History-dependent dimensional stability of paper

History-dependent dimensional behavior of paper has been formulated within the framework of the general linear theory of viscoelasticity and the classical lamination theory. The effect of the drying history of the papermaking process was incorporated by introducing the residual stress in the reference configuration which was taken at the final drying stage in this study. This permits us to account for complex dimensional and form changes of paper in the converting and end use processes.In order to determine the prediction performance of the computer simulation model developed, in-plane and out-of-plane dimensional responses under cyclic humidity changes were predicted on the basis of hygroviscoelastic data of paper. The simulation examples demonstrated typical irreversible dimensional responses of paper both for the in-plane dimensional change and the curvature change (curl). The computer code can easily deal with the non-uniform distribution of 1) anisotropic viscoelastic properties, 2) hygrothermal properties, and 3) moisture and temperature through the thickness.     

Rheological properties of dilute polymer solutions: An extended thermodynamic approach

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

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

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

The effect of dissolved polymers on the rheological properties of coating colours

Coating colours used for the coating of paper and board consist mainly of a mineral pigment, which is very often clay, a synthetic binder such as a styrenebutadiene latex, dispersion agents and water retention aids. The latter are often water soluble polymers. These polymers have a very strong influence on the rheological properties of the coating colours, both on the strain rate dependence of the apparent viscosity and on the viscoelasticity. The effects of two different grades of carboxymethylcellulose (CMC) and one grade of hydroxyethylcellulose (HEC), on the rheological properties at room temperature of a clay-based coating colour at pH 8, have been investigated. It is concluded that the high values of the dynamic modulus of the colours are due to interactions between the cellulose derivatives and the solid particles, i.e. mainly the clay particles. For HEC this interaction is associated with adsorption of the polymeric molecules on the clay particles. In the case of CMC, the adsorption is strongly retarded by the presence of the dispersant (a polyacrylate salt). It is suggested that the marked elasticity of the CMC-containing colour in addition to a possible polymer adsorption may be due to charge interactions and/or depletion flocculation. The effect of CMC and HEC on the water-retention properties of the colour is also discussed.     

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

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

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

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

Simple linear viscoelastic models of dilute solutions of polymer molecules and emulsion droplets

The complex viscosity of microemulsions shows relaxation processes of which the largest relaxation time is about 10^–5 s or less. This time can be attributed to relaxation of stresses in the surface of emulsion droplets pertaining to interfacial tension. Superimposed on a spherical droplet surface shape fluctuations can occur due to thermal energies. Our aim is to show the influence of thermal shape fluctuations on the complex viscosity of emulsions. The method used in the derivation has also been applied to inflexible rods to demonstrate its feasibility by showing the formal rheological equivalence of in length thermally fluctuating rods and Rouse's simple model of polymers. The emulsion results have been applied to a dilution series of a non-ionic microemulsion.     

Stress optical measurement of the third normal stress difference in polymer melts under oscillatory shear

Results are reported for the dynamic moduli,G andG, measured mechanically, and the dynamic third normal stress difference, measured optically, of a series bidisperse linear polymer melts under oscillatory shear. Nearly monodisperse hydrogenated polyisoprenes of molecular weights 53000 and 370000 were used to prepare blends with a volume fraction of long polymer, _L, of 0.10, 0.20, 0.30, 0.50, and 0.75. The results demonstrate the applicability of birefringence measurements to solve the longstanding problem of measuring the third normal stress difference in oscillatory flow. The relationship between the third normal stress difference and the shear stress observed for these entangled polymer melts is in agreement with a widely predicted constitutive relationship: the relationship between the first normal stress difference and the shear stress is that of a simple fluid, and the second normal stress difference is proportional to the first. These results demonstrate the potential use of 1,3-birefringence to measure the third normal stress difference in oscillatory flow. Further, the general constitutive equation supported by the present results may be used to determine the dynamic moduli from the measured third normal stress difference in small amplitude oscillatory shear. Directions for future research, including the use of birefringence measurements to determineN ₂/N ₁ in oscillatory shear, are described.     

