A low frequency torsional rheometer

Summary An instrument has been developed for measuring the viscoelastic behaviour of polymer melts at low frequencies, in the range 10^–3 to 50 Hz. The sample is contained between a cone and a fixed plate, or between parallel plates. The moving member is driven in torsional oscillation through a torsion wire. The amplitude of the resulting oscillation is compared in amplitude and phase with the driven end of the torsion wire. The amplitudes are measured digitally using optical diffraction gratings, and either an oscilloscope or a high-speed ultra-violet recorder is used to determine the phase angle between the two signals. The moving member is supported on an air bearing, which provides a very low friction support with a high degree of positional control thus giving a well defined sample geometry. The torsion wire is driven using a vibrator with a d.c. drive amplifier fed from a very low frequency oscillator. The sample temperature is controlled to better than 0.01 °C, with temperature gradients across the sample of a similar order of magnitude. The temperature range of the instrument is from –50 °C to +200 °C.The angular resolution of the measuring system is 3 × 10^–5 radius, so that an accuracy of better than ±1% in the amplitude measurements can be obtained with the amplitude of shear in the sample kept sufficiently low that a linear stress-strain relation is maintained.With 3 figures     

The crossover between linear and non-linear mechanical behaviour in polymer solutions as detected by Fourier-transform rheology

 The application of oscillatory shear strain leads, in the non-linear regime, to the appearance of higher harmonic contributions in the shear stress response. These contributions can be analyzed as spectra in Fourier space, with respect to different frequencies, amplitudes and phase angles. In this article, we present an application of this new characterization method to a solution of the linear homopolymer polyisobutylene. The degree of non-linear response during oscillatory shear is quantified using the normalized intensity of the third harmonic contribution. We were able to show experimentally on polyisobutylene that there is an immediate onset of the non-linear response even for very small shear strain amplitudes. Received: 21 June 1999/Accepted: 21 August 1999     

A Rheotens-based setup for the constant strain rate uniaxial extension of uncured elastomers

A novel experimental setup for the uniaxial extension of uncured elastomers is presented, and room temperature experiments at constant Hencky strain rate are performed by means of a commercial Rheotens tensile tester originally designed for the determination of the melt strength of polymer melts. Successful results are obtained for materials related to many aspects of the elastomers production, namely, gum elastomers and carbon black compounds. Stress growth experiments are reported for filled and unfilled high-cis-polybutadiene, and the extensional behavior is related to the carbon black dispersion. Although originally thought as an experimental tool for polymer melts, the proposed Rheotens setup can also perform constant strain rate tensile testing on thermoplastic rubbers. Stress-strain experiments are performed on a microphase separated polystyrene-b-poly(ethylene butylene)-b-polystyrene (SEBS) copolymer and related blends with polypropylene, showing the effect of a constant deformation rate on the network response. Relaxation experiments after cessation of extensional flow are also reported for the investigated materials. With respect to commonly used tensile testing procedures for elastomers at constant elongation rate and time decreasing strain rate, a complete and accurate investigation of the extensional behavior of many uncured elastomers can be carried out with the additional advantage of using a reduced amount of material.     

On the propagation of elastic waves through composite media

Summary With the aid of an ultrasonic pulse technique, the propagation of elastic waves (longitudinal as well as transverse) through polyurethane rubbers filled with different amounts of sodium chloride particles was studied. The velocity of both longitudinal and transverse waves was found to increase with filler content. From the measured wave velocities, the effective modulus for longitudinal waves,L, bulk modulus,K, and shear modulus,G, were calculated according to the relations for a homogeneous isotropic material. All three moduli appear to be monotonously increasing functions of the filler content over the whole experimentally accessible temperature range (–70 °C to + 70 °C forL andK;}-70 °C to about –20 °C forG) and they, moreover, reflect the glassrubber transition of the binder.Poisson's ratio,, was found to decrease with increasing filler content and show a rise at the high temperature side of the experimentally accessible temperature range (about –20 °C) as a result of the approach of the glass-rubber transition.In addition to the velocities, the attenuation of both longitudinal and transverse waves was measured in the temperature ranges mentioned. It was found that in the hard region tan _L as well as tan _G are independent of the filler content within the accuracy of the measurements. In the rubbery region, however, tan _L, increases with increasing filler content.Finally, the experimental data are compared with a simple macroscopic theory on the elastic properties of composite media.     

