Linear Viscoelasticity of Liquid-Crystalline Polymers

A linear (small-amplitude) periodic shear deformation of anisotropic viscoelastic liquids obeying the Akay–Leslie rheological model is considered. The frequency dependences of the real and imaginary components of the complex shear modulus and complex normal-stress coefficient are determined. A comparison between calculation results and test data on the shear flow of poly(-benzylglutamate) in m-cresol is carried out. It is stated that, if the material is characterized by some initial orientation, both components of the complex shear modulus contain a multiplier which depends on the degree of the initial orientation and increases the values of the components compared with those for an initially isotropic material. The model predicts that, in a periodic shear flow, the components of shear and normal stresses are constant and, like the components of shear modulus, are independent of deformation frequency. If the parameter d ₀ of the Akay–Leslie model is equal to zero, the values of its other parameters can be determined from experimental results on periodic shear flow.     

Thixotropy of filled-polyethylene melts subjected to periodic shear deformation

As a result of the action of periodic finite-amplitude shear deformations filled high-pressure polyethylene melts exhibit thixotropic properties. The effect of the previous deformation history on the frequency dependence of the complex dynamic shear modulus is investigated.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR Riga. Translated from Mekhanika Polimerov, Vol. 4, No. 5, pp. 927–931, September–October, 1968.     

Rheology and molecular structure of polyethylene melts 1. Melt identification from mechanical properties

It is proposed to use periodic deformation for the identification of the molecular structure of polyethylenes. By comparing the dependence of the complex and apparent viscosities on frequency and shear rate, respectively, it is shown that these functions are not equivalent for low-density polyethylene melts. The need for a numerical characteristic of the rheological functions, which should be related to the numerical characteristics of the molecular structure of the polymer, is established. The possibilities of using generalized relations for investigating the molecular structure are discussed. It is shown that the dynamic viscosity of polyethylene melts, described by a three-parameter equation, quite accurately reflects the viscoelastic properties of polyethylene melts and makes it possible, with the aid of the calculated function of the relaxation spectrum, to construct a frequency dependence of the modulus corresponding to the experimental data. Three numbers characterizing the viscoelasticity of polyethylene, which must be related with three molecular characteristics, are established.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR, Riga. Translated from Mekhanika Polimerov, No. 3, pp. 523–532, May–June, 1975.     

Harmonic distrotions under nonlinear periodic deformation of fluid polymers

Conclusions 1. It has been shown for a number of viscoelastic fluid systems that under nonlinear periodic deformation, the contribution of the third harmonic of the stress to the fundamental does not exceed 20% of the amplitude.2. In the case of clay soil and melt of filled polyethylene, the shape of the stress waves is essentially definable by the relative phase angle of the third harmonic of the stress and is practically independent of the deformation amplitude in a growing nonlinear range of deformation.3. In the case of the polyethylene melt, the amplitude dependence of the phase angles of the stress harmonics is in satisfactory agreement with the analysis of model I. With increasing deformation amplitude, the modulus vector of the first harmonic rotates counterclockwise and remains in the first trigonometric quadrant; the modulus vector of the third harmonic passes from the second to the third quadrant, and the modulus vector of the fifth harmonic passes from the second to the fourth quadrant via the third.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR, Riga. Translated from Mekhanika Polimerov, No. 5, pp. 893–898, September–October, 1978.     

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.     

Effect of filler on relaxation-time spectra of filled polymers

The frequency and temperature dependence of the complex shear modulus G* and tan δ of epoxide compositions with various fillers have been studied. Relaxation-time spectra of filled polymers with various fillers have been plotted by the Ninomi-Ferry method. The principles governing changes in the shape of the spectrum curves with increase in filler concentration have been observed, enabling conclusions to be drawn on the effect of the filler on the change in properties of a polymer matrix and the deformation conditions of the polymer layers between the filler particles.     

