Showing papers in "Rheologica Acta in 1998"

Fourier-transform rheology

Abstract: Oscillatory shear of polymeric liquids in the non-linear regime generates higher harmonic contributions in the shear stress response. These non-linear contributions are analyzed in Fourier space with respect to the different frequencies and intensities. Simulated and experimental Fourier rheology spectra for atactic poly(propylene) melts are shown.

Influence of molecular structure on rheological properties of polyethylenes

Abstract: Elastic properties of melts of a long-chain branched low density polyethylene (LDPE) with a broad molecular mass distribution and a short-chain branched linear low-density polyethylene (LLDPE) with a more narrow molecular mass distribution were investigated by creep recovery measurements in shear. The results obtained by means of a magnetic bearing torsional creep apparatus in the linear-viscoelastic region, showed that the steady state recoverable compliance of the LLDPE is greater by a factor of two than that of the LDPE. In the short-time region up to 1000 s, however, the time-dependent recoverable compliance of the LDPE is higher than that of the LLDPE. The retardation times for the LLDPE are considerably longer than for the LDPE. For the LDPE the temperature dependence of the entanglement transition is consistent with that of the terminal zone of the creep compliance. The activation energy of 58 kJ/mole lies in the typical range for long-chain branched polyethylenes. In the case of the LLDPE the creep compliances can be shifted to give a mastercurve with an activation energy of 34 kJ/mole, whereas the recoverable compliances do not follow the time-temperature superposition principle. The molecular characterization using TREF showed that the LLDPE has a bimodal branching structure. In addition to a short-chain branched component, a low percentage of a linear constituent with high molecular mass was found. It is postulated that this linear component forms a dispersed phase in the matrix of the short-chain branched constituent. The resulting interfacial tension could be the reason for the long retardation times, the high steady state recoverable compliance and the fact that the time-temperature superposition principle is not fulfilled in the case of the LLDPE investigated.

Study on the constitutive equation with fractional derivative for the viscoelastic fluids – Modified Jeffreys model and its application

Abstract: Based on the classic linear viscoelastic Jeffreys model, a modified Jeffreys model is suggested. The corresponding five-parameter equation with fractional derivatives of different orders of the stress and rate of strain is stated and the characteristic material functions of the linear viscoelasticity theory, such as the dynamic moduli, are derived. The comparison between the measured dynamic moduli of Sesbania gel and xanthan gum and the theoretical predictions of the proposed phenomenological model shows an excellent agreement.

The role of viscoelasticity in polymer sintering

Abstract: An experimental study for polymer sintering has been carried out using pairs of powder particles. Although in many cases Newtonian sintering models successfully describe polymer sintering, they predict a faster coalescence rate than that observed with the polypropylene copolymer resins used in this study, indicating that factors other than the surface tension and the viscosity play a role in polymer sintering. Observations of coalescence under the microscope and rotational molding experiments suggest that melt elasticity slows down the process. Based on these findings, a mathematical model describing the complete polymer sintering process for viscoelastic fluids has been developed. The approach was similar to that of Frenkel (1945) and the convected Maxwell constitutive equations were used together with the quasi-steady state approximation. The proposed viscoelastic sintering model is capable of predicting the sintering rate slowdown observed in this study.

Compliance of actin filament networks measured by particle-tracking microrheology and diffusing wave spectroscopy

Abstract: We monitor the time-dependent shear compliance of a solution of semi-flexible polymers, using diffusing wave spectroscopy (DWS) and video-enhanced single-particle-tracking (SPT) microrheology. These two techniques use the small thermally excited motion of probing microspheres to interrogate the local properties of polymer solutions. The solutions consist of networks of actin filaments which are long semi-flexible polymers. We establish a relationship between the mean square displacement (MSD) of microspheres imbedded in the solution and the time-dependent creep compliance of the solution, <Δr 2(t)>=(k B T/πa)J(t). Here, J(t) is the creep compliance, <Δr 2(t)> is the mean-square displacement, and a is the radius of the microsphere chosen to be larger than the mesh size of the polymer network. DWS allows us to measure mean square displacements with microsecond temporal resolution and Angstrom spatial resolution. At short times, the mean square displacement of a 0.96μm diameter sphere in a concentrated actin solution displays sub-diffusion. <Δr 2(t)>∝t , with a characteristic exponent =0.78±0.05, which reflects the finite rigidity of actin. At long times, the MSD reaches a plateau, with a magnitude that decreases with concentration. The creep compliance is shown to be a weak function of polymer concentration and scales as J p ∝c –1.2±0.3. This exponent is correctly described by a recent model describing the viscoelasticity of semi-flexible polymer solutions. The DWS and video-enhanced SPT measurements of the compliance plateau agree quantitatively with compliance measured independently using classical mechanical rheometry for a viscous oil and for a solution of flexible polymers. This paper extends the use of DWS and single-particle-tracking to probe the local mechanical properties of polymer networks, shows for the first time the proportionality between mean square displacement and local creep compliance, and therefore presents a new, direct way to extract the viscoelastic properties of polymer systems and complex fluids.