High-temperature pressure-shear plate impact experiments using pure tungsten carbide impactors

The pressure-shear plate impact experiment has been modified to test materials at high temperatures (up to 700°C). Together with the high strain rates characteristic of this experiment (10⁶ s^–1), the high-temperature capability allows the shearing resistance of materials to be measured under conditions unattainable with other testing equipment. The compressive and shear responses of pure tungsten carbide at different temperatures are presented, as well as the results of one test on OFHC copper at a temperature of 691°C and a shear strain rate of 1.4×10⁶ s^–1.     

Mechanisch-dynamische Untersuchungen an Phenol-Formaldehyd-Preßmassen in Abhängigkeit vom Füllstoffgehalt

Zusammenfassung Mit Hilfe des Torsionsschwingungsversuchs wurde an Phenolharzpreßmassen der Einfluß verschiedener Zusatzstoffe (Glaskugeln unterschiedlicher Korngröße, Gesteinsmehl, Zeolithe) auf den Schubmodul und die mechanische Dämpfung im Temperaturbereich von –180°C bis +240°C untersucht.Mit steigendem Füllstoffanteil wurde eine Erhöhung der Speicher- und Verlustmodulwerte festgestellt, wobei das mechanisch-dynamische Verhalten der gefüllten Proben auch bei höherem Gehalt an Füllstoff deutlich vom viskoelastischen Verhalten des Grundwerkstoffs bestimmt wird.Die Untersuchungen haben gezeigt, daß neben der Konzentration, der Art und der Gestalt der Zusatzstoffe auch die Größe der Füllstoffteilchen und deren Haftung mit der Harzmatrix die wichtigsten Einflußgrößen für die mechanischen Eigenschaften von Phenolharz-Verbundwerkstoffen darstellen.Ein Vergleich der erzielten Meßergebnisse mit den theoretischen Voraussagen über die Schubmodulerhöhung von Teilchenverbundsystemen ergab eine recht befriedigende Übereinstimmung. Wesentlich erscheint, daß bei allen derartigen Verbundsystemen die Korngröße und die Korngrößenverteilung im Bereich um 10^–3 mm bis 10^–4 mm liegen sollte.

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Summary The effect of various inorganic fillers (glass beads of different particle size range, barium sulfate powder, zeolites) on the dynamic-mechanical properties at about 1 Hz of phenol-formaldehyde thermosets have been determined over a range of temperatures from –180°C to +240°C. Increasing the filler content of the specimens increased the storage and loss moduli. In all cases the mechanical behaviour of the composites is dominated by the viscoelastic properties of the resin matrix. The experimental results are compared with theoretical predictions for shear moduli vs. filler content, as known from publications.

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Vorgetragen auf der Jahrestagung der Deutschen Rheologen in Berlin vom 28.–30. April 1975.

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Mit 19 Abbildungen und 1 Tabelle     

Effect of sepiolite (magnesium silicate) on the dynamic properties of butadiene-styrene rubber vulcanizates

The influence of the new mineral filler Pansil, a natural magnesium silicate (sepiolite), on the properties of SBR vulcanizates is studied and compared with other synthetic silicas and a carbon black N-330 (HAF) at various filler concentrations.A series of dynamic tests was carried out in traction-compression and shear at various frequencies, temperatures and strain amplitudes.The so-called Payne effect was observed as the strain amplitude was increased. The variation of tan with the dynamic deformation was more pronounced in the Pansil filled compounds. The needle-shaped nature and the large internal surface (mesopores) of the new mineral filler may give rise to a high adsorption of rubber chain segments with the subsequent increase in heat generation. However, when the Pansil was treated with a silane coupling agent (Silane A-189) the heat generation decreased.By applying the time-temperature superposition principle, master curves for the storage modulus and loss factor tan were derived over a wide frequency range.     

Coupling between flow and diffusion at polymer/polymer interfaces: large amplitude oscillatory shear experiments

 Coupling between flow and diffusion at symmetric polymer/polymer interfaces has been investigated. Polystyrene/polystyrene sandwich assemblies were subjected to large-amplitude oscillatory shear (LAOS) using a sliding-plate rheometer (SPR) and the stress was monitored as a function of time. The results were treated using a new model combining Wagner's model with the theory of Doi and Edwards. The model explicitly expresses the influence of the strain and stress amplitudes frequency and time on the self-diffusion process. The apparent self-diffusion coefficient was found to increase with welding time, in agreement with our previous results obtained using small-amplitude oscillatory shear measurements. However, it was found in the present case that the self-diffusion coefficient depends strongly on the strain and stress amplitudes and frequency, and its steady state value was found to be larger than that determined from small-amplitude oscillatory shear measurements. It appears that the large strain oscillatory shear field continuously increases the density of chain ends at the interface and thus increases the flux of mass transport. Received: 30 January 2001 Accepted: 12 June 2001     