Velocity and pressure distribution in the gap of a disk extruder

The axisymmetric two-dimensional flow of a polymer melt in the plane gap of a disk extruder produced by the normal stress effect is considered. The polymer is assumed to be a nonlinear viscoelastic medium, whose strain history is expressed by means of kinematic matrices. A rheological equation of state of the medium, in which all the invariants of the kinematic matrices are function of strain rate intensity, is established. The laws of distribution of the radial and tangential velocity components over the gap are found from the solution of the equations of motion, and expressions are obtained for the radial pressure distribution and the integral thrust.Volgograd Polytechnic Institute. Translated from Mekhanika Polimerov, No. 3, pp. 515–521, May–June, 1971.     

Self-reinforcement of liquid-crystal polymers at static and dynamic loading

The self-reinforcement effect of a solid uniaxially oriented SVM-K liquid-crystal polyamide and a copolyester of hydroxybenzoic and hydroxynaphthoic acids has been investigated by tensile-strength, stress-relaxation, and dynamic methods. The samples were prepared by spinning from lyotropic solution (SVM-K) and from a thermotropic melt (polyester). The tensile-strength and stress-relaxation tests were performed on complex fibers and the dynamic test on single fibers. The set of stress-strain curves, changing from a convex shape with two linear sections (at room temperature) to a concave shape (at high temperatures) is shown for both materials in Fig. 1. There is a pronounced difference between the deformation mechanisms at low and high strains in the stability of rigidity. At high temperatures the rigidity becomes less than the initial one during deformation and the current modulus at high strains has the same value within large ranges of temperatures and strains (Fig. 2). A low-deformation transition of another physical parameter than the yield-stress has been found. The stress-strain diagram for both investigated polymers has been generalized by using the constant value of the current modulus for the normalization of the stress value (Fig. 3). The stress-relaxation phenomena are shown to be anomalous. At high temperatures the stress-relaxation intensity decreases with increasing deformation, i.e., after deformation the polymer is characterized by a stability of rigidity which is higher than the initial value (Fig. 4). The dynamic modulus appears to increase with increasing deformation rate (Fig. 5). Due to these peculiarities the liquid-crystal polymers must be considered not only as normal high-modulus reinforcements for composite materials but also as materials, self-reinforcing under loading.Translated from Mekhanika Kompozitnykh Materialov, Vol. 30, No. 4, pp. 435–441, July–August, 1994.     

Rheological Properties of Nanosized AlN Powder Suspensions for Advanced Ceramics

The rheological properties (flow curves and viscoelastic behavior) of injection molding suspensions of a plasma-processed AlN nanosized powder (nanopowder) in paraffin are investigated over a broad range of shear rates (0.07–1350 s^–1). Two viscosity plateaux are observed on the flow curves and two values of the yield stress are obtained. The lower value of the strain amplitude (0.66%), exceeding the linearity limit of periodic shear, is restricted by the rheometer resolution. The ultrasound treatment and shear deformation of suspensions affect the structure of particle packing, which is responsible for the dependence of their rheological properties on the prehistory of mechanical actions.     

Method of investigating the extension of high-elastic polymers

A method has been developed for studying the deformation of polymers in a field with a longitudinal velocity gradient. The changes in the longitudinal viscosity and modulus of high elasticity of polyisobutylene in uniaxial tension at constant extension and strain rates are compared.Mekhanika Polimerov, Vol. 4, No. 2, pp. 343–348, 1968     

Variation of the frequency and amplitude of periodic deformation in a Weissenberg rheogoniometer

The stresses that develop in the material due to changes in the frequency or amplitude of periodic deformation in a Weissenberg rheogoniometer are described. Examples of stress buildup and relaxation are presented for a filled low-density polyethylene melt.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR, Riga. Translated from Mekhanika Polimerov, No. 5, pp. 936–938, September–October, 1970.     

Nonlinear shear response of fluid polymers during periodic deformation. Basic harmonics

Conclusions 1. A model with a relaxation spectrum independent of accumulated elastic strains describes the combination of data on the amplitude and frequency dependences of the components of the shear modulus in terms of basic harmonics for low-molecular-weight polyisobutylene and a filled-polyethylene melt.2. The greater the amplitude of the shear strain, the broader the region of invariance of the relaxation functions relative to the amplitude of the rate of oscillatory shear.3. The kinetic (s) function affects the amplitude dependences of the modulus in terms of basic harmonics. Its effect is significantly greater on the real component of the modulus than on the imaginary one.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR, Riga. Translated from Mekhanika Polimerov, No. 6, pp. 1093–1100, November–December, 1977.     

