveil new quantitative details of the initial Kelvin–Helmholtz waves and their spatial and temporal evolution into vortex shedding and the effect of the second subharmonic on the first vortex pairing. The second-subharmonic effect hastens alternate first pairings of the rollers, with the result that pairing is completed at two downstream locations. The pairings that occur closer to the knife-edge are more organized (laminar) than those occurring farther downstream (transitional). This effect is corroborated using Taylor’s hypothesis to compute the vorticity distributions from the measured velocity field and a pseudo-spectral simulation of the temporal evolution of the mixing layer. Received: 26 March 1998/Accepted: 2 March 1999     

Predicting the onset of DNA supercoiling using a non-linear hemitropic elastic rod

Elastic rod models provide a means to interpret single molecule DNA experiments as well as predict DNA behavior under physiological conditions. Here we use an elastic rod model to predict the stability boundary (critical torque vs. applied tension) for single molecule DNA experiments in which the molecule is subjected to applied tension and twist. We discuss the shortcomings of the usual isotropic rod model. We then derive a consistent non-linear material law from the general representation for a hemitropic (chiral) rod. Finally, we present results of a standard bifurcation analysis predicting the stability boundary. We find results from the non-linear hemitropic rod to match the data closely.     

Elastic properties of polyethylene melts at high shear rates with respect to extrusion

At high shear rates a steady state of shear flow with constant shear rate, constant shear stress, and constant recoverable shear strain is observed in the short-time sandwich rheometer after some few shear units already. The melt exhibits rather high elastic shear deformations and the recovery occurs at much higher speed than it is observed in the newtonian range. The ratio of first normal stress difference and twice the shear stress, being equal to the recoverable strain in the second-order fluid limit, significantly underestimates the true elastic shear strains at high shear rates. The observed shear rate dependence of shear stress and first normal stress difference as well as of the (constrained) elastic shear strain is correctly described on the basis of a discrete relaxation time spectrum. In simple shear a stick-slip transition at the metal walls is found. Necessary for the onset of slip is a critical value of shear stress and a certain amount of elastic shear deformation or orientation of the melt.     

Predicting thermal conductivity of liquid suspensions of nanoparticles (nanofluids) based on rheology

A methodology is proposed for predicting the effective thermal conductivity of dilute suspensions of nanoparticles (nanofluids) based on rheology.The methodology uses the rheological data to infer microstructures of nanoparticles quantitatively,which is then incorporated into the conventional Hamilton-Crosser equation to predict the effective thermal conductivity of nanofluids.The methodology is experimentally validated using four types of nanofluids made of titania nanoparticles and titanate nanotubes dispersed in water and ethylene glycol.And the modified Hamilton-Crosser equation successfully predicted the effective thermal conductivity of the nanofluids.