Fractal-time stochastic processes and dynamic functions of polymeric systems

Dynamic material functions of polymeric systems are calculated via a defect-diffusion model. The random motion of defects is modelled by a fractaltime stochastic process. It is shown that the dynamic functions of polymeric solutions can be approximated by the defect-diffusion process of the mixed type. The relaxation modulus of Kohlrausch type is obtained for a fractal-time defect-diffusion process, and it is shown that this modulus is capable of portraying the dynamic behavior of typical viscoelastic solutions.The Fourier transforms of the Kohlrausch function are calculated to obtain and. A three-parameter model for and is compared with the previous calculations. Experimental measurements for five polymer solutions are compared with model predictions. D rate of deformation tensor - G(t) mechanical relaxation modulus - H relaxation spectrum - I(t) flux of defects - P _n (s) probability of finding a walker ats aftern-steps - P generating function ofP _n (s) - s(t) fraction of surviving defects - , () gamma function (incomplete) - ₀ zero shear viscosity - ^* () complex viscosity - frequency - t _n n-th moment - F[] Fourier transform - f ^* (u) Laplace transform off(t) - , components of ^* - G _f, _f ^* fractional model - G ₃, ₃ ^* three parameter model - complex conjugate ofz - material time derivative ofD     

Apparent thickening behavior of dilute polystyrene solutions in extensional flows

An experimental investigation was undertaken to study the apparent thickening behavior of dilute polystyrene solutions in extensional flow. Among the parameters investigated were molecular weight, molecular weight distribution, concentration, thermodynamic solvent quality, and solvent viscosity. Apparent relative viscosity was measured as a function of wall shear rate for solutions flowing from a reservoir through a 0.1 mm I.D. tube. As increased, slight shear thinning behavior was observed up until a critical wall shear rate was exceeded, whereupon either a large increase in or small-scale thickening was observed depending on the particular solution under study. As molecular weight or concentration increased, decreased and, the jump in above , increased. increased as thermodynamic solvent quality improved. These results have been interpreted in terms of the polymer chains undergoing a coil-stretch transition at . The observation of a drop-off in at high (above ) was shown to be associated with inertial effects and not with chain fracture due to high extensional rates.     

Rheological models for gypsum plaster pastes

Shear stress and shear rate data obtained for gypsum plaster pastes were correlated by means of different rheological models. The pastes were prepared from a commercial calcium sulfate hemihydrate at various water/plaster ratios ranging from 100/150 to 100/190. The tests were performed at 25°C using a rotating coaxial cylinder viscosimeter. The measurements were accomplished by applying a step-wise decreasing shear rate sequence. Discrimination among the models was made: (1) on the basis of the fitting goodness; (2) by checking the physical meaning of the calculated parameters; (3) on the basis of the stability of the parameters and of their prediction capacity beyond the limits of the experimental data. In the light of above, the Casson model seemed to be most effective for application to gypsum plaster pastes. K Consistency - n Power-law index - N Number of experimental data - P Number of parameters - Shear rate (s^–1) - ₀ Viscosity (Pa · s) - _d Dispersing medium viscosity (Pa · s) - _p Plastic viscosity (Pa · s) - Viscosity at zero shear rate (Pa · s) - Viscosity at infinite shear rate (Pa · s) - [] Intrinsic viscosity - ² Variance - Shear stress (Pa) - ₀ Yield stress (Pa) - Solid volume fraction - _m Maximum solid volume fraction     

Neck propagation as a shock wave

Neck propagation in the stretching of elastic solid filaments having a yield point was analyzed using the space one-dimensional thin filament governing equations developed previously by the authors and other researchers. Constitutive model for the filament was assumed to be expressible as engineering tensile stress(X) (tensile force) given as a function of elongational strain with the(X) curve having a yield point maxima followed by a minima and a breaking point greater than the yield point maxima. Also incorporated into the model is the hysteresis of irreversible plastic deformation. When inertia is taken into consideration, the thin filament equations were found to reduce to the nonlinear wave equation ² (X)/ ² =C ₁ ² X/ ² where is Lagrangean space coordinate, is time, andC ₁ is inertia coefficient. The above nonlinear wave equation yields a solutionX(, ) having a stepwise discontinuity inX which propagates along the axis. The zero speed limit of the step wave solution was found to describe the above neck propagation occurring in solid filaments. Furthermore, it was recognized that the nonlinear wave equation was known for many years to also govern the plastic shock wave which propagates axially within a metal rod subjected to a very strong impact on its end. The one-dimensional atmospheric shock wave also was known to be governed by the nonlinear wave equation upon making certain simplifying assumptions. The above and other evidences lead to the conclusion that neck propagation occurring in the extension of solid filament obeying the above(X) function can be formally described as a shock wave.     