An experimental investigation of negative wakes behind spheres settling in a shear-thinning viscoelastic fluid

Abstract: We present detailed ex- perimental results examining "neg- ative wakes" behind spheres settling along the centerline of a tube con- taining a viscoelastic aqueous poly- acrylamide solution. Negative wakes are found for all Deborah numbers (2.43 ≤ De(c ˙ ) ≤ 8.75) and sphere-to- tube aspect ratios (0.060 ≤ a/R≤ 0.396) examined. The wake structures are investigated using laser-Doppler velocimetry (LDV) to examine the centerline fluid velocity around the sphere and digital particle image velocimetry (DPIV) for full-field velocity profiles. For a fixed aspect

Viscoelasticity of low molecular weight polymers and the transition to the entangled regime

Abstract: The viscoelasticity of unentangled polystyrene melts has been investigated in terms of terminals parameters: zero-shear viscosity, steady-state compliance and relaxation spectrum. The Rouse model applies well for molecular weights lower than the average molecular weight between entanglements, providing that one takes into account the proper variations of the radius of gyration. Moreover, local motions at the scale of Kuhn segments have to be considered in order to describe correctly the relaxation modes intermediate between the terminal zone and the glassy plateau. On the other hand, reptation models are commonly used for describing the entangled regime. We propose an expression of the shear modulus which accounts not only for the terminal modes (reptation, tube length fluctuations and tube renewal), but also for the relaxation modes responsible for the plateau zone and the transition of the glassy plateau. A crossover region between the unentangled and untangled regimes is located around . When the molecular weight increases, a shift transfer of Rouse modes towards reptation modes occurs. That leads to a continuity of the expression of the shear modulus over the entire range of molecular weights.

High-frequency viscoelasticity of crosslinked actin filament networks measured by diffusing wave spectroscopy

Abstract: We study the short-time relaxation dynamics of crosslinked and uncrosslinked networks of semi-flexible polymers using diffusing wave spectroscopy (DWS). The networks consist of concentrated solutions of actin filaments, crosslinked with increasing amounts of α-actinin. Actin filaments (F-actin) are long semi-flexible polymers with a contour length 1–100μm and a persistence length of 5–15μm; α-actinin is a small 200kDa homodimer with two actin-binding sites. Using the large bandwidth of DWS, we measure the mean-square-displacement of 0.96μm diameter microspheres imbedded in the polymer network, from which we extract the frequency-dependent viscoelastic moduli via a generalized Langevin equation. DWS measurements yield, in a single measurement, viscoelastic moduli at frequencies up to 105Hz, almost three decades higher in frequency than probed by conventional mechanical rheology. Our measurements show that the magnitude of the small-frequency plateau modulus of F-actin is greatly enhanced in the presence of α-actinin, and that the frequency dependence of the viscoelastic moduli is much stronger at intermediate frequencies. However, the frequency-dependence of loss and storage moduli become similar for both crosslinked and uncrosslinked networks at large frequencies, G′(ω)∝G′′(ω)∝ω0.75±0.08. This high-frequency behavior is due to the small-amplitude, large-frequency lateral fluctuations of actin filaments between entanglements.

Using instrumental inertia in controlled stress rheometry

Abstract: We describe a new method for characterizing the non-linear behavior of complex fluids at both small and large deformations. For creep measurements, we use the coupling between the instrumental inertia and the material‘s elasticity to follow the rheological behavior of a solution of iota carrageenan both above and below the yield stress. It is shown that this coupling selectively excites one particular frequency of the relaxation spectrum. An analytical calculation is used to quantify the non-linear behavior near the yield stress. The “free“ oscillations observed during the first few seconds allow us to choose the most appropriate mechanical model. Comparison with experiment shows that even above the yield stress, a linear model can still give independently reliable information about the changes in each element of the mechanical model. A comparison of free and forced oscillations in controlled stress rheometry shows both experimentally and theoretically the conditions under which the use of free oscillations is advantageous.

