A rheological investigation of solid soap

Summary The rheological behaviour of solid soaps has been investigated over several orders in time and shear by means of creep experiments, measurement of stressstrain curves at constant shear rate and dynamic experiments. The modulus at small deformations is almost constant over a frequency range of 10^–3–10³ Hz; a transition from linear to non-linear behaviour has been observed at a strain of about 10^–3. The results suggest that some kind of network structure is responsible for the rheological behaviour of soap.

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Zusammenfassung Das Theologische Verhalten von Hartseifen wurde für mehrere Größenordnungen von Zeit und Schubgeschwindigkeit untersucht mittels Kriechversuche, Messung der Spannungs-Deformationskurven bei konstanter Schubgeschwindigkeit und dynamischer Experimente. Der Modul bei geringen Deformationen ist fast konstant im Frequenzbereich von 10^–3–10³ Hz; ein Übergang von linear zu nicht-linear wurde bei einer Deformation von etwa 10^–3 beobachtet. Die Ergebnisse lassen auf eine netzartige Struktur schließen, die für das Theologische Verhalten der Seife verantwortlich ist.

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The authors are indebted to Mr.C. J. Nederveen of the Central Laboratory T. N. O., Delft for the dynamic measurements, and thank Mr.D. W. Brinkman of the Unilever Research Laboratory, Vlaardingen for experimental assistance.     

A comprehensive experimental study of the rheological behaviour of HDPE.

Extensional properties of four high density polyethylenes with different molecular weights and molecular weight distributions are presented. The samples have already been well characterized in shear and non-isothermal extensional flow. The data were collected at 180 °C for elongational rates between 3 · 10^–1 and 10^–4s^–1. Some qualitative and quantitative generalizations of the results are given.     

Experience in making rheological measurements at high pressures

Summary We review the difficulties encountered in the design and operation of apparatus for rheological studies on liquids at pressures up to 900 MN m^–2 and temperatures from –30 to 120°C. Such rheological information is required in connection with elastohydrodynamic lubrication in which high pressures and shear rates are encountered.With 3 figures     

Generalized rheological model of cavitating condensed media

It is shown that development of cavitation in solid–plastic, liquid–plastic, and liquid media can be modeled using a rheologically equivalent, cavitating viscoelastoplastic body containing microcavities in the initial state. An energy inequality is derived that defines the loading conditions for a body with microcavities under which the body enters a cavitating state, i.e., the concentration of microcavities increases by more than an order of magnitude. A generalized rheological equation of state is formulated; analytical dependences of the modulus of volume elasticity, volumetric (second) viscosity, and the relaxation time of tensile stresses on the volume concentration of cavitational hollows in the model viscoelastoplastic body are derived.     

The rheological properties of saliva

Summary Saliva is a complex biological fluid that cannot be effectively studied by conventional methods such as theFerranti-Shirley Viscometer. Testing with theWeissenberg Rheogoniometer shows that saliva is viscoelastic and that the dynamic viscosity falls from 400-0.1 Poise over the frequency range 2.5×10^–3 to 10 Hertz. The calculated elastic contribution can be correlated with dry weight content.Dynamic viscosity and shear modulus are both reduced in storage, by proteolytic enzymes. The mucolytic agent Ascoxal also brings about a reduction in these parameters but by a different mechanism. A comparison of the results with those obtained previously for sputum, shows, that saliva may be a suitable model system for assessing mucolytic agentsin vitro.

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Zusammenfassung Speichel ist eine komplexe biologische Flüssigkeit, die mit konventionellen Methoden, wie z. B. demFerranti-Shirley-Viskosimeter, nicht umfassend untersucht werden kann. Studien mit einemWeissenberg-Rheogoniometer zeigen, daß Speichel viskoelastisch ist und daß seine dynamische Viskosität über einen Frequenzbereich von 2,5 · 10^–3 bis 10 Hz von 400 Poise auf 0,1 Poise fällt. Die berechnete elastische Komponente kann mit dem Trockengewichtsanteil korreliert werden.Dynamische Viskosität und Schermodul werden gemeinsam bei Lagerung von proteolytischen Enzymen reduziert. Das mukolytisch aktive Ascoxal reduziert auf andere Art ebenfalls diese Parameter. Ein Vergleich dieser Ergebnisse mit denen, die für Sputum erhalten werden, zeigt, daß Speichel ein günstiges Modellsystem ist, um mukolytisch aktive Stoffe in vitro zu testen.

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Paper presented to the British Society of Rheology Conference on Rheology in Medicine and Pharmacy, London, April 14–15, 1970.     

Modeling of blood rheological behavior in unsteady-state shearing flows

Issues of blood flow modeling under unsteady-state conditions at moderate shear rates are considered using a blood rheological model accounting both for the viscoelastic properties and the thixotropy caused by erythrocyte aggregation. The resulting shear stress versus time relations for single shear rate steps and the dependence of the complex viscosity components on the shear rate amplitude in oscillating shear flow show good qualitative correspondence with the experimental data reported in the literature.Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 6, pp. 26–30, November–December, 1995.     