Melt viscosity of linear and branched poly(butyleneisophthalate)

Linear and branched poly(butyleneisophthalate) samples were synthesized and characterized in terms of the intrinsic viscosity, the molecular weight and the melt viscosity over a wide range of shear rates at 200 °C. An exponent of about 4.6 in the equation relating ₀ to was found for linear samples; this high value is probably due to the high content of cyclic oligomers in low molecular weight samples. Both linear and branched samples exhibited Newtonian behaviour over a rather wide range of shear rates, but for any given melt-viscosity, the branched samples became shear thinning at lower shear rates than the linear ones. Our experimental data were found to fit a previously proposed correlation between the melt viscosity ratio ( _{0, b} / _{0, 1} ) and a branching index quite well.     

Generalized characteristic of polymer blend melt viscosity

A very simple reduction procedure is suggested for the blend viscosities of different polymer pairs. This procedure is based on the comparison of the blend viscosity, normalized either to the matrix or to the disperse phase viscosity, with the viscosities ratio of the initial polymers ( _m / _d ). We have obtained, for 13 different pairs containing 30% of the second component, the universal linear dependencies, mutual analysis of which allows connection of their special points with the stream morphology. The fibrillous morphology takes place in the range of _m / _d = 0, 1–5. Simultaneous, the thin skin consisting of the disperse phase polymers is formed. These results confirm the predominant role of the viscosities ratio in fibrillar composite material formation in comparison with the interphase tension phenomena.     

Slit die viscometry at shear rates up to 5 × 106s−1: An analytical correction for small viscous heating errors

If the viscosity can be expressed in the form = (T)f(), the walls are at a constant temperatureT ₀, and the extra stress, velocity and temperature fields are fully developed, then the wall shear rate can be calculated by applying the Weissenberg-Rabinowitsch operator toF _c Q instead of to the flow rateQ, whereF _c is a correction factor which differs from 1 when the temperature field is non-uniform; the isothermal equation relating the wall shear stress and pressure gradient is still valid. For the case in whcih = ₀|| ⁿ /(1 +(T–T ₀)), wheren, ₀, and are independent of shear stress and temperatureT, an exact analytical expression forF _c in terms of the Nahme-Griffith numberNa andn is obtained. Use of this expression gives agreement with data obtained for degassed decalin ( = 2.5 mPa s) from a new miniature slit-die viscometer at shear rates up to 5 × 10⁶s^–1; here, the correction is only 7%,Na is 1.3, andGz, the Graetz number at the die exit, is 119. For a Cannon standard liquidS6 ( = 9 mPa s), agreement extends up to 5 × 10⁵s^–1; at 2×10⁶s^–1 (whereNa = 7.2 andGz = 231), the corrections are 11% (measured) and 36% (calculated).Notation x, y Cartesian coordinates - v _x ,v velocity inx-direction, dimensionless velocity - p _xx ,p _yy normal stress onx- andy-planes - N ₁ first normal stress difference - shear stress ony-planes acting inx-direction - _w value of shear stress at the wall - shear rate, shear rate at the wall - Q, Q flow rate (Eqs. (2.13), (2.15)) - T, T ₀ temperature, temperature at the wall - ø, dimensionless temperature (Eqs. (2.24), (2.25)) - h, w half of die height, width of die - R diameter of a tube - , ₀ viscosity, viscosity atT = T ₀ - viscosity-temperature coefficient - k thermal conductivity - c _p specific heat at constant pressure - n, m dimensionless parameters characterizing shear stress dependence of viscosity - Na Nahme Griffith number (Eq. (2.21)) - Gz Graetz number (Eq. (5.1)) - F _c viscous heating correction factor (Eq. (2.18)) - ( ) a function characterizing temperature dependence of viscosity (Eq. (2.8)) - J _k ( ) Bessel function of the first kind This paper is dedicated to Professor Hanswalter Giesekus on the occasion of his retirement as Editor of Rheologica Acta.     