Smectic rheology

We have studied the oscillatory shear response of three thermotropic smectic-A liquid crystalline materials with no external aligning field (other than the necessary presence of rheometer plates). Two are polymers (one main-chain and one side-chain) and the other is a small molecule smectic. All three exhibit the classical linear response to oscillatory shear characteristic of a viscoelastic solid at sufficiently small strain amplitudes and frequencies. However, for strain amplitudes exceeding a small critical value, these materials exhibit a strongly nonlinear response to strain, which is characterized in detail. While the low-strain moduli and the critical strain of the three smectics are considerably different, the nonlinear response has some universal character which is presumably related to the low energy for the formation of defects in smectic liquid crystals.     

Modelling of frequency- and amplitude-dependent material properties of filler-reinforced rubber

Filler-reinforced elastomers are extremely complicated materials with pronounced deformation and temperature history-dependent material properties. In the current paper, the dynamic material behaviour is investigated and modelled. To this end, a carbon black-filled rubber compound is loaded with harmonic deformations under different frequencies and amplitudes and the stationary stress response is evaluated in terms of the storage and the loss modulus or, equivalently, in terms of the dynamic modulus and the loss angle. In this essay, detailed experimental investigations of the dynamic material properties of carbon black-filled elastomers are provided and a new three-dimensional constitutive approach of finite nonlinear viscoelasticity to represent the observed material behaviour is developed.     

A torsional creep instrument and a torsional pendulum,both with accurate temperature control

Summary This paper describes a torsional pendulum and a torsional creep instrument. With the pendulum shear moduli between 10⁶ and 10¹⁰ N/m² can be measured at frequencies from 0.1 to 20 Hz. The creep instrument is suitable for measurement of shear compliances lower than 10^–7 m²/N in the time range from 1 to 10⁵ seconds. In both instruments, specimens are kept at the right temperature by blowing heated nitrogen gas through a surrounding thermostatic chamber. The signal of a platinum resistance thermometer, provided in each chamber, automatically controls the heating of the gas. Temperatures from –180 to +300 °C can be maintained with an absolute accuracy of ±1 °C and a long term stability of ±0.05 °C. It is shown that one cannot directly compare one and the same shear property, calculated from the shear modulus as measured with the pendulum as well as from the shear compliance as measured with the creep instrument. This is due to differences in the temperature of one thermostatic chamber over against the other. Finally, the paper presents a method to reduce these differences to ±0.1 °C, although the absolute accuracy of temperature control remains ±1 °C.

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Zusammenfassung Die Arbeit beschreibt ein Torsionspendel und eine Torsions-Kriechapparatur. Mit dem Pendel können Schermoduli zwischen 10⁶ und 10¹⁰ N/m² bei Frequenzen zwischen 0,1 und 20 °C gemessen werden. Die Kriechapparatur ist geeignet für die Messung von Scherkomplianzen kleiner als 10^–7 m²/N in Zeiten zwischen 1 bis 10⁵ sec. In beiden Geräten werden die Proben durch das Einblasen von erhitztem Stickstoff durch eine umgebende thermostatische Kammer bei der richtigen Temperatur gehalten. Die Anzeige eines Platin-Widerstandsthermometers, das in jeder Kammer angebracht ist, kontrolliert automatisch die Erwärmung des Gases. Es können Temperaturen zwischen –180 und +300 °C mit einer absoluten Genauigkeit von ±1 °C und einer Langzeitstabilität von ±0,05 °C eingestellt werden. Es wird gezeigt, daß ein direkter Vergleich der gleichen Schereigenschaft, die zum einen aus dem mit dem Pendel gemessenen Schermodul und zum anderen aus der mit der Kriechapparatur ermittelten Kriechkomplianz errechnet wird, nicht möglich ist. Das beruht auf Temperaturdifferenzen zwischen den thermostatisierten Kammern.Abschließend stellt die Arbeit eine Methode vor, um diese Differenzen auf ±0,1 °C zu senken. Die absolute Genauigkeit der Temperaturkontrolle bleibt bei ±1 °C.

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Paper presented at the Conference on Experimental Rheology, University of Bradford, April 17–19, 1968.     