An appraisal of rheological models as applied to polymer melt flow

Summary An attempt is made at giving an appraisal of some representative rheological models of both differential and integral type, using the standard rheological measurements of six polymer melts. Experimental data obtained were the steady shear viscosity and the first normal stress difference by means of aWeissenberg rheogoniometer over the range of shear rates: 10^–2 ~ 10 sec^–1, and by means of aHan slit/capillary rheometer over the range of shear rates: 10 ~ 10³ sec^–1. Also measured by means of theWeissenberg rheogoniometer were the dynamic viscosity and dynamic elastic modulus over the range of frequencies: 0.3 × 10^–2 ~ 3 × 10² sec^–1. Rheological models chosen for an appraisal are theSpriggs 4-constant model, theMeister model, and theBogue model.It is found that the capability of the three models considered is about the same in their prediction of the rheological behavior of polymer melts in simple shearing flow. It is pointed out however that, due to the ensuing mathematical complexities, the usefulness of these models is limited to the study of flow problems associated with simple flow situations. Therefore, in analysing the complex flow situations often encountered with various polymer processings, the authors suggest use of the empirical models of the power-law type for both the viscosity and normal stress functions.With 11 figures, 4 schemas and 1 table     

Peculiar features in the rheological behavior of electrorheological suspensions

Studies have been made of concentrated (up to 60%) diatomite suspensions in transformer oil, the structure and theological properties of which depend on an applied electric field. Studies have been conducted of steady-state and transient regimes of straining involving continuous and periodic shear. The structure in such suspensions is formed in the presence of an electric field of 10^–3 –10² duration. The suspensions under continuous stationary strain behave as non-Newtonian fluids with a yield stress dependent on electric intensity. Under periodic deformation conditions the test suspensions exhibit elasticity which abruptly diminishes with increasing deformation amplitude.     

Topics in thermodynamics of rheological behaviours

Survey of results recently obtained by the author about hereditary behaviour, Gibbs equation, caloric equation of state, local equilibrium, reversible accessibility, use of internal variables, behaviour classification. Toward a new and unified approach: thermodynamics in natural variables.Invited paper, presented at the First Conference of European Rheologists at Graz (Austria) April 14–16, 1982.     

A method for calculating rheological and morphological properties of constant-volume polymer blend models in inhomogeneous shear fields

We show how to formulate two-point boundary-value problems in order to compute fully-developed laminar channel and tube flow profiles for viscoelastic fluid models. The formulation is applied to Couette and pressure-driven flows separately, or a combination of both. The application of this methodology is illustrated analytically for the Upper-Convected Maxwell Model, and it is applied computationally for the Phan-Thien/Tanner and Giesekus Models. Numerical solutions exist for the last two models [J.Y. Yoo, H.C. Choi, On the steady simple shear flows of the one-mode Giesekus fluid, Rheol. Acta 28 (1989) 13–24; P.J. Oliveira, F.T. Pinho, Analytical solution for fully developed channel and pipe flow of Phan-Thien–Tanner fluids, J. Fluid Mech. 387 (1999) 271–280; M.A. Alves, F.T. Pinho, P.J. Oliveira, Study of steady pipe and channel flows of a single-mode Phan-Thien–Tanner fluid, J. Non-Newtonian Fluid Mech. 101 (2001) 55–76], allowing verification of the computational technique. Subsequently, the computational algorithm is applied to the constant-volume polymer blend models of Maffettone and Minale [P.L. Maffettone, M. Minale, Equation of change for ellipsoidal drops in viscous flow, J. Non-Newtonian Fluid Mech. 84 (1999) 105–106 (Erratum), J. Non-Newtonian Fluid Mech. 78 (1998) 227–241] and Dressler and Edwards [M. Dressler, B.J. Edwards, The influence of matrix viscoelasticity on the rheology of polymer blends, Rheol. Acta 43 (2004) 257–282; M. Dressler, B.J. Edwards, Rheology of polymer blends with matrix-phase viscoelasticity and a narrow droplet size distribution, J. Non-Newtonian Fluid Mech. 120 (2004) 189–205]. Rheological and morphological properties of the model blends are thus obtained as functions of the spatial position within the channel, applied pressure drop, and shear rate at the wall.     

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.     

A rheological measurement of three synovial fluids

Summary Using aWeissenberg Rheogoniometer, three samples of bovine synovial fluid were tested at room temperature (60 °F) at shear rates from 1.0 × 10^–2 to 9.0 × 10³ sec^–1.There is no apparent explanation for the absence (or small value outside the instruments' range) of normal stress in ankle fluid A. No information was available as to the rearing environment of the animals.It is clear, however, that synoval fluid can exhibit a high elastic component. The shear rate to which the fluid is subjected during the normal action of the joint is probably quite as high as the maximum value used in these tests.     

