Representation of the rheological properties of polymer melts in terms of complex fluidity

In dynamic rheological experiments melt behavior is usually expressed in terms of complex viscosity ^* () or complex modulusG ^* (). In contrast, we attempted to use the complex fluidity ^* () = 1/µ ^* () to represent this behavior. The main interest is to simplify the complex-plane diagram and to simplify the determination of fundamental parameters such as the Newtonian viscosity or the parameter of relaxation-time distribution when a Cole-Cole type distribution can be applied. ^* () complex shear viscosity - () real part of the complex viscosity - () imaginary part of the complex viscosity - G ^* () complex shear modulus - G() storage modulus in shear - G() loss modulus in shear - J ^* () complex shear compliance - J() storage compliance in shear - J() loss compliance in shear - shear strain - rate of strain - angular frequency (rad/s) - shear stress - loss angle - ^* () complex shear fluidity - () real part of the complex fluidity - () imaginary part of the complex fluidity - ₀ zero-viscosity - ₀ average relaxation time - h parameter of relaxation-time distribution     

An experimental study of exit pressures for polymer melts

A slit die apparatus is used to measure exit pressures for five different polymer melts. Viscosity data obtained from the same apparatus agree well with values obtained from a cone-and-plate rheometer or a capillary rheometer. Except for a PVC sample where thermal degradation was found to occur, the exit pressures obtained by linear extrapolation of the measured pressure profiles are all positive, and increase with increasing shear stress. The values of the first normal stress difference calculated according to the exit pressure theory are of the right order of magnitude and in some cases correlate satisfactorily with values measured in a cone-and-plate rheometer. However, the high sensitivity of the exit pressure values to the method of extrapolation and the wild scatter of exit pressure data for some materials make it difficult to use the exit pressure method as a routine procedure for accurate determination of the first normal stress difference.     

Rheological properties of dilute polymer solutions: An extended thermodynamic approach

It is shown that extended irreversible thermodynamics can be used to account for the shear rate and frequency dependences of several material functions like shear viscosity, first and second normal stress coefficients, dynamic viscosity and storage modulus. Comparison with experimental data on steady shearing and small oscillatory shearing flows is performed. A good agreement between the model and experiment is reached in a wide scale of variation of the shear rate and the frequency of oscillations. The relation between the present model which includes quadratic terms in the pressure tensor and the Giesekus model is also examined.     

Comparison of linear viscoelastic constitutive equations for non-uniform polymer melts

Linear-viscoelastic properties of polydisperse and randomly-branched polymer melts were fit with several proposed relaxation functions by non-linear regression. Three polymer systems were investigated, including 1) crosslinked polyethylenes, 2) polydisperse linear poly(dimethylsiloxane)s, and 3) Marlex polyethylenes, which are polydisperse and probably contain long-chain branching. Four relaxation functions were evaluated, including the Rouse, reptation, stretched-exponential, and stretched-exponential-power-law (SEPL) relaxation functions. The SEPL best described each series of polymers, and therefore may be a general relaxation function for non-uniform polymer melts. The flow activation energy for crosslinked polyethylene may be coupled to a breadth-of-relaxation index, indicating that a coupling between a characteristic short relaxation time and longest relaxation time, as suggested by Ngai and Plazek (J. Polym. Sci. Polym. Phys. Ed. 1985, 23:2159–2180), may hold for some non-uniform polymers.     

The role of short chain molecules for the rheology of polystyrene melts.

Atactic polystyrenes of narrow molar mass distribution with average molar masses larger than the critical molar massM _c were mixed with similar polystyrenes of molecular masses lower thanM _c . Linear viscoelastic melt properties of these binary blends were measured with a dynamic viscometer of the concentric cylinder type. One of the experimental findings is that the time-temperature shift factorsa _T are dependent on the composition of the samples. This can be understood, if free volume due to chain-ends is taken into account. A computer-fitted WLF-equation being modified in a proper way leads to the following results: At the glass-transition-temperature the fraction of free volume in polystyrene of infinite molar mass is only 0.015. At a temperature of 180 °C the mean value of the free volume at a chain end is 0.029 nm³ for the polystyrene investigated.     