Rheological characteristics of glass-fibre-filled polypropylene melts

The rheological properties of glass fibre-filled polypropylene melts have been investigated. A high pressure capillary rheometer has been used for the experimental study. The effect of shear rate, temperature, and fibre concentration on the melt viscosity and viscoelastic properties have been studied. An equation has been proposed to correlate the melt viscosity with shear rate, temperature and fibre content. A master curve relation on this basis has been brought out using the shift factora _T . a _T shift factor (=/ _r ) - A _i coefficients of the polynomical of eq. (1) (i = 0, 1, 2, ,n) - B constant in the AFE equation (eq. (2)) (Pa s) - B constant in eq. (3) - D extrudate diameter - d capillary diameter - activation energy at constant shear rate (kcal/mole) - E activation energy at constant shear stress (kcal/mole) - T melt temperature (K) - X fraction glass fibre by weight - shear rate (s^–1) - shear viscosity (Pa s) - normal stress coefficient (Pa s²) - ₁ – ₂ first normal-stress difference (Pa) - shear stress (Pa) - r at reference temperature     

The steady shear viscosity of filled polymeric liquids described by a linear superposition of two relaxation mechanisms

Filled polymeric liquids often exhibit apparent yielding and shear thinning in steady shear flow. Yielding results from non-hydrodynamic particle—particle interactions, while shear thinning results from the non-Newtonian behavior of the polymer melt. A simple equation, based on the linear superposition of two relaxation mechanisms, is proposed to describe the viscosity of filled polymer melts over a wide range of shear rates and filler volume fraction.The viscosity is written as the sum of two generalized Newtonian liquid models. The resulting equation can describe a wide range of shear-thinning viscosity curves, and a hierarchy of equations is obtained by simplifying the general case. Some of the parameters in the equation can be related to the properties of the unfilled liquid and the solid volume fraction. One adjustable parameter, a yield stress, is necessary to describe the viscosity at low rates where non-hydrodynamic particle—particle interaction dominate. At high shear rates, where particle—particle interactions are dominated by interparticle hydrodynamics, no adjustable parameters are necessary. A single equation describes both the high and low shear rate regimes. Predictions of the equation closely fit published viscosity data of filled polymer melts. n power-law index - n ₁,n ₂ power-law index of first (second) term - shear rate - steady shear viscosity - ₀ zero-shear rate viscosity - _{0, 1}, _{0, 2} zero-shear rate viscosity of first (second) term - time constant - ₁, ₂ time constant of first (second) term - µ _r relative viscosity of filled Newtonian liquid - ₀ yield stress - ø solid volume fraction - ø _m maximum solid volume fraction     