Influence of molecular structure on rheological properties of polyethylenes: I. Creep recovery measurements in shear

Abstract: Elastic properties of melts of a long-chain branched low density polyethylene (LDPE) with a broad molecular mass distribution and a short-chain branched linear low-density polyethylene (LLDPE) with a more narrow molecular mass distribution were investigated by creep recovery measurements in shear. The results obtained by means of a magnetic bearing torsional creep apparatus in the linear-viscoelastic region, showed that the steady state recoverable compliance of the LLDPE is greater by a factor of two than that of the LDPE. In the short-time region up to 1000 s, however, the time-dependent recoverable compliance of the LDPE is higher than that of the LLDPE. The retardation times for the LLDPE are considerably longer than for the LDPE. For the LDPE the temperature dependence of the entanglement transition is consistent with that of the terminal zone of the creep compliance. The activation energy of 58 kJ/mole lies in the typical range for long-chain branched polyethylenes. In the case of the LLDPE the creep compliances can be shifted to give a mastercurve with an activation energy of 34 kJ/mole, whereas the recoverable compliances do not follow the time-temperature superposition principle. The molecular characterization using TREF showed that the LLDPE has a bimodal branching structure. In addition to a short-chain branched component, a low percentage of a linear constituent with high molecular mass was found. It is postulated that this linear component forms a dispersed phase in the matrix of the short-chain branched constituent. The resulting interfacial tension could be the reason for the long retardation times, the high steady state recover: able compliance and the fact that the time-temperature superposition principle is not fulfilled in the case of the LLDPE investigated.

Visual observation of development of sharkskin melt fracture in polybutadiene extrusion

Abstract: We studied the sharkskin melt fracture phenomena of polybutadiene (PBD), which exhibits similar flow properties and instabilities to linear low density polyethylene (LLDPE). The advantages of using PBD are that it exhibits larger distortions and slower development due to its high viscosity. By using a video camera with close-up lenses focused at the die exit, we observed the development of sharkskin in profile. It was shown that the sharkskin melt fracture develops with the cohesive failure at the die exit due to a peeling of surface layers as described by Howell and Benbow (1962). Oddly enough, this mechanism is similar to that proposed by Ovaici et al. (1998) for the extrusion of chocolate. A soap solution coating around the die exit to induce a slippery interface eliminated the sharkskin fracture, similar in the effect of fluoro-elastomer coating with LLDPE. Based on our visual observations, we qualitatively modeled the sharkskin fracture by modifying Cogswell‘s (1977) idea on exit stretching at the die exit and the force balance of Ovaici et al. on the ring formation of the chocolate extrusion.

Effect of variations in counterion to surfactant ratio on rheology and microstructures of drag reducing cationic surfactant systems

Abstract: Rheology, drag reduction and cryo-TEM experiments were performed on Arquad 16–50/NaSal and Ethoquad O/12/NaSal surfactant systems at different counterion-to-surfactant ratios and at constant low surfactant concentrations, 5 mM, appropriate for drag reduction. The molar ratio of counterion-to-surface was varied from 0.6 to 2.5. All the surfactant systems described here are viscoelastic and drag reducing. The viscoelasticity and drag reducing effectiveness increase with increase in counterion/surfactant ratio. Network are present in the solutions with high ratio, and they are viscoelastic. However, shear is needed to induce network formation for solutions at low ratio. Cryo-TEM images confirm the existence of thread-like micelles which form entanglement networks, and show that the micellar network becomes denser with increasing counterion/surfactant ratio in one surfactant series. Both increase in the counterion/surfactant ratio and increase in the shear rate result in shorter relaxation times.