Measurement of rheological and ultrasonic properties of food and synthetic polymer melts

A slit die viscometer has been used in conjunction with a co-rotating twin screw extruder to study the rheological behaviour of maize grits, potato powder and low density polyethylene, as a function of feed rate, screw speed and temperature. The shear viscosity of both maize and potato decreased with increasing feed rate. Increasing the temperature or screw speed at any given feed rate also reduced the viscosity. The ultrasonic velocity through the material has also been shown to be sensitive to the extruder operating conditions. Overall, the ultrasonic velocity decreased as screw speed and temperature increased and feed rate decreased.     

An investigation of the viscoelastic properties of molten polypropylene

Two series of polypropylene samples of different molecular weight, the first obtained directly from polymerization reactions and the second from controlled thermal degradation, were studied by dynamic testing in the melt state. Several viscoelastic parameters were determined, and correlated with weight-average molecular weightM _w . It is found that theM _w -dependence of the two series is rather different.     

Rheological and drag reduction characteristics of xanthan gum solutions

The rheological and turbulent drag reducing characteristics of commercial and purified xanthan gum solutions of concentrations 50–500 ppm have been studied with and without addition of 100 ppm NaCl. The purification by soxlet extraction of xanthan gum using 95% ethanol is effective in removing low-molecular-weight impurities from xanthan. The increased content of higher molecular-weight xanthan in purified xanthan is evident from rheological and drag reduction behavior. The addition of 100 ppm salt to dilute solutions introduces semi-flexibility in xanthan gum solution without occurrence of self-association. The change in molecular behavior in the presence of salt is evident from rheological normal-stress and turbulent drag reduction behaviors.     

Melt viscosity of linear and branched poly(butyleneisophthalate)

Linear and branched poly(butyleneisophthalate) samples were synthesized and characterized in terms of the intrinsic viscosity, the molecular weight and the melt viscosity over a wide range of shear rates at 200 °C. An exponent of about 4.6 in the equation relating ₀ to was found for linear samples; this high value is probably due to the high content of cyclic oligomers in low molecular weight samples. Both linear and branched samples exhibited Newtonian behaviour over a rather wide range of shear rates, but for any given melt-viscosity, the branched samples became shear thinning at lower shear rates than the linear ones. Our experimental data were found to fit a previously proposed correlation between the melt viscosity ratio ( _{0, b} / _{0, 1} ) and a branching index quite well.     

A differential constitutive equation for polymer melts

A modification of the Giesekus constitutive equation is derived by incorporating (approximately, via the Peterlin approximation) the finite extensibility of polymer molecules into dumbbell kinetic theory along with the anisotropic hydrodynamic drag suggested by Giesekus. The constitutive equation that is obtained retains much of the simplicity of Giesekus' constitutive equation, but it involves terms that are cubic in the stress as well as those that are quadratic. It is shown that the constitutive equation quantitatively describes the steady elongational viscosity of the IUPAC polymer melt A (including the strain softening of the melt), but it cannot describe the elongational and shear viscosities simultaneously. It is also shown that the constitutive equation satisfies the Lodge-Meissner relation for shear strains less than unity.     

Rheological characterization of highly branched poly(ethyleneterephthalate)

Linear and highly branched poly(ethyleneterephthalate) samples were synthesized and characterized in terms of intrinsic viscosity, molecular weight and melt viscosity over a wide range of shear rates at several temperatures, in the range from 265° to 295 °C. Linear samples exhibited Newtonian behavior over a wide range of shear rates, while the branched ones became shear thinning at relatively low shear rates. Our experimental data, as well as data previously reported, were found to be described by a proposed correlation between the melt viscosity ratio and a branching index. Moreover, the activation energy for melt flow was found for the highly branched samples to be a little higher than that of the linear samples.     