Viscosity measurements with a magnetoviscometer in the zero-shear and transition region of polypropylenes

Streaming of a non-Newtonian fluid around a sphere is of special importance not only for measuring viscosities with falling spheres, but also for many problems connected with polymer processing. Using the mentioned measuring principle, attention has to be paid to the following points: The sphere is moving in a fluid (melt) of finite extension which requires the application of wall and perhaps end corrections. These are possibly not the same for Newtonian and non-Newtonian fluids. To calculate the viscosity with the help of Stokes law the steady-state velocity is necessary, and it is essential, how long it takes the sphere to reach it. To compare our results with other data, an average shear rate has to be calculated, since there is no uniform shear rate around the sphere. Velocities being very low in our experiments result in very small Reynolds numbers (Re < 10^–3), which allows the application of Stokes law practically without corrections.The experiments were performed at zero shear and in the transition region above. It turned out, that it is usually not possible to extrapolate from shear-dependent viscosity data to zero-shear viscosity.Dedicated to Prof. A. Neckel on the occasion of his 60th birthday     

Pressure driven flow of dilute polymer solutions in a channel: Analytic results for very small and for very large channels

Kinetic theory of dilute macromolecular solutions is applied to pressure driven flow in a small channel where wall- (and interfacial) layers have to be reckoned with. The complete rheology is studied. It turns out that for very small channels both the shear stress and the normal stress are an order of magnitude larger than corresponding quantities in simple shear. On the other hand, when the channel is so wide that the wall layers are very thin in comparison, agreement with results appropriate for simple shear is found. The volume flow rate-pressure difference relation is derived and compared to the prediction which utilizes the slip velocity concept. For very small channels, this concept is five orders of magnitude off, but reproduces asymptotically correct results for very large channels.     

Bimodal model of slurry viscosity with application to coal-slurries. Part 1. Theory and experiment

The rheological behavior of stable slurries is shown to be characterized by a bimodal model that represents a slurry as made up of a coarse fraction and a colloidal size fine fraction. According to the model, the two fractions behave independently of each other, and the non-Newtonian behavior of the viscosity is solely caused by the colloidal fraction, while the coarse fraction increases the viscosity level through hydrodynamic interactions. Data from experiments run with colloidal coal particles of about 2–3 µm average size dispersed in water show the viscosity of these colloidal suspensions to exhibit a highly shearrate-dependent behavior and, in the high shear limit, to match very closely the viscosity of suspensions of uniform size rigid spheres although the coal volume fraction must be determined semi-empirically. Different amounts of coarse coal particles are added to the colloidal suspension and the viscosity of the truly bimodal slurries measured as a function of shear rate. In agreement with the bimodal model, the measured shear viscosities show the coarse fraction to behave independently of the colloidal fraction and its contribution to the viscosity rise to be independent of the shear rate. It is shown that the shear rate exerted on the colloidal fraction is higher than that applied by the viscometer as a result of hydrodynamic interactions between the coarse particles, and that it is this effective higher shear rate which is necessary to apply in the correlations. For determining the coal volume fraction a relatively simple and quite accurate measurement technique is developed for determining the density and void fraction of coarse porous particles; the technique directly relates volume fraction to mass fraction.     

Bimodal model of slurry viscosity with application to coal-slurries. Part 2. High shear limit behavior

It is shown that in a truly bimodal coal-water slurry the hydrodynamic interactions between the coarse particles impose on the fine fraction a shear rate higher than that applied externally by the viscometer walls. A semi-empirical function of the coarse volume fraction is obtained for this correction factor to the applied shear rate. The derivation of this shear correction factor is based on lubrication concepts and introduces the maximum packing fraction,ø _m, at which flow can take place.ø _m is obtainable from a simple dry packing experiment. It is shown that the contribution of the coarse particles to the viscosity rise can be successfully described by a viscosity model employing the same concepts used to derive the shear correction factor. The bimodal model is applied in the high shear limit to polymodal coal slurries with a continuous particle size distribution. In the model, the contribution of the coarse particles to the viscosity rise is taken from separate viscosity measurements for the coarse coal particles, while the contribution to the viscosity of the fine coal particles is taken to be that given by the measured viscosity of colloidal suspensions of monomodal rigid spheres. It is shown that there is a ratio of coarse to fine fraction volumes in the continuous size distribution, corresponding to a specific separating particle size, for which the measured viscosities of the polymodal slurries match almost perfectly over the whole solids volume fraction range with the viscosity values obtained using the bimodal approach. The match is found to be relatively insensitive to the precise value of the separating particle size.     