On pipe diameter effects in surfactant drag-reducing pipe flows

Abstract: Remarkable power saving in a fluid transport system is possible if the surfactant drag reduction technology is used Application of surfactant drag reduction to district heating and cooling systems has been investigated in the past The establishment of the scale-up law in drag-reducing pipe flows is one of the most important problems in this application Main purpose of this study is aimed to develop a reliable scale-up law in surfactant drag-reducing flows As the basic data of surfactant solutions, both non-Newtonian viscosity and viscoelasticity were experimentally determined A turbulent eddy diffusivity model based on the Maxwell model was employed to estimate the drag reduction of surfactant solutions The predictions by the turbulence model developed in this study with proper rheological characteristics of surfactant solutions has resulted in a reliable estimation of the pipe diameter effect in surfactant drag-reducing flows over the pipe diameter range from 11 to 150mm

Rheological analysis of highly concentrated w/o emulsions

Abstract: A series of highly concentrated lipophilic cosmetic emulsions were analysed, in order to determine their rheological and textural properties, as a function of their microstructure. The originality of this study lies in the methodology used, especially the shear-stress scanning analysis. The results of a very powerful and comprehensive dynamic rheological analysis suggest the existence of two critical volume fraction values: besides the “close-packed” value φ c , a “slack-packed” value φ0, close to 0.60 could be demonstrated. It has been shown that the close-packed structure is stable under shear; in constrast, the slack-packed configuration, defined as φ0<φ<φ c is unstable under shear. A comparison with theoretical models, especially that of Princen, showed good agreement and allowed the close-packed value φ c to be defined more precisely as 0.67. The gap between 0.67 and 0.74 is probably indicative of a highly polydisperse distribution, as confirmed by microscopic analysis. Flow experiments confirmed the validity of Princen‘s model.

Nonlinear rheology and flow-induced structure in a concentrated spherical silica suspension

Abstract: In hard-sphere suspensions of solid particles, the stress has the Brownian (thermodynamic) and hydrodynamic components σB and σH, the former reflecting the anisotropy of the particle distribution while the latter being determined by the hydrodynamic interaction between the particles. These two components exhibit nonlinearities under steady shear flow with different mechanisms. The nonlinearity of σB results from the particle distribution insensitive to the shear rate, while σH becomes nonlinear due to flowinduced clustering of the particles. These structural origins of the nonlinearities were confirmed from flow-SANS experiments.

Fast flow behavior of highly entangled monodisperse polymers

Abstract: When a stick-slip transition of an extremely large magnitude occurs in capillary flow of a highly entangled melt, a significant flow can be generated in the barrel. At a constant piston pressure, this barrel flow reduces the actual pressure available at the die entry that produces the capillary flow in the die. Experiments on linear monodisperse polybutadienes (PBd) show that a significant correction due to this barrel flow must be made to obtain a reliable characterization of the interfacial stick-slip transition. The interfacial flow discontinuity transition exhibits hysteresis behavior similar to that of linear polyethylenes. When a large pressure loss occurs in the barrel due to a massive stick-slip transition, the die wall stress may drop below the hysteresis loop, causing a new self-regulated flow oscillation to take place at a constant applied pressure.

Experimental and conceptual problems in the rheological characterization of wheat flour doughs

Abstract: Wheat flour dough is an industrially important material and a better understanding of its rheological behavior could have long ranging impact on the agricultural and the food processing industries. However, rheological characterization of dough is proving to be difficult due to a range of testing issues and anomalies in flow behavior. In a cone-and-plate rheometer wheat flour doughs “roll-out” of the gap before steady state viscosities can be established, as discussed by Bloksma and Nieman (1975). However, the mirror image of the transient viscosity-time plot obtained using a cone-and-plate viscometer has been used to obtain an estimate of steady shear viscosity behavior (Gleissle, 1975). To check this transient methodology for doughs, a second method, in addition to cone-and-plate transient flow, for determination of the shear viscosity, was needed. For this, capillary extrusion was chosen. Both a piston-driven and pressure driven capillary rheometer were employed. End corrections were determined to provide information on both the shear viscosity and, following Binding (1988), the extensional viscosity of the doughs. There are few data available on end corrections for doughs, though published data by Kieffer indicate that the corrections are unexpectedly very high. In this present work it was found that the end correction experiments were very difficult and imprecise in part due to the time-dependent nature of the doughs and difficulties in preparing replicate batches required to compare dies of differing L/R values. Further it was unexpectedly found that the samples, though prepared by normal mixing procedures to the “optimum” level, were so heterogeneous that large fluctuations in the pressure at constant output rate (in the piston-driven rheometer) and in output rate at constant pressure (in the pressure-driven instrument) were observed. These fluctuations could be eliminated by overmixing of the doughs, but overmixed doughs are of little practical interest. Although the problems encountered in this work were significant, it was encouraging that even these preliminary studies indicate that rheological measurements are effective in differentiating between spring and winter wheats. Defining a constitutive model for dough rheology still remains a major challenge, as results from one type of testing do not corroborate the findings from a different type of testing.

