Normal stresses in non-Newtonian polymer flows

The calculation of the normal stresses from the flow curve is considered on the basis of the method of correlation of the frequency and stationary characteristics of flowing polymer systems. Simple expressions are given for finding the initial normal stress coefficient and the high-elastic modulus from the point corresponding to the beginning of non-Newtonian flow. A necessary condition for the appearance of normal stresses is a viscosity anomaly. It is shown that for a bounded value of the initial normal stress coefficient to exist the derivative of the effective viscosity with respect to shear rate must be zero at the initial point.Topchiev Institute of Petrochemical Synthesis, Academy of Sciences of the USSR, Moscow. Translated from Mekhanika Polimerov, No. 3, pp. 506–514, May–June, 1971.     

Relation between the shear and longitudinal viscosity coefficients for concentrated polymer solutions

A relation between the shear and longitudinal viscosity coefficients is obtained on the basis of the theory of flow of polymeric systems in the single relaxation time approximation. A comparison of the shear and longitudinal viscosity coefficients for polymer melts and solutions shows that the relation obtained is valid over a broad stress region.Institute of Chemical Physics, Academy of Sciences of the USSR, Moscow. Scientific-Research Institute of Synthetic Fibers, Moscow. Translated from Mekhanika Polimerov, No. 1, pp. 124–131, January–February, 1973.     

Correlation of the effective and complex dynamic viscosities of viscose

The results of comparative measurements of viscosity of viscose in the steady-state flow and harmonic vibration regimes are presented. It is shown that in order to describe the dependence of the effective viscosity on the velocity gradients in the steady-state flow regime it is possible to employ the mathematical apparatus of the phenomenological theory used in dynamic investigations. The operating regimes of automatic viscometers intended for measuring the maximum Newtonian viscosity of viscose are determined.All-Union Scientific-Research Institute of Synthetic Fiber, Moscow Region. Translated from Mekhanika Polimerov, No. 4, pp. 756–759, July–August, 1973.     

On the theory of non-Newtonian polymer flow

The Eyring-Frenkel theory of viscosity of low-molecular liquids has been extended to solutions of high-molecular compounds. It is shown that there are flow units of different sizes in the system, their mean size being proportional to the molecular weight of the polymer. An expression is obtained for the non-Newtonian viscosity of polymer solutions. In the limiting case of high shear rates the viscosity of the solution coincides with that of the solvent. At low shear rates Flory's empirical relation for the viscosity of polymer solutions is theoretically obtained.Mekhanika Polimerov, Vol. 2, No. 5, pp. 779–784, 1966     

On the theory of non-Newtonian polymer flow

Shear flow of polymers is examined on the assumption that the main contribution to polymer viscosity is made by the dissipation of energy in the destruction of the fluctuation network. A simple physicomechanical model of the flow process is proposed and used to obtain an expression for the polymer viscosity in terms of certain functions reflecting the influence of the molecular structure.Mekhanika Polimerov, Vol. 2, No. 3, pp. 429–434, 1966     

Effect of the molecular weight of polystyrene on the viscosity of concentrated solutions

The viscosity of solutions of polystyrene of various molecular weights (from 1.04 · 10² to 3.8 · 10⁵) in a poor solvent (decalin) and a good solvent (ethylbenzene) has been measured at temperatures from 15 to 70°C over a broad range of shear stresses from 10² to 10⁶ dyne/cm². The nature of the solvent has a considerable influence on the critical molecular weight and the absolute value of the viscosities of the solutions over the entire range of molecular weights and on the form of the flow curves of decalin solutions of polystyrene as a function of temperature. The heat of activation of viscous flow increases with increase in molecular weight and shear stress on the interval 20–80°C. The results obtained are explained in terms of the effect of the molecular weight of the polymer, the nature of the solvent, stress and temperature on structure formation in the solution and on the orientation of the macromolecules and structures in the flow process.Ural Gor'kii State University, Sverdlovsk. Translated from Mekhanika Polimerov, No. 5, pp. 920–926, September–October, 1970.     