Temperature and concentration dependent viscosity and gelation temperature of ABA triblock copolymer solutions

In solutions of ABA-triblock copolymers in a poor solvent for A thermoreversible gelation can occur. A three-dimensional dynamic network may form and, given the polymer and the solvent, its structure will depend on temperature and polymer mass fraction. The zero-shear rate viscosity of solutions of the triblock-copolymer polystyrene-polyisoprene-polystyrene in n-tetradecane was measured as a function of temperature and polymer mass fraction, and analyzed; the polystyrene blocks contained about 100 monomers, the polyisoprene blocks about 2000 monomers. Empirically, in the viscosity at constant mass fraction plotted versus inverse temperature, two contributions could be discerned; one contribution dominating at high and the other one dominating at low temperatures. In a comparison with theory, the contribution dominating at low temperatures was identified with the Lodge transient network viscosity; some questions remain to be answered, however. An earlier proposal for defining the gelation temperature T _gel is specified for the systems considered, and leads to a gelation curve; T _gel as a function of polymer mass fraction.Mathematical symbols {} functional dependence; e.g., f{x} means f is a function of x - p _log logarithm to the base number p; e.g., ¹⁰log is the common logarithm - exp exponential function with base number e - sin trigonometric sine function - lim limit operation - – in integral sign: Cauchy Principal Value of integral, e.g., - derivative to x - partial derivative to x Latin symbols dimensionless constant - b constant with dimension of absolute temperature - constant with dimension of absolute temperature - B dimensionless constant - c mass fraction - dimensionless constant - constant with dimension of absolute temperature - d ^* dimensionless constant - D{0} constant with dimension of absolute temperature - e base number of natural (or Naperian) logarithm - g distribution function of inverse relaxation times - G relaxation strength relaxation function - h distribution function of relaxation times reaction constant enthalpy of a molecule - H Heaviside unit step function - i complex number defined by i ² = –1 - j{0} constant with dimension of viscosity - j index number - k Boltzmann's constant - k _H Huggins' coefficient - m mass of a molecule - n number - N number - p index number - s entropy of a molecule - t time - T absolute temperature Greek symbols as index: type of polymer molecule - as index: type of polymer molecule - shear as index: type of polymer molecule - shear rate - small variation; e.g. T is a small variation in T relative deviation Dirac delta distribution as index: type of polymer molecule - difference; e.g. is a difference in chemical potential - constant with dimension of absolute temperature - (complex) viscosity - constant with dimension of viscosity - [] intrinsic viscosity number - inverse of relaxation time - chemical potential - number pi; circle circumference divided by its diameter - mass per unit volume - relaxation time shear stress - angular frequency     

The flow past a sphere in a cylindrical tube: effects of intertia,shear-thinning and elasticity

Numerical solutions are presented for the flow past a sphere placed at the centreline of a cylindrical tube for Reynolds numbers ranging from 0 to 150, using a boundary element method. Fluids are modelled by a variety of constitutive equations including the Newtonian, the Carreau and the Phan-Thien-Tanner models. The influence of inertia, shear-thinning and fluid elasticity on the flow field, drag and the pressure drop force-drag ratio is examined. Some results are compared with available experimental data.     

The motion of rodlike particles in the pressure-driven flow between two flat plates

The motion of freely suspended rodlike particles has been observed in the pressure-driven flow between the two flat plates of a Hele Shaw flow cell at low Reynolds numbers. Data are reported for rodlike particles with aspect ratios of 12.0 suspended in a Newtonian fluid for gap thickness to particle length ratios of 3, 6, and 20; and for rodlike particles with aspect ratios between 5 and 8 in a non-Newtonian fluid (79.25 wt.% water, 20.2 wt.% glycerine, and 0.55 wt.% polyacrylamide). For the Newtonian fluid, the time-dependent orientation of the particles near and far from walls was shown to be in quantitative agreement with Jeffery's theory for ellipsoids suspended in a simple shear flow if an effective aspect ratio is calculated from the experimental period of rotation. Particles aligned with the flow direction and less than a particle half-length from a wall interacted irreversibly with the wall. For the non-Newtonian fluid, the timedependent orientation far from a wall was shown to be in qualitative agreement with Leal's theory for a second-order fluid; however, particles that were aligned with the flow direction and were near walls did not rotate.