Stability of the boundary layer of a non-Newtonian liquid obeying a power-type rheological law

The stability of the stationary (steady-state) laminar boundary layer of a non-Newtonian liquid obeying a power-type rheological law at a semiinfinite plate situated in a longitudinal flow is analyzed. An approximate formula is derived for estimating the minimum Reynolds number at which the flow loses stability with respect to slight two-dimensional perturbations. Calculations of the point of stability loss for aqueous solutions of carboxyl methyl cellulose are presented.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 2, pp. 121–124, March–April, 1971.     

Management of applied rheological research

Summary Management of a section carrying out applied rheological research is discussed. The paper is concerned with the organisation of research, the equiping of laboratories, the training of staff, the choice of profitable projects and optimum use of available resources.

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Zusammenfassung Die auftretenden Probleme bei der Leitung einer Abteilung für die angewandte rheologische Forschung werden beschrieben. Unter anderem befaßt sich die Arbeit mit der Planung der Forschung, der Ausstattung der Laboratorien, der Einweisung der Angestellten, der Wahl der wertvollsten Projekte und der optimalen Ausnutzung der zur Verfügung stehenden Mittel.

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

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 flows of a liquid with a power-type rheological law in the presence of a constant transverse velocity component

Plane shear flows of dilatant liquids are considered in the presence of a constant transverse velocity component of the liquid; this component arises from uniform injection (or suction) at the bounding surfaces. It is shown that the presence of transverse drift in the liquid influences the rate of propagation of the leading edge of the shear waves, and this has a number of effects on the flows.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 4, pp. 15–21, July–August, 1973.     

On-line measurements of the rheological properties of fermentation broth

The paper is concerned with measurements of rheological properties of fermentation broth. An on-line rheometer, Rheohelix-1, based on the application of a helical screw impeller rotating in a draught tube has been constructed. The instrument was used for measurements of the rheological parameters of fermentation broth of Aspergillus niger in a submerged fermentation process. The results of rheological and some standard measurements have been compared and proved the applicability of the instrument.Presented at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

In-line measurement of rheological properties of polymer melts

Shear viscosity (), first normal stress difference (N ₁), and extensional viscosity ( _E ) of polymer melts measured under processing conditions are important in process modeling, quality control, and process control. A slit rheometer that could simultaneously measure , N ₁, and the planar extensional viscosity ( _p ) was designed and tested by attaching it in-line to a laboratory model single-screw extruder. A tube (circular cross-section) rheometer to measure and the uniaxial extensional viscosity ( _u ) simultaneously was also designed and tested. Two commercial grades of LDPE (low density polyethylene) with melt index values of 6 and 12 were used as test materials for the study. Exit and hole pressure methods were used to estimate N ₁, and the entrance pressure drop method using the analyses of Cogswell, Binding, and Gibson (the last analysis used with the axisymmetric case only) was used to estimate _E .The hole pressure method was considered better than the exit pressure method to estimate N ₁ (due to the greater susceptibility of the latter to experimental errors). From the hole pressure method N ₁ was obtained from 100 kPa to 500 kPa over a range of shear rates from 40 s^–1 to 700 s^–1. Among the analyses used to estimate the extensional viscosity, Cogswell's is recommended due to its simpler equations without loss of much information compared to the other analyses. The range of extension rates achieved was 1 to 30 s^–1. The combination of the hole pressure and entrance pressure drop methods in a slit rheometer is a feasible design for a process rheometer, allowing the simultaneous measurement of the shear viscosity, first normal stress difference and planar extensional viscosity under processing conditions. Similarly, combining the entrance pressure drop measurements with a tube rheometer is also feasible and convenient.     

Effect of droplet size on the rheological properties of highly-concentrated w/o emulsions

Rheological properties of highly concentrated emulsions of the water-in-oil type were studied. Water phase (concentration approximately 91%) consists of a supersaturated aqueous solution of nitrate salts; water comprises less than 20% by mass. The average size of droplets, D, in the emulsions was varied. It was found that the emulsions are non-Newtonian liquids and flow curves measured in a sweep regime of shearing have clear low-shear-rate Newtonian domain. The complete flow curves are fitted by the Cross equation. The elastic modulus is practically constant in a very wide frequency range. Hence the viscoelastic relaxation processes might be expected at times >>100 s and in the short-term side of the curve at approximately 0.01 s. The elastic modulus (measured in oscillating testing and in elastic recovery as well) is proportional to D^-2 while the Newtonian viscosity is proportional to D^–1.The time effects were observed: it was found that the emulsions behave as rheopectic materials because prolonged shearing results in an increase of viscosity in the low shear rate domain of several orders of magnitude.Presented in part at the First Annual European Rheological Conference, Guimarães, Portugal, 11–13 September 2003     

Correlation between rheological properties of polyolefin melts and solutions and their molecular structure

Conclusion In this work a method has been described to determine the weight average molecular weight and the branching of polyolefins and this by means of very simple physical measurements. The branching index can very easily be separated in a small and long chain branching index. The knowledge of the molecular weight and this branching index permits us to derive a generalised masterrheogram for all kinds of polyolefins which also explains the degree of non-Newtonian behaviour.Paper read at the Annual Meeting of the German Rheologists, Berlin-Dahlem, May 20–21, 1968.