Multicritical phenomena in flow of viscoelastic liquids. 1. Zaremba-Fromm-De Witt liquid

It has been shown that multicritical phenomena caused by nonlinearity of viscosity and high elasticity, and forced anisotropy at finite shear rates take place during flow of viscoelastic polymer melts which are isotropic in the resting state. The sign of the low-frequency asymptotic values of the dynamic viscosity and elasticity measured during steady flow is a criterion of the appearance of instability. These arguments are illustrated by the solution and analysis of the complex reaction to low-amplitude, periodic shear of a steady-flowing, very simple viscoelastic liquid — ZFD liquid. It was shown that the instability of viscoelastic liquids for a given steady shear rate is due to the effect of perturbations lasting for no less than some limiting value and its manifestations are caused by superposition of different types of instability — multicritical phenomena.Translated from Mekhanika Kompozitnykh Materialov, Vol. 31, No. 4, pp. 555–572, July–August, 1995.The study was conducted based on Topic 93,177 of the Latvian Science Council.     

Molecular mechanism of oriented crystalline polymers

It is shown with reference to linear polyethylene that the deformation of an oriented crystalline polymer takes place as a result of elongation of the coiled parts of the macromolecules in the amorphous zones owing to conversion of gauche into extended trans isomers. The decrease in coiled isomer content when the specimen is deformed by approximately 5% is accompanied by a small number of chemical bond breakages. Repeat deformation by the same amount does not result in any additional breakage of polymer chains.A. F. Ioffe Physicotechnical Institute, Academy of Sciences of The USSR, Leningrad. Translated from Mekhanika Polimerov, No. 4, pp. 584–588, July–August, 1973.     

Breakage of the polymer chains in Kapron oriented at various temperatures

Infrared spectroscopy has been used to detect a considerable reduction in the number of broken macromolecules in Kapron oriented at elevated temperatures, particularly in the region above 140°C. This is a consequence of weakening of the hydrogen bonds and an increase in the mobility of the amide groups in the crystalline parts of the polymer as the temperature rises.Ioffe Physicotechnical Institute, Academy of Sciences of the USSR, Leningrad. Translated from Mekhanika Polimerov, No. 4, pp. 649–653, July–August, 1971.     

Forced viscosity anisotropy of polymers

For two-dimensional flow the viscosity of an anisotropic medium is determined by two quantities. In relation to polymer melts, one of these corresponds to the viscosity for tension in the direction of orientation and the other to viscosity for shear in planes parallel to the orientation. By solving the problem of the flow of such a medium in a plane convergent channel and making optical-polarization measurements we were able to observe and quantitatively describe this phenomenon.Mekhanika Polimerov, Vol. 1, No. 5, pp. 13–18, 1965     

Dynamic deformation of a stationary rubber flow

The effect of dynamic deformation on the stationary flow of a rubber composition has been experimentally investigated for comparable values of the stationary and dynamic strain rates. The dependence of the effective viscosity on the stationary shear rate is not equivalent to its dependence on the periodic shear rate amplitude. An expression is given for calculating the effective viscosity in the case of combined stationary and dynamic shear deformation. The effectiveness of the dynamic deformation, estimated in terms of the effective viscosity, depends on whether it is superimposed on the stationary flow at constant stationary shear rate or at constant stress. It is proposed to estimate the effectiveness of dynamic deformation of a stationary non-Newtonian flow in terms of the change in the power of the stationary forces. When the effective viscosity is reduced by dynamic deformation of the stationary flow, the power of the stationary forces increases at constant shear stress and falls at constant stationary shear rate.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR, Riga. Translated from Mekhanika Polimerov, No. 3, pp. 489–496, May–June, 1971.     