Generalized characteristic of polymer blend melt viscosity

A very simple reduction procedure is suggested for the blend viscosities of different polymer pairs. This procedure is based on the comparison of the blend viscosity, normalized either to the matrix or to the disperse phase viscosity, with the viscosities ratio of the initial polymers ( _m / _d ). We have obtained, for 13 different pairs containing 30% of the second component, the universal linear dependencies, mutual analysis of which allows connection of their special points with the stream morphology. The fibrillous morphology takes place in the range of _m / _d = 0, 1–5. Simultaneous, the thin skin consisting of the disperse phase polymers is formed. These results confirm the predominant role of the viscosities ratio in fibrillar composite material formation in comparison with the interphase tension phenomena.     

Linear and branched poly(butyleneisophthalate): Activation energy for melt flow

Several poly(butyleneisophthalate)s of different molecular weight, both linear and randomly branched, were synthetized by bulk polymerization and studied in the molten state with a capillary rheometer in the temperature range 190–220°C. The viscosity shift factors showed to be well correlated to temperature by an Arrhenius-type equation. The melt-flow activation energy at constant shear stressE was found to be 15±1 kcal/mol for both linear and branched samples, whereas for polydisperse poly(butyleneterephthalate) and poly(ethyleneterephthalate) it was found previously that random long-chain branching substantially increases the activation energy.An analysis of our results and of those available in the literature shows that the influence of branches on the temperature coefficient of viscosity of polymers is still a subject open to discussion.     

Rheological properties of lightly crosslinked carboxy copolymers in aqueous solutions

The rheological properties of a series of lightly crosslinked carboxy copolymers in aqueous solutions have been evaluated in steady shear and dynamic oscillatory modes. Viscosity profiles and the behavior of storage modulus are related to the chemical composition of the copolymers and their crosslinking density. A maximum in viscosity and in storage modulus which depends on the type of crosslinking agent used is explained by a combination of a chain entanglement mechanism and a closely-packed spheres model. The recovery of viscosity and storage modulus after shearing is very fast and is related to the very fast rearrangement of the microgel structure as a function of time.     

Effect of secondary zone dimensions on melt fracture manifestations of high density polyethylene

An experimental study was performed on melt fracture phenomena in extrusion of high density polyethylene. The purpose of the work was to study the sensitivity of melt fracture driven roughness to the size of recirculation zones, viz. secondary zones. The experimental apparatus consists of a right angle die and a hypodermic needle used as a capillary. The position of the needle relative to the die was adjusted using a special fixture. The roughness of the extrudate was studied as a function of penetration depth. A developed procedure provides a comparison between profile lengths of extruded strands. The computed mean, median, and mode values for roughness were presented as a function of capillary position. A qualitative analysis was conducted for the force oscillations during extrusion with a separate set of dies, equipped with the fixed capillaries of identical lengths and different depths of penetration. It was observed that the oscillatory pattern is sensitive to the sizes of the secondary zones. This qualitative observation supports the conclusions from the quantitative analysis that the roughness of the extrudate can be controlled through an adjustment of the secondary zone sizes.Partly presented at the 58th Annual Meeting of the Society of Rheology, Tulsa, Oklahoma, October 20–23, 1986     

Rheological characteristics of sewage sludge: A granuloviscous material

Problems have been experienced in the screw conveying of a centrifuge dewatered sewage sludge, at about 66% by weight water content. The rheology of the sludge was therefore tested in a viscometer in which the normal stress between the platens could be controlled. Rough platens were used to measure internal shear strengths while smooth steel platens were used to study wall slip.The sludge displayed a number of the characteristics of a granuloviscous material. It was found to possess high initial shear strength, but rapidly softened with shear to lower steady-state strengths. The initial shear strength increased with increasing normal stress, indicating that the sludge was frictional. The initial strength was lower against the smooth platen.The steady-state shear strengths were both rate and stress dependent using the rough platen, and this internal shear strength could be described by a frictional pseudoplastic equation. Using the smooth platen the material was nearly rate independent, and was best described by a Coulomb friction equation. At the higher rates the wall shear strengths were lower than the internal shear strengths.The strengths (both initial and steady-state) were characterised by a high degree of variability from sample to sample, and also showed marked hysteresis with the rough platen. They did not show any consistent variation with moisture content.In terms of screw conveying, the major conclusion is that smooth walls to the flights of the screw and barrel of the conveyor are desirable.     

