New laboratory tests to measure rheological properties of paper coatings in transient and steady-state flows

The paper describes pertinent laboratory tests to characterize the rheological properties of paper coatings with regard to blade coating over a very wide range of shear rates in both transient and steady-state shear flows. Shear rates as high as 10⁶ s^–1 can be reached by means of a gas-driven capillary rheometer. Examples for the evaluation of end effects, wall effects, and coating thixotropy are given. A stiff and fast Couette rheometer is used to determine flow curves and the shear stress overshoot in step shear rate tests. The primary normal stress difference can be measured up to 10⁴ s^–1 by means of a high shear cone-plate rheometer with piezo transducer. A correct evaluation of the measurements has to take into account inertia contributions to the normal force. First results using a sinusoidal modulation of the shear rate are presented.Paper presented at: International Symposium on Pigment Coating Structure and Rheology, Helsinki, Febr. 8–9, 1989     

Shear-induced crystallization of PB-1 up to processing-relevant shear rates

Two experimental methods to study shear-induced crystallization of poly(butene-1) (PB-1) in the high shear rate region are presented: one using a concentric cylinder rheometer and the other a capillary rheometer equipped with a cylindrical die. The crystallization onset time (t _on) is used as the parameter to monitor crystallization progress through the output signal from each device. By combining the new data with the results from a previous paper (2005) in which a plate–plate rheometer was used, onset time data covering a shear rate range from 10^-4 to 500 s^-1 at temperatures 99–107°C are obtained. In this range, a decrease in onset time spanning five decades is observed. The onset times obtained from the capillary rheometer are larger compared to those from the other two methods, which can be explained from the different type of flow. The data also confirm the procedure to construct a temperature-invariant curve, which can be extended to high shear rates for three PB-1 samples having different molecular weight distributions. The slope of the fitted curve for all three cases is −1, which suggests that a critical value is required for shear-induced crystallization. The morphology of the formed crystals (spherulitic or rod-like) depends on the molecular weight, but this does not affect the validity of the T-invariant curve. Above the melting point, it is shown that the amount of long chains influences the temperature limit where shear-induced crystallization can still take place.The paper was presented at AERC 2005, Grenoble, with the title “Shear-Induced Crystallization of Polybutene-1 Covering a Wide Shear Rate Range.”An erratum to this article can be found at     

Model analysis of nonlinear viscoelastic behaviour by use of a single integral constitutive equation: Stresses and birefringence of a polystyrene melt in intermittent shear flows

Summary A single integral constitutive equation with strain dependent and factorized memory function is applied to describe the time dependence of the shear stress, the primary normal-stress difference, and, by using the stress-optical law, also the extinction angle and flow birefringence of a polystyrene melt in intermittent shear flows. The theoretical predictions are compared with measurements. The nonlinearity of the viscoelastic behaviour which is represented by the so called damping function, is approximated by a single exponential function with one parametern. The damping constantn as well as a discrete relaxation time spectrum of the melt can be determined from the frequency dependence of the loss and storage moduli.

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Zusammenfassung Eine Zustandsgleichung vom Integraltyp mit einer deformationsabhängigen und faktorisierten Gedächtnisfunktion wird zur Beschreibung der Zeitabhängigkeit der Schubspannung, der ersten Normalspannungsdifferenz und, unter Verwendung des spannungsoptischen Gesetzes, auch des Auslöschungswinkels und der Strömungsdoppelbrechung einer Polystyrol-Schmelze bei Scherströmungen herangezogen. Die theoretischen Voraussagen werden mit Messungen verglichen. Die Nichtlinearität des viskoelastischen Verhaltens, repräsentiert durch die sogenannte Dämpfungsfunktion, wird durch eine einfache Exponentialfunktion mit nur einem Parametern angenähert. Die Dämpfungskonstanten kann, wie auch ein diskretes Relaxationszeitspektrum der Schmelze, aus der Frequenzabhängigkeit der Speicher- und Verlustmoduln bestimmt werden.

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a _i weight factor of thei-th relaxation time - a _T shift factor - C stress-optical coefficient - n flow birefringence in the shear flow plane - shear relaxation modulus - G() shear storage modulus - () shear loss modulus - H() relaxation time spectrum - h( _t,t ² ) damping function - M _w weight-average molecular weight - M _n number-average molecular weight - n damping constant - p ₁₂ shear stress - p ₁₁ –p ₂₂ primary normal stress difference - t current time - t past time - extinction angle - ( — _i) delta function - time and shear rate dependent viscosity - | ^*| absolute value of the complex viscosity - shear rate - _t,t relative shear strain between the statest andt - memory function - angular frequency - relaxation time - _i i-th relaxation time of the line spectrum - time and shear rate dependent primary normal stress coefficient - s steady-state value - t time dependence - ° linear viscoelastic behaviour With 6 figures and 1 table     

Correlation between the gel time and quiescent/quasi-quiescent crystallization onset time of poly(butene-1) as determined from rheological methods

A comparison between two quantities concerning quiescent crystallization of polymer melts, namely the quiescent crystallization onset time (t _on,q) and gel time (t _gel), is performed using rheological methods. It was found that t _gel as measured from the evolution of loss angle (tan δ) occurs slightly earlier than t _on,q, defined as the time required for the viscosity to reach twice its steady-state value. The change of viscosity with time was measured with Small Amplitude Oscillatory Shear (SAOS) method. Two alternative methods to measure t _on,q are studied: by continuous shear at a very small shear rate and by creep method. A very good agreement from all the three methods was achieved, indicating the robust nature of this quantity. Finally, the gel times for different PB-1 samples are considered. When the difference in crossover angular frequencies (ω _x ) of the samples is taken into account in performing t _gel experiments, it can be shown that the temperature dependence of t _gel for the samples are the same. However, for samples having high molecular weight t _gel measurements are problematic. In this case, t _on,q serves as an easier tool to compare the crystallization behaviour of different samples.     