Linear and non linear rheology of a wormlike micellar system in presence of sodium tosylate

Abstract: In this experimental work, we investigate the influence of an organic counterion, sodium tosylate, on the rheological properties of an aqueous solution of CTAB at the concentration of 0.05M. With this system we can clearly see shear thickening for small salt concentrations C s and only shear thinning behavior at higher C s characterized by a linear evolution of η=f(γ) in a log-log representation. In these evolutions it is only in a very small domain of concentrations of the salt (near C s =0.035M) that we can observe a nearly constant plateau of the shear stress against shear rate. The values of σ0 (characterizing the stress plateau), G 0 (the plateau modulus) and τR (the relaxation time) obtained by dynamical rheological measurements, allow to compare experimental results obtained to predicted values of the theory of Cates corresponding to the occurrence of shear induced banding structures.

Sensitivity analysis of the Bagley correction to shear and extensional rheology

Abstract: The excess pressure losses due to end effects in the capillary flow of two linear low-density polyethylene resins (LLDPE) were studied. These losses were first determined experimentally by using two methods: 1) by extrapolating experimental data of pressure drop versus length-to-radius ratios (L/R) to zero capillary length and 2) by means of using orifice dies (L/R≅0). Both methods resulted in practically the same end corrections. Numerical simulation was also used to model this important aspect of experimental rheology. The constitutive equations used in the simulations are a multimode K-BKZ equation, a multimode Phan-Thien/Tanner, and finally a purely viscous Carreau equation. It was found that the numerical predictions agreed qualitatively but underestimated the experimental data for the various geometries used to determine the end effects. Furthermore, it is demonstrated that the entrance pressure loss is also insensitive to extensional rheology, while it depends more strongly on the shear rheology. This finding raises doubts as to the usefulness of end pressure (known also as Bagley correction) as a method of determining the extensional viscosity of polymer melts at high rates.

Structure and rheology of heat-set gels of globular proteins

Abstract: The structure and the rheology of systems resulting from heating at 80°C isoelectric solutions of bovine serum albumin (BSA) in the concentration range 10–200mg/ml were studied. Small-angle neutron scattering measurements view the systems as being formed of large aggregates of micrometric size with a close packed arrangement of denatured protein molecules. No indication of a fractal structure stands out. The viscoelastic behaviour is linear up to about 5% strain, except in the BSA concentration range 30–90mg/ml where the linearity limit is below 1% strain. The viscoelastic response was analysed in the linear domain, or as close as possible to it, by combining the results of dynamic and creep recovery measurements. The dependence on concentration of the steady state viscosity, of the steady state compliance, and of the average retardation time shows a marked change around a concentration C0∼50mg/ml, corresponding probably to a percolation threshold.

Rheological behavior of cellulose/monohydrate of n-methylmorpholine n-oxide solutions. Part 1: Liquid state

Abstract: Steady-state and dynamic experiments have been performed on solutions containing cellulose dissolved in monohydrate of N-methylmorpholine N-oxide (NMMO). The dependence of the zero-shear viscosity η0, and of the terminal relaxation time τc, on concentration, average degree of polymerization (DP) and temperature are discussed. The behavior of this semi-rigid, polymolecular polymer in solution differs from that of flexible monodisperse ones. The slope of the plot of log (η0) versus, on the one hand, log (c) at fixed molecular weight (DP) = 600, and, on the other hand, log (DP) at fixed concentration (c = 5% w/w) are equal to 4.6 and 5 respectively, instead of 3.4 in the concentrated region. Experimental data for the shear modulus were fitted using the classical Doi-Edwards equation with a log normal distribution of relaxation time. This distribution is compared to the distribution of DP.