Viscous heating correction for thermally developing flows in slit die viscometry

In the thermally developing region, d _yy /dx| _y=h varies along the flow direction x, where _yy denotes the component of stress normal to the y-plane; y = ±h at the die walls. A finite element method for two-dimensional Newtonian flow in a parallel slit was used to obtain an equation relating d _yy /dx/ _y=h and the wall shear stress ₀ at the inlet; isothermal slit walls were used for the calculation and the inlet liquid temperature T₀ was assumed to be equal to the wall temperature. For a temperature-viscosity relation /₀ = [1+(T–T₀]^–1, a simple expression [(hd _yy /dx/ _y=h )/ _w0] = 1–[1-F _c(Na)] [M()+P(Pr) ·Q(Gz ^–1)] was found to hold over the practical range of parameters involved, where Na, Gz, and Pr denote the Nahme-Griffith number, Graetz number, and Prandtl number; is a dimensionless variable which depends on Na and Gz. An order-of-magnitude analysis for momentum and energy equations supports the validity of this expression. The function F _c(Na) was obtained from an analytical solution for thermally developed flow; F _c(Na) = 1 for isothermal flow. M(), P(Pr), and Q(Gz) were obtained by fitting numerical results with simple equations. The wall shear rate at the inlet can be calculated from the flow rate Q using the isothermal equation.Notation x,y Cartesian coordinates (Fig. 2) - , dimensionless spatial variables [Eq. (16)] - dimensionless variable, : = Gz(x)^–1 - dimensionless variable [Eq. (28)] - t,t ^* time, dimensionless time [Eq. (16)] - , velocity vector, dimensionless velocity vector - _x , velocity in x-direction, dimensionless velocity - _y , velocity in y-direction, dimensionless velocity - V average velocity in x-direction - _yy , ^* normal stress on y-planes, dimensionless normal stress - shear stress on y-planes acting in x-direction - _w , _w ^* value of shear stress stress at the wall, dimensionless wall shear stress - _w0, _w0 ^* wall shear stress at the inlet, dimensionless variable - , ^* rate-of-strain tensor, dimensionless tensor - wall shear rate, wall shear rate at the inlet - Q flow rate - T, T ₀, temperature, temperature at the wall and at the inlet, dimensionless temperature - h, w half the die height, width of the die - l,L the distance between the inlet and the slot region, total die length - T ₂, T ₃, T ₄ pressure transducers in the High Shear Rate Viscometer (HSRV) (Fig. 1) - P, P2, P3 pressure, liquid pressures applied to T ₂ and T ₃ - , ₀, ^* viscosity, viscosity at T = T ₀, dimensionless viscosity - viscosity-temperature coefficient [Eq. (8)] - k thermal conductivity - C _p specific heat at constant pressure - Re Reynolds number - Na Nahme-Griffith number - Gz Graetz number - Pr Prandtl number     

Rheological behavior of water-creosote and creosote-water emulsions

The effect of temperature on the steady-shear viscosity of two base emulsions (water-in-creosote (w/o) and creosote-in-water (o/w)) and a pigment emulsified creosote (PEC) was investigated. The PEC is a water-in-creosote emulsion which contains also a solid, micronised pigment, and is used industrially as a wood preservative. All three emulsions exhibited shear thinning characteristics at different temperatures. The viscosity-shear rate relationships follow a modified Quemada model. A temperature-superposition method using the reduced variables / and t _c was applied to yield a master plot for each of these emulsions at different temperatures. The effect of creosote concentration on the viscosity of four other o/w emulsions at different temperatures was also studied. The same reduced variables were able to produce a temperature-concentration superposition plot for all of the o/w emulsion results.The effective (average) radius of the globules (dispersed phase) was found to increase with increasing temperature for the base w/o and the PEC emulsion. The collision theory could be used to explain the increase in the droplet size. However, while little overall variation in globule size was observed for the o/w emulsions, microscopic observation indicated an increase in the proportion of large diameter droplets with temperature at the highest creosote concentration (60%). A creaming effect (phase concentration) was observed with these emulsions at higher temperatures, precluding an accurate estimate of droplet size based on collision theory.Seconded from Koppers Coal Tar Products, Newcastle, N.S.W., Australia.     

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.     

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     

Material functions generated by the complex viscosity

Based on the complex viscosity model various steady-state and transient material functions have been completed. The model is investigated in terms of a corotational frame reference. Also, BKZ-type integral constitutive equations have been studied. Some relations between material functions have been derived. C ^–1 Finger tensor - F[], (F ^–1[]) Fourier (inverse) transform - rate of deformation tensor in corotating frame - h(I, II) Wagner's damping function - J (x) Bessel function - m parameter inh (I, II) - m(s) memory function - m _k, n_k integers (powers in complex viscosity model) - P principal value of the integral - parameter in the complex viscosity model - rate of deformation tensor - shear rates - [], [] incomplete gamma function - (a) gamma function - steady-shear viscosity - ^* complex viscosity - , real and imaginary parts of ^* - ₀ zero shear viscosity - ⁺, ₁ ⁺ stress growth functions - ^–, ₁ ^- stress relaxation functions - (s) relaxation modulus - ₁(s) primary normal-stress coefficient - ø(a, b; z) degenerate hypergeometric function - ₁, ₂ time constants (parameters of ^*) - frequency - extra stress tensor     

A three-parameter model describing the experimental relation between shear stress and shear rate for laminar flow of aqueous polymer solutions