Macromolecular mechanics

The fundamentals of "macromolecular" mechanics are outlined and approximate quantitative relations are established between the parameters of the mechanical properties of elastically stretched macromolecules and the characteristics of the mechanical properties of polymers determined at significant uniaxial deformations. This new scientific approach is based on the assumption of "framework connectivity." The conditions of internally compensated mechanical equilibrium at the molecular level are investigated. Several variants of simple geometric models of the "framework" reinforcing the stretched polymer are proposed. A system of quantities characterizing the mechanical properties of the polymer and the "framework" is developed. According to the theory, the stress in the "framework" macromolecules, considered as a molecular elastic continuum, substantially exceeds the stress in the stretched polymer. The nature of the internal stresses and elastic aftereffect in glassy crystalline polymers subjected to significant deformation is reinterpreted.Moscow. Translated from Mekhanika Polimerov, No. 2, pp. 221–231, March–April, 1971.     

Dynamic properties of certain unvulcanized rubbers in the high-elastic and fluid states

The dynamic properties of a series of unvulcanized rubbers (cis-polybutadienes, Na-polybutadiene, cis-polyisoprene, butyl rubber, polyisobutylene, and ethylene-propylene copolymer) have been investigated in a low-frequency dynamic testing machine and a frequency rheometer on the frequency range from 5 · 10^–2 to 4.5 · 10³ Hz at temperatures of 25 and 60°C. At these temperatures the mechanical loss factor is the most sensitive criterion of transitions from one physical state of the polymer to another. For all the specimens investigated on the experimental range of angular frequencies the modulus of the complex dynamic viscosity and the effective viscosity determined under static conditions coincide, assuming the equivalence of angular frequencies and shear rates.A. V. Topchiev Institute of Petrochemical Synthesis, Academy of Sciences of the USSR, Moscow. Translated from Mekhanika Polimerov, No. 4, pp. 698–703, July–August, 1969.     

Flow of a nonlinear viscoelastic liquid in cylindrical channels

The problem of nonrectilinear steady-state flow of a nonlinear viscoelastic liquid in an arbitrary cylindrical channel is examined. On the assumption that the cross flows are insignificant as compared with the longitudinal flows an equation of state is derived for the flow regime in question. A variational principle established for steady-state flows of the investigated media is proposed as the basis of a method of solving problems of the flow of polymer materials in arbitrary cylindrical channels. The flow of a polymer solution in rectangular channels is investigated.Institute of Mechanics, AS UkrSSR, Kiev. Translated from Mekhanika Polimerov, Vol. 4, No. 6, pp. 1103–1111, November–December, 1968.     

Changes in the fine structure of polycaprolactam induced by hydrostatic pressure

The effect of high (up to 22,000 atm) hydrostatic pressure on the interplanar spacings and corresponding diffraction maxima in polycaprolactam has been investigated. The observations are interpreted in terms of the compressibility anisotropy relative to the amorphous and crystalline regions of the polymer and possible elastic deformation of the amorphous zones leading to tensile stresses in the crystalline regions that relax as the polymer ages owing to processes associated with changes in the conformations of the macromolecules and the number of crosslinks between segments.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR, Riga. Translated from Mekhanika Polimerov, Vol. 4, No. 4, pp. 579–585, July–August, 1968.     

Comparative estimate of the molding capacities of injection molding machines with plunger and screw plastication

An analysis of the mold filling process, based on the equation of nonisothermal flow of an amorphous polymer melt, shows that for thin moldings the molding capacity of the machine, estimated as the maximum shot length, has a limit that does not depend on the pressure at the mold inlet and is determined by the flow rate of the polymer in the mold. As shown by an analysis of the process of compaction of the polymer in the system preceding the mold, this flow rate is many times less for plunger plastication, which is responsible for the reduced molding capacity of plunger machines. The effect can be eliminated by compressing the polymer before injecting it into the mold.Moscow Institute of Chemical Machine Building. Translated from Mekhanika Polimerov, No. 2, pp. 367–372, March–April, 1970.     