Rheological properties of carbon black-filled blends of liquid-crystalline copolyester with thermoplastic polysulfone

Rheological properties of a two-phase polymeric blend containing LCCPE of poly(ethylene terephthalate) and p-hydroxybenzoic acid and thermoplastic polysulfone with varying concentrations of polymeric components and particulate filler have been studied. The theological behavior of such blends at different temperatures is governed by variation of the degree of ordering of LC-CPE macromolecules associated with the phase transition in the CPE at 260°C. Experimental results are discussed on the basis of concepts of compatibility of polymeric components in the melt or, if the system is incompatible, of the degree of interphase interaction between the components, as well as the impact of the filler and of the shear straining conditions on structurization in the system and compatibility. The filler exerts a compatibilizing effect on blend components, while the shear stress encourages the phase separation in the system. An extremal variation of viscosity of the LC-CPE/carbon black, silica and talk blends with the filler concentration on both at the flow in a uniform shear stress field and at the capillary flow has been found. Normalization of the filler concentration with respect to its specific surface yields a unified concentration dependence of the relative viscosity of LC-CPE filled with solid particles of various natures and specific surfaces.     

The nonlinear viscoelastic response of carbon black-filled natural rubbers

Three series of tensile relaxation tests are performed on natural rubber filled with various amounts of carbon black. The elongation ratio varies in the range from λ=2.0 to 3.5. Constitutive equations are derived for the nonlinear viscoelastic behavior of filled elastomers. Applying a homogenization method, we model a particle-reinforced rubber as a transient network of macromolecules bridged by junctions (physical and chemical cross-links, entanglements and filler clusters). The network is assumed to be strongly heterogeneous at the meso-level: it consists of passive regions, where rearrangement of chains is prevented by surrounding macromolecules and filler particles, and active domains, where active chains separate from temporary nodes and dangling chains merge with the network as they are thermally agitated. The rate of rearrangement obeys the Eyring equation, where different active meso-domains are characterized by different activation energies. Stress–strain relations for a particle-reinforced elastomer are derived by using the laws of thermodynamics. Adjustable parameters in the constitutive equations are found by fitting experimental data. It is demonstrated that the filler content strongly affects the rearrangement process: the attempt rate for separation of strands from temporary nodes increases with elongation ratio at low fractions of carbon black (below the percolation threshold) and decreases with λ at high concentrations of filler.     

Nonlinear viscoelastic properties of MR fluids under large-amplitude-oscillatory-shear

Nonlinear viscoelastic properties of the MR fluid, MRF-132LD, under large-amplitude oscillatory shear were investigated. This was accomplished by carrying out the experiments under the amplitude sweep mode and the frequency sweep mode, using a rheometer with parallel-plate geometry. Investigations under the influence of various magnetic field strength and temperatures were also conducted. MR fluids behave as nonlinear viscoelastic or viscoplastic materials when they are subjected to large-amplitude shear, where the storage modulus decreases rapidly with increasing strain amplitude. Hence, MR fluid behaviour ranges from predominantly elastic at small strain amplitudes to viscous at high strain amplitudes. Large-amplitude oscillatory shear measurements with frequency sweep mode reveal that the storage modulus is independent of oscillation frequency and approaches plateau values at low frequencies. With increasing frequency, the storage modulus shows a decreasing trend before increasing again. This trend may be explained by micro-structural variation. In addition, the storage modulus increases gradually with increasing field strength but it shows a slightly decreasing trend with temperature.     

Constitutive modelling of the amplitude and frequency dependency of filled elastomers utilizing a modified Boundary Surface Model

A phenomenological uniaxial model is derived for implementation in the time domain, which captures the amplitude and frequency dependency of filled elastomers. Motivated by the experimental observation that the frequency dependency is stronger for smaller strain amplitudes than for large ones, a novel material model is presented. It utilizes a split of deformation between a generalized Maxwell chain in series with a bounding surface plasticity model with a vanishing elastic region. Many attempts to capture the behaviour of filled elastomers are found in the literature, which often utilize an additive split between an elastic and a history dependent element, in parallel. Even though some models capture the storage and loss modulus during sinusoidal excitations, they often fail to do so for more complex load histories. Simulations with the derived model are compared to measurements in simple shear on a compound of carbon black filled natural rubber used in driveline isolators in the heavy truck industry. The storage and loss modulus from simulations agree very well with measurements, using only 7 material parameters to capture 2 decades of strain (0.5–50% shear strain) and frequency (0.2–20 Hz). More importantly, with material parameters extracted from the measured storage and loss modulus, measurements of a dual sine excitation are well replicated. This enables realistic operating conditions to be simulated early in the development process, before an actual prototype is available for testing, since the loads in real life operating conditions frequently are a combination of many harmonics.     