Summary A three-parameter model is introduced to describe the shear rate — shear stress relation for dilute aqueous solutions of polyacrylamide (Separan AP-30) or polyethylenoxide (Polyox WSR-301) in the concentration range 50 wppm – 10,000 wppm. Solutions of both polymers show for a similar rheological behaviour. This behaviour can be described by an equation having three parameters i.e. zero-shear viscosity ₀, infinite-shear viscosity , and yield stress ₀, each depending on the polymer concentration. A good agreement is found between the values calculated with this three-parameter model and the experimental results obtained with a cone-and-plate rheogoniometer and those determined with a capillary-tube rheometer.

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Zusammenfassung Der Zusammenhang zwischen Schubspannung und Schergeschwindigkeit von strukturviskosen Flüssigkeiten wird durch ein Modell mit drei Parametern beschrieben. Mit verdünnten wäßrigen Polyacrylamid-(Separan AP-30) sowie Polyäthylenoxidlösungen (Polyox WSR-301) wird das Modell experimentell geprüft. Beide Polymerlösungen zeigen im untersuchten Schergeschwindigkeitsbereich von ein ähnliches rheologisches Verhalten. Dieses Verhalten kann mit drei konzentrationsabhängigen Größen, nämlich einer Null-Viskosität ₀, einer Grenz-Viskosität und einer Fließgrenze ₀ beschrieben werden. Die Ergebnisse von Experimenten mit einem Kegel-Platte-Rheogoniometer sowie einem Kapillarviskosimeter sind in guter Übereinstimmung mit den Werten, die mit dem Drei-Parameter-Modell berechnet worden sind.

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a Pa^–1 physical quantity defined by:a = {1 – ( / ₀)}/ ₀ - c l concentration (wppm) - D m capillary diameter - L m length of capillary tube - P Pa pressure drop - R m radius of capillary tube - u m s^–1 average velocity - v _r m s^–1 local axial velocity at a distancer from the axis of the tube - shear rate (–dv _r /dr) - local shear rate in capillary flow - s^–1 wall shear rate in capillary flow - Pa s dynamic viscosity - _a Pa s apparent viscosity defined by eq. [2] - ( _a ) Pa s apparent viscosity in capillary tube at a distanceR from the axis - ₀ Pa s zero-shear viscosity defined by eq. [4] - Pa s infinite-shear viscosity defined by eq. [5] - l ratior/R - kg m^– density - Pa shear stress - ₀ Pa yield stress - _r Pa local shear stress in capillary flow - _R Pa wall shear stress in capillary flow _R = (PR/2L) - _v m³ s^–1 volume rate of flow With 8 figures and 1 table     

Influence of the formation of associations of macromolecules on the rheo-optical properties of their dilute solutions. I. Theory

Assuming the formation of doublets in the flow according to a mass action law, the shear rate and the concentration dependence of the extinction angle, of the birefringence, and of the average coil expansion are calculated for dilute solutions of flexible macromolecules. It is shown that this reversible association process has a strong influence on the measurable parameters in a flow birefringence experiment. c concentration (g/cm³) - h ² mean square end-to-end distance at shear rate - h ₀ ² mean-square end-to-end distance at zero-shear rate - n refractive index of the solution (not very different from the solvent for a very dilute solution) - E mean coil expansion - K ₀,K constant of the mass action law - M molecular weight - R _G gas constant - T absolute temperature - ₁ – ₂ optical anisotropy of the segment - ₀ Deborah number: - Deborah number: - shear rate - ₀, reduced concentration - _s viscosity of the solvent - [] ₀ intrinsic viscosity at zero-shear rate - [] intrinsic viscosity at shear rate - extinction angle - N _a Avodagro's number - _n magnitude of the birefringence     

Determination of the steady-state shear viscosity from measurements of the apparent viscosity for some common types of viscometers

Considering a number of model fluids, the relation between the (measurable) apparent viscosity _a and the (true) shear viscosity is studied for some commonly used viscometers, like capillary, slit, plate-plate and concentric cylinders (including the influence of the bottom of the cylinder), as well as for one laboratory type of viscometer. As long as is a purely monotonic function, a shift factor < 1 allows one to deduce from _a . Though in general variable, it frequently suffices for practical purposes to use a constant shift factor (the constant being characteristic of the type of viscometer used). This does not apply to dilute solutions or any fluids with two plateau values for . For plastic fluids, it is shown that Casson or Bingham behavior can — if valid at all — only describe the high shear stress limit of _a .     