Rheometry towards complex flows: Squeeze flow technique

Disk-like samples are submitted to controlled squeezing forces between parallel plates and the time-dependent sample height is measured. Isothermal tests at constant force enable the determination of viscosity functions of melts. Experiments using a constant disk radius and a constant disk volume are compared. Creep and creep recovery tests are made possible by a height-dependent control of the force. The evaluation of a pressure-dependent yield stress is demonstrated for wax powder. The squeeze flow technique is of advantage for systems with a layer structure or matrices containing long fibres or mats. In non-isothermal experiments on solidifying materials, either by crystallization or polymerization, the total deformation and the speed of solidification in processes like stamp moulding can be determined.     

Orientation effects and rheology of short glass fiber-reinforced thermoplastics

The rheology of polyolefines, polyamide 6, and polystyrene-acrylonitrile filled with glass fibers of different concentrations and aspect ratios have been investigated in simple shear flow, capillary rheometry, and uniaxial elongation. A comparison is made with unfilled and glass bead-filled melts. Fiber orientation was investigated by X-ray microradiography.Steady-state viscosities are obtained on fibers aligned parallel to the direction of flow. Entrance pressure losses, the shape of the viscosity function, and the appearance of a yield stress are depending on the fiber aspect ratio. The temperature dependence of the viscosity function is not significantly different from that of the unfilled melt.Transient shear stresses were measured on samples of different initial orientations of the fibers. The change of fiber orientation during shear flow gives rise to a pronounced overshoot of shear stress and normal stress difference. Elastic strains in shear are increased by the fibers but elastic elongational strains are reduced. Mechanisms are proposed to explain the experimental observations.Dedicated to Dr. D. Heinze on the occasion of his 60th birthday.     

Diffusion pore imaging with generalized temporal gradient profiles

In porous material research, one main interest of nuclear magnetic resonance diffusion (NMR) experiments is the determination of the shape of pores. While it has been a longstanding question if this is in principle achievable, it has been shown recently that it is indeed possible to perform NMR-based diffusion pore imaging. In this work we present a generalization of these previous results. We show that the specific temporal gradient profiles that were used so far are not unique as more general temporal diffusion gradient profiles may be used. These temporal gradient profiles may consist of any number of “short” gradient pulses, which fulfil the short-gradient approximation. Additionally, “long” gradient pulses of small amplitude may be present, which can be used to fulfil the rephasing condition for the complete profile. Some exceptions exist. For example, classical q-space gradients consisting of two short gradient pulses of opposite sign cannot be used as the phase information is lost due to the temporal antisymmetry of this profile.     

Combined slit and plate–plate magnetorheometry of a magnetorheological fluid (MRF) and parameterization using the Casson model

We describe a magneto-slit die of 0.34 mm height and 4.25 mm width attached to a commercial piston capillary rheometer, enabling the measurement of apparent flow curves of a magnetorheological fluid (MRF) in the high shear rate regime (apparent shear rates 276 up to 20,700 s^???1, magnetic flux density up to 300 mT). The pressure gradient in the magnetized slit is measured via two pressure holes. While the flux density versus coil current without MRF could directly be measured by means of a Hall probe, the flux density with MRF was investigated by finite element simulations using Maxwell® 2D. The true shear stress versus shear rate is obtained by means of the Weissenberg–Rabinowitsch correction. The slit die results are compared to plate–plate measurements performed in a shear rate regime of 0.46 up to 210 s^???1. It is shown that the Casson model yields a pertinent fit of the true shear stress versus shear rate data from plate–plate geometry. Finally, a joint fit of the slit and plate–plate data covering a shear rate range of 1 up to 50,000 s^???1 is presented, again using the Casson model. The parameterization of the MRF behavior over the full shear rate regime investigated is of relevance for the design of MR devices, like, e.g., automotive dampers. In the Appendix, we demonstrate the drawbacks of the Bingham model in describing the same data. We also show the parameterization of the flow curves by applying the Herschel–Bulkley model.     

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.     

Asymmetrical hippocampal connectivity in mesial temporal lobe epilepsy: evidence from resting state fMRI

Background

Recent studies have shown that the human right-hemispheric auditory cortex is particularly sensitive to reduction in sound quality, with an increase in distortion resulting in an amplification of the auditory N1m response measured in the magnetoencephalography (MEG). Here, we examined whether this sensitivity is specific to the processing of acoustic properties of speech or whether it can be observed also in the processing of sounds with a simple spectral structure. We degraded speech stimuli (vowel /a/), complex non-speech stimuli (a composite of five sinusoidals), and sinusoidal tones by decreasing the amplitude resolution of the signal waveform. The amplitude resolution was impoverished by reducing the number of bits to represent the signal samples. Auditory evoked magnetic fields (AEFs) were measured in the left and right hemisphere of sixteen healthy subjects.

Results

We found that the AEF amplitudes increased significantly with stimulus distortion for all stimulus types, which indicates that the right-hemispheric N1m sensitivity is not related exclusively to degradation of acoustic properties of speech. In addition, the P1m and P2m responses were amplified with increasing distortion similarly in both hemispheres. The AEF latencies were not systematically affected by the distortion.

Conclusions

We propose that the increased activity of AEFs reflects cortical processing of acoustic properties common to both speech and non-speech stimuli. More specifically, the enhancement is most likely caused by spectral changes brought about by the decrease of amplitude resolution, in particular the introduction of periodic, signal-dependent distortion to the original sound. Converging evidence suggests that the observed AEF amplification could reflect cortical sensitivity to periodic sounds.