Normal stress measurements

An apparatus designed to measure the dynamic viscoelastic response of polymer melts is described. Dynamic elasticity (G) and viscosity () can be measured over a frequency range 10^–2-10^–3 Hz and at temperatures up to 350 °C. The sample under test is held in a cone and plate assembly. A small strain is introduced by driving the plate with a variable speed synchronous motor and off-centre cam at low frequencies and by an electromagnetic vibrator at high frequencies. The amplitudes of the cone and plate are detected using the optical lever principle and photocell strips. The phase difference between the cone and plate is measured from a recorder trace at low frequencies and by direct reading on a meter at high frequencies.Results are described of measurements on silicone fluids, and on commercial grades of polyethylene with different molecular weight distributions and degrees of branching.A discussion is given of the correlation between the dynamic viscosity measurements and those taken under steady-flow conditions.Paper presented at the Conference on Experimental Rheology, University of Bradford, April 17–19, 1968. — Original paper published in J. Sci. Instruments Series 2,1, 1102–1112 (1968).     

Viscoelastic plastic rheological model for particle filled polymer melts

A viscoelastic plastic model for suspension of small particles in polymer melts has been developed. In this model, the total stress is assumed to be the sum of stress in the polymer matrix and the filler network. A nonlinear viscoelastic model along with a yield criterion were used to represent the stresses in the polymer matrix and the filler network, respectively. The yield function is defined in terms of differential equations with an internal parameter. The internal parameter models the evolution of structure changes during floc rupture and restoration. The theoretical results were obtained for steady and oscillatory shear flow and compared with experimental data for particle filled thermoplastic melt. The experimental data included the steady state shear strress over a wide range of shear rates, the transient stress in a start up shear flow, stress relaxation after cessation of a steady state shear flow, the step shear and the oscillatory shear flow at various amplitudes.     

A linear viscoelastic model for solid polyethylene

Stress relaxation tests have been carried out on a blue, pipe grade PE 80 medium density polyethylene (BP Chemicals), to provide thermo-viscoelastic rheology for use in calculating thermal stresses in pipe production. Stresses up to 4 MPa were used, with strains up to about 2%, in tests at temperatures from 23° to 90°C. Within this range a linear viscoelastic model was applicable, provided the initial ramp strain rate was less than 7×10^–5 s^–1. The stress relaxation data was fitted directly by a model incorporating an elastic response to volumetric strains, and a generalised linear solid model, consisting of two Maxwell elements and a purely elastic element in parallel, for deviatoric strains. Arrhenius type temperature dependence of relaxation times and shear moduli is found, and within experimental accuracy the temperature dependence of all these model parameters is the same. As a consequence, and provided that the duration of the strain ramp is sufficiently short relative to relaxation times, the model leads to time-temperature superposition of the relaxation moduli, using the same shift factor on both the response magnitude and time axes.     

Viscoelastic melt rheology and time–temperature superposition of polycarbonate–multi-walled carbon nanotube nanocomposites

This work investigates the linear and non-linear viscoelastic melt rheology of four grades of polycarbonate melt compounded with 3 wt% Nanocyl NC7000 multi-walled carbon nanotubes and of the matching matrix polymers. Amplitude sweeps reveal an earlier onset of non-linearity and a strain overshoot in the nanocomposites. Mastercurves are constructed from isothermal frequency sweeps using vertical and horizontal shifting. Although all nanocomposites exhibit a second plateau at ～10⁵ Pa, the relaxation times estimated from the peak in loss tangent are not statistically different from those of pure melts estimated from cross-over frequencies: all relaxation timescales scale with molar mass in the same way, evidence that the relaxation of the polymer network is the dominant mechanism in both filled and unfilled materials. Non-linear rheology is also measured in large amplitude oscillatory shear. A comparison of the responses from frequency and amplitude sweep experiments reveals the importance of strain and temperature history on the response of such nanocomposites.     

Peculiarities of rheological behavior of filled polymer melts in uniaxial stretching

The peculiarities of theological behavior of filled polymer melts in uniaxial extension in a wide range of strain rates (from 2× 10^–5 to 1 × 10^–1 s^–1) have been studied. Linear polyethylene and 1,4-polybutadiene containing up to 21.5 vol.% of carbon black, silica, calcium carbonate or glass fibers were used. It has been found that the transition from uniform to nonunion stretching due to the neck formation is typical of all specimen compositions, when they approach steady-state straining. Depending on the structure and rheological characteristics of the compositions general conditions for this transition have been established. The general regularities for varying the rheological characteristics of filled polymers in the course of their uniform stretching have been recognized. These regularities depend on the molecular characteristics of the polymer matrix and the presence in the compositions of the structural framework of high disperse filler or the network formed by the entangled fibers. Using polyethylene compositions it has been shown that the introduction of small amounts of disperse or fibrous fillers can give rise to acceleration of the relaxation process in filled polymers.