Wall slip of mayonnaises in viscometers

Abstract: The shear flow of mayonnaise is generally characterized by an apparent yield stress, shear thinning in steady flow, stress overshoots upon inception of flow and other time-dependent effects. These observations are usually understood to be the result of structural rearrangement within the material. Additionally and separately, the possibility that emulsions may exhibit apparent wall slip on a microscopic scale at a solid-liquid boundary has been reported by some researchers. Thus, observed rheological behavior is likely to be the result of the interplay between these two phenomena. In the present work, it is demonstrated that when measurements are sought to be made on mayonnaise using rotational viscometers visible wall slip occurs, rendering such instruments ineffective for the purpose of making viscosity measurements even at shear rates as low as 10–3s–1. The factors that influence the onset and extent of slip are investigated with the help of parallel plate viscometers, and it is concluded that the observed “yielding” of mayonnaise is actually an artifact of the onset of macroscopic slip. Slip effects are also found in capillary flow but are ameliorated with increasing shear rate. To circumvent these problems, it is proposed that extensional viscometry be employed for determining the flow behavior of mayonnaises.

Microstructure constitutive equation for discotic nematic liquid crystalline materials

Abstract: Four different microstructure constitutive equations (CEs) for discotic nematic liquid crystals based on Doi‘s modified nematodynamics theory are formulated. Their dynamic and steady state responses under simple shear flows are computed and analyzed in terms of the tensor order parameter Q, the orientation director triad (n, m, l), and the uniaxial S and biaxial P alignments. A unit sphere description of the director triad is used to characterize and classify the various predicted stable orientation states, and to discuss and analyze their multi-stabilities as a function of dimensionles shear rate. Various attractors, steady and periodic, are also identified and their stability is discussed in detail for all the CEs. A validation procedure based on the predicted microstructural response along with bifurcation diagrams of the individual CE and representative experimental observations as well as theoretical results is implemented, and used to select the most appropriate CE. The selected CE predicts, under shear, the simultaneous presence of stable in-plane (steady and periodic) states and out-of-plane steady state, and the classical transition among the in-plane periodic and steady states with increasing shear rate. The excellent performance of the selected CE in shear flows strongly suggests that it is a reliable contribution towards the formulation of a process model for mesophase pitch spinning.

The relevance of entry flow measurements for the estimation of extensional viscosity of polymer melts

Abstract: The extensional viscosity of some flexible chain polymers and a thermotropic liquid crystalline polymer was measured in uniaxial extensional flow at constant extension rate. Power law functions were found for the dependence of the extensional viscosity at constant accumulated strain on strain rate. The stress growth curves were compared with measurements in axisymmetric entry flow, where both elongation and shear occur. The comparison showed that the values of the extensional viscosity calculated from the measurements in the entry flow correspond to the ones calculated from the viscosity growth measured in uniaxial elongation and averaged over extensional strain equal to what is accumulated on the fluid as it flows from the barrel into the capillary.

Fluid inertia in large amplitude oscillatory shear

Abstract: Homogeneous shearing is required in sliding plate flow experiments with one plate fixed and the other oscillating. However, when fluid inertia becomes significant, the velocity gradient and the stress will not be uniform. MacDonald et al. (1969) and Schrag (1977) investigated this effect for a linear viscoelastic fluid. However, linear viscoelasticity does not describe the behavior of melts in large amplitude oscillatory shear (LAOS). Jeyaseelan et al. (1993) have shown that the Berkeley kinetic network model does accurately describe the LAOS behavior of polymer melts. In this work, the Berkeley model is solved for LAOS in sliding plate flow with fluid inertia, by numerical integration of spatially discretized forms of the governing equations. Nonlinear viscoelasticity is predicted to aggravate the effects of fluid inertia in LAOS and experiments confirm this. Specifically, fluid inertia amplifies the first harmonic and produces no even harmonics. Operating limits are presented graphically for minimizing inertial effects in LAOS experiments.

Molecular orientation, “Region I” shear thinning and the cholesteric phase in aqueous hydroxypropylcellulose under shear

Abstract: Birefringence and flow visualization are used to study molecular orientation, texture, and the cholesteric nature of a 60 wt% aqueous hydroxypropylcellulose solution at low to moderate shear rates. There is a sharp transition in behavior at a shear rate near 0.5 s–1. Below this rate, the sample shows “Region I” shear thinning, takes on a frosted appearance, has low flow-induced orientation, and exhibits faint optical diffraction characteristic of cholesteric liquid crystals. Upon flow cessation from low rates, a highly organized cholesteric phase showing bright optical diffraction is re-formed in around 5min. Above the critical shear rate, the sample exhibits much higher orientation and a striped texture which is readily apparent with or without polarized light illumination. Upon flow cessation, molecular orientation decays significantly for up to around 400 s; however, the striped textures established during shear persist. It is suggested that persistence of the cholesteric phase under shear is responsible for the occurrence of Region I shear thinning at low shear rates in this solution.