Rheological properties of service weathered road bitumens

A study was carried out of the rheological properties of service weathered bitumens and their properties were compared with road performance. Bitumen from 39 test sites was recovered from the uppermost layer of stone particles covering the road surfacing and tested under dynamic and transient loading. Dynamic testing was carried out under forced sinusoidal loading. Testing under transient loading was mainly with a viscosity test conducted at 45°C, but some creep testing in compression was conducted at 0°C. From the results of dynamic testing, master curves of modulus and loss angle were constructed, spanning over ten decades in loading frequency. The hyperbolic expressions of Dickinson and Witt successfully described the frequency dependence of bitumen modulus and loss angle. The Williams, Landel and Ferry (WLF) equation, with newly derived coefficients, described the temperature dependence of the shift factor (or Newtonian viscosity) for the temperature range –10 to 60°C. Attempts were made to compare the measured transient response with that calculated from dynamic results. The result of the viscosity test conducted at 45°C as an indicator of modulus at low temperatures was assessed. Surfacing distress increased as the bitumen viscosity or modulus increased, however service performance of the bitumens was best correlated with the modulus calculated at conditions representative of traffic stressing and lowest site temperature. The changes in the rheological properties of bitumens induced by weathering is discussed.     

Transient stress responses predicted by the internal viscosity model in elongational flow

Predictions are made for the elongational-flow transient rheological properties of the dilute-solution internal viscosity (IV) model developed earlier by Bazua and Williams. Specifically, the elongational viscosity growth function _e ⁺ (t) is presented for abrupt changes in the elongational strain rate . For calculating _e ⁺, a novel treatment of the initial rotation of chain submolecules is required; such rotation occurs in response to the macroscopic step change of at t = 0. Representative are results presented for N = 100 (N = number of submolecules) and = 1000 f and 10000 f (where is the IV coefficient and f is the bead friction coefficient), using h ^* = 0 (as in the original Rouse model) for the hydrodynamic interaction. The major role of IV is to cause the following changes relative to the Rouse model: 1) abrupt stress jump at t = 0 for _e ⁺; 2) general time-retardance of response. There is no qualitative change from the Rouse-model prediction of unbounded il growth when exceeds a critical value ( ), and calculations of submolecule strains at various show that the unbounded- _e ^– behavior arises from unlimited submolecule strains when . However, the time-retardance could delay such growth beyond the timescale of most experiments and spinning processes, so that the instability might not be detected. Finally, _e ⁺ (t) and _e ( ) in the limit are presented for N = 1 and compared with exact predictions for the analogous rigid-rod molecule; close agreement lends support for the new physical approximation introduced for solving the transient dynamics for any N.     

Stability of Couette flow of liquids with power law viscosity

The stability of the Couette flow of the liquid with the power law viscosity in a wide annular gap has been investigated theoretically in this work with the aid of the method of small disturbances. The Taylor number, being a criterion of the stability, has been defined using the mean apparent viscosity value in the main flow. In the whole range of the radius ratio, R _i /R _o and the flow index, n, considered (R _i /R _o 0.5, n = 0.25–1.75 ), the critical value of the Taylor number Ta _c is an increasing function of the flow index, i.e., shear thinning has destabilizing influence on the rotational flow, and dilatancy exhibits an opposite tendency.In the wide ranges of the flow index, n > 0.5, and the radius ratio, R _i /R _o > 0.5, the wide-gap effect on the stability limit is predicted to be almost the same for non-Newtonian fluids as for Newtonian ones. The ratio on the critical Taylor numbers for non-Newtonian and Newtonian fluids: Ta _c (n) and Ta _c (n = 1) obey a generalized functional dependence: Ta _c (n)/Ta _c (n = 1) = g(n), where g(n) is a function corresponding to the solution for the narrow gap approximation.Theoretical predictions have been compared with experimental results for pseudoplastic liquids. In the range of the radius ratio R _i /R _o > 0.6 the theoretical stability limit is in good agreement with the experiments, however, for R _i /R _o < 0.6, the critical Taylor number is considerably lower than predicted by theory.