Molecular weight distribution from rheological measurements

Summary A simple and reliable relative method to derive the molecular weight distribution of linear polymers is proposed.It is shown that both the zero-shear viscosity, ₀, and the intrinsic viscosity, [], have a logarithmic dependence on the weight average molecular weight, , and the polydispersity, . The coefficients of these relationships can be determined by applying a multiple regression analysis to a series of samples for which andQ are known.By making use of the two established relationships, the determination of andQ for a given polymer sample reduces to the experimental measurement of its ₀ and [].An analysis has been performed to estimate to what extent experimental errors on ₀ and [] affect the calculated molecular weight distribution.It has been found that only the experimental error on [] contributes heavily to the final error on the polydispersity.

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Zusammenfassung Es wird eine einfache und zuverlässige Relativmethode vorgeschlagen, um die Uneinheitlichkeit linearer Polymere abzuleiten.Es wird gezeigt, daß alle beide, Nullschergradient-viskosität ₀, und Grenzviskositätszahl [], einfach logarithmisch vom Gewichtsmittel des Molekulargewichts , und vom Polymolekularitätsindex , abhängig sind.Die Koeffizienten dieser Beziehungen können mit statistischer Analyse festgesetzt werden, wenn undQ einer Probenreihe bekannt sind.Mit den zwei vorher festgesetzten Beziehungen besteht die Bestimmung von undQ einer gegebenen Polymersprobe nur aus den experimentellen Massen seiner ₀- und []-Werte.Eine Analyse wurde ausgeführt, um die Bedeutung des experimentellen Irrtums über die berechnete Uneinheitlichkeit zu wissen.Es wurde gefunden, daß ein experimenteller Irrtum betreffs [] schwer an endlichem Irrtum der Uneinheitlichkeit teilnimmt.

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With 2 figures and 2 tables     

An experimental study on effects of solid concentration and ζ-potential on pseudoplastic flow of suspensions

The pseudoplastic flow of suspensions, alumina or styrene-acrylamide copolymer particles in water or an aqueous solution of glycerin has been studied by the step-shear-rate method. The relation between the shear rate,D, and the shear stress,, in the step-shear-rate measurements, where the state of dispersion was considered to be constant, was expressed as = AD ^1/2 +CD. The effective solid volume fraction,ø _F, andA were dependent on the shear rate and expressed byø _F =aD ^b andA = D . Combining the above relations, the steady flow curve was expressed by = D ^{1/2 +} + ₀ (1 – a D ^b/0.74)^–1.85 D, where ₀ is the viscosity of the medium.With an increase in solid volume fraction and a decreases in the absolute value of the-potential, the flow behavior of the suspensions changed from Newtonian ( = = b = 0), slightly pseudoplastic ( = b = 0), pseudoplastic ( = 0) to a Bingham-like behavior.The change in viscosity of the medium had an effect on the change in the effective volume fraction.     

Pure liquids described as concentrated cluster dispersions

The Fulcher-Tammann-Hesse-Vogel equation, ln = A + B/(T – T ₀ ), is shown to be equivalent to the general viscosity-composition relationship, ln _r =k f /(1 – f ), for binary mixtures. The Cailletet-Mathias law of the Rectilinear Diameter is rearranged to represent a density mixture formula for two components. Temperature-independent viscosities and densities can then be calculated for dense, solid cluster fractions, dispersed in a low-density, low-viscosity non-clustered continuous phase. The cluster fraction decreases with temperature. The value ofT ₀ is shown to be related to the liquid- or solid-like behavior of the clusters. For liquids with a vapor pressure < 1 mm Hg at the melting point, the calculated cluster volume fraction suggests close packing of clusters, ranging in shape from monodisperse spheres to polydisperse non-spherical particles. Examples are given for molecular liquids, molten metals, and molten salts. The size of the clusters is estimated from the heat of evaporation.