Comparison of different shear rheometers with regard to creep and creep recovery measurements

Abstract: The performance of two shear rheometers with regard to creep and creep recovery measurements is investigated. The first one is a commercially available stress-controlled rheometer that uses an air bearing, and the second one is a magnetic bearing torsional creep apparatus that was built at the Institute of Polymer Materials in Erlangen. The creep and creep recovery measurements were performed in the linear-viscoelastic regime of two polyethylene melts at a temperature of 150°C. The creep compliances of the polyethylenes measured by both rheometers are in excellent agreement. The recoverable compliances of both polyethylene melts, however, have lower values in the case of the commercial rheometer than in the case of the magnetic bearing rheometer. The experimental parameters of creep recovery experiments and the features of the two bearings that are responsible for the different results of the two rheometers are discussed. The influence of the level of the applied shear stress on the short time behavior is investigated as well as the residual torque of the bearings which influences the long time region of the recoverable compliances. Also addressed are the influence of the momentum of inertia of the rotor and the bearing friction which is different for the two rheometers.

Steady shear viscosity of short fibre suspensions in thermoplastics

Abstract: The rheological behaviour of a polyethylene, two polyamides and a silicone oil filled with different fibre contents are studied in capillary rheometry. The viscosity increase induced by the fibres is important for the silicone oil, and negligible for the polyethylene. The polyamide is intermediate. The same classification stands for the pressure loss in the convergent channel upstream from the capillary. A constitutive equation based on a cell model which takes into account the shear-thinning behaviour of the matrix is built. The predictions of the model are in correct agreement with the measurements.

Determination of the molecular weight distribution of linear polymers by inversion of a blending law on complex viscosities

Abstract: The method presented in this paper allows to calculate the molecular weight distribution (MWD) of linear homopolymer melts from the complex shear modulus data measured in a wide frequency domain. An empirical blending law on complex viscosities is first developed; as a consequence, the variations of the storage and loss modulus as a function of MWD are presented. This simulation demonstrates also the role of the shape of the MWD itself, and shows that one should not postulate a priori the shape of the MWD. An efficient numerical approach based on a Tikhonov regularization method with constraint is used to solve this ill-posed problem; the MWD is hence derived without any assumption on its shape. This method is first applied on simulated data to prove its numerical efficiency. Then the inversion method is applied on complex moduli data of various commercial polymers (polypropylene, polyethylene and polystyrene) and on an artificial mixture of polystyrene that have been presented in the literature. For amorphous polymers, the coupling of the terminal relaxation domains with the transition region at higher frequency leads to errors in the low molecular weight tail: one way to solve this problem is to cut off the experimental data at the high frequencies. This general method needs only a few physical parameters, namely the scaling law for the Newtonian viscosity η0=f(M w ) and the plateau modulus G N 0, and leads to reasonable results with respect to the simplicity of the viscoelastic model used.

Dynamic shear and compressional behavior of polydimethylsiloxanes : Ultrasonic and low frequency characterization

Abstract: The dynamic rheological properties of a series of entangled polydimethylsiloxanes are investigated. Rheometrical shear measurements are first reported for three different molecular weight samples, together with ultrasonic tests, thus allowing to obtain dynamic shear master curves over ten decades. Winter‘s model for slightly polydisperse polymers is used and works well in this case. This provides an example of the applicability of this model. The propagation of longitudinal waves in the MHz range for the same PDMSs is studied next. The results are analyzed and combined with static measurements of the compressibility. They indicate that different relaxation mechanisms have to be considered in shear and compression, and that the ratio between volume and shear viscosity is frequency dependent, with a preponderance for shear effects at higher frequencies. Shear and compressional relaxational mechanisms are also well separated. Moreover, it is verified that the shear and compressional moduli are independent of the molecular weight in the transition region, above a certain frequency. This frequency corresponds to a wavelength comparable to the distance between entanglements, in the case of shear waves.