Viscosity,rubber elasticity,and viscoelasticity of concentrated polymer solutions

The results of a comparative investigation of the effect of the nature of the polymer and the solvent on the viscosity, rubber elasticity, and viscoelasticity of concentrated polymer solutions in the region of linear mechanical behavior are presented. It is established that in the case of nonpolar polymers the solvent affects only the free volume of the solution, whereas for polar polymers it also affects the entanglement network. This leads to the equality of the viscosities of solutions of nonpolar polymers in different solvents when compared in corresponding states (relative to the glass transition temperature) and to the dependence of the shear modulus of solutions of polar polymers on the nature of the solvent and temperature. It is shown that there is a universal relaxation spectrum in the flow zone for solutions of different polydisperse polymers after normalization with the shear modulus and the natural relaxation time determined as the ratio of the viscosity to the shear modulus.A. M. Gor'kii Ural State University, Sverdlovsk, A. V. Topchiev Institute of Petrochemical Synthesis, Academy of Sciences of the USSR, Moscow. Translated from Mekhanika Polimerov, No. 4, pp. 729–736, July–August, 1973.     

Investigation of the state of water sorbed by an organic polymer by high-resolution1H nuclear magnetic resonance and differential thermal analysis

Conclusions The results of the experimental investigation of a moist organic composite by high-resolution NMR and DTA indicate a change in the structure of water, due to an interaction between the water molecules and the macromolecules when water is sorbed by the organic polymer. A part of the sorbed water molecules is strongly bound to the macromolecules; their mobility is very low and is not recorded by high-resolution NMR. As the moisture content of the composite increases, molecules of water appear, the mobility of which is intermediate between the strongly bound and free water molecules in the macrospace. This part of the molecules is represented in the NMR spectrum by a broadened and shifted line and a shift of the endothermic peak towards lower temperatures is observed on the thermal analysis diagrams. The weakly bound water can be detected in the composite starting at a moisture content of 5–8%.Translated from Mekhanika Kompozitnykh Materialov, No. 2, pp. 317–320, March–April, 1990.     

Rheological properties of polymers in the fluid state

The possibilities and conditions of correlation are determined for the principal rheological characteristics of single-phase polymer systems measured for one-dimensional shear deformation in steady-state flow regimes, on transition from rest to steady-state flow, and in harmonic vibration regimes. Special significance attaches to the quantitative results of measuring the high-elastic properties of the polymer systems. It is shown that the Lodge theory, describing the flow behavior of high-elastic media, is well-founded in the linear region of deformation, i.e., for the limiting case of shear rates and shear stresses tending to zero, whereas the Mooney-Rivlin-Weissenberg theories are not in accord with the experimental data even in this limiting deformation regime.Topcheiv Institute of Petrochemical Synthesis, Academy of Sciences of the USSR, Moscow. Translated from Mekhanika Polimerov, Vol. 5, No. 1, pp. 164–181, January–February, 1969.     

Effect of fillers on the viscosity and viscoelasticity of low-density polyethylene melts. Communication 1

An investigation of low-density polyethylenes filled with up to 30% by volume dispersed particles, has shown that for both the matrix and the composites the apparent viscous flow activation energy does not depend on the shear stresses and increases starting from a certain filler concentration at which the conformation range in the matrix is depleted. The dependence of the relative viscosity of the compositions on the volume filler content is satisfactorily described by an equation that contains the reduced filler concentration, defined as the ratio of the nominal filler concentration to the limiting concentration at which the adsorption layers on the particles extend throughout the matrix. The thickness of the polymer layer adsorbed on the particles must be determined from the specific exterior particle surface, with allowance for the volume of the polymer in the sorption space of the porous filler.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR, Riga. Translated from Mekhanika Polimerov, No. 3, pp. 478–486, May–June, 1976.