Theory of flow of concentrated polymer solutions and melts

Starting from the concept of a polymer system as a collection of macromolecules forming an effective network, an expression is obtained for the stress tensor of a flowing concentrated polymer solution or melt. It is shown that the variation of the effective viscosity of polymer systems is associated with the orientation of the macromolecules and changes in the equilibrium number of nodes during flow. A system of equations describing the flow of polymer systems characterized by a gradient dependence of the effective viscosity and normal stresses in shear is written in the single relaxation time approximation.Institute of Chemical Physics, Moscow Region, Academy of Sciences of the USSR. Translated from Mekhanika Polimerov, Vol. 4, No. 4, pp. 724–730, July–August, 1968.     

A new method of measuring the viscoelastic properties of polymer systems in fluid and highly elastic states using forced vibrations in the ultralow-frequency region

A method is considered for measuring the dynamic mechanical characteristics of polyer systems using forced vibrations in the ultralow-frequency region down to 10^–6 Hz. The essence of this method lies in the fact that during the measurement process the motion of the polymer sample is controlled with a set amplitude and frequency, and the dynamic characteristics of the polymer are determined from the controlling mechanical stress. The method is illustrated using the results of measurements of the components of the complex modulus for polybutadiene over a wide range of temperatures and frequencies without making use of superimposition.The Central Constructional Bureau for Prototype Instrument Construction, Academy of Sciences of the USSR, Moscow. Translated from Mekhanika Polimerov, No. 2, pp. 344–347, March–April, 1976.     

Variation of the elasticoviscous characteristics of a heavily filled rubber after periodic shear deformation

The results of an investigation of the recovery of the elasticoviscous characteristics after thixotropic reduction by periodic deformation in the nonlinear zone are reported. The rate of recovery of the mechanical properties depends on the deformation frequency and the previous history of dynamic deformation is shown to affect the dependence of the elasticoviscous characteristics on the shear rate gradient. The effects of stationary and dynamic deformation regimes on the relaxation spectrum of the material are compared.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR, Riga. Translated from Mekhanika Polimerov, No. 3, pp. 528–533, May–June, 1969.     

The pulsating viscous flow superposed on the steady laminar motion of incompressible fluid in a circular pipe

Summary An exact solution of pulsating laminar flow superposed on the steady motion in a circular pipe is presented under the assumption of parallel flow to the axis of pipe. Total mass of flow on time average is found to be identified with that given byHagen-Poiseuille's low calculated on the steady component of pressure gradient. The phase lag of velocity variation from that of pressure gradient increases from zero in the steady motion to 90° in the pulsation of infinite frequency. Integration of work for changing kinetic energy of fluid through one period is vanished, while that of dissipation of energy by internal friction remains finite and excess amount caused by the components of periodic motion is added to the components of steady flow.It is found that the given rate of mass flow is attained in pulsating motion by giving the same amount of average gradient of pressure as in steady flow, but that excess works to the steady case are necessary for maintenance of this motion.

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Zusammenfassung Eine exakte Lösung der pulsierenden laminaren Strömung in einem Kreisrohr wird angegeben mit der Annahme, dass die Richtung dem Geschwindigkeitsvektor der Rohrachse parallel ist. Die Durchflussmenge stimmt überein mit der aus der stationären Druckgefällekomponente gerechneten Menge. Für die Erhaltung der Bewegung dagegen ist die der Dissipation entsprechende Extraarbeit notwendig. Die Quantität dieser Arbeit hängt ab von den Frequenzen der Stromschwingungen.

     

Mechanical properties of blends of liquid crystalline copolyesters with polyprophylene

Conclusions A significant effect of the addition of LCP on the mechanical properties and their anisotropy has been established. Already, if one considers the shape of curves of the stress-strain relationship it can be seen that curves typical for semicrystalline polymers (pure polypropylene) with clearly visible yield point and significant cold drawing leading to an anisotropic stiffening are changing into curves without yielding and with a brittle failure (LC-rich blends). Generally, the tensile elasticity modulus increases with increasing LCP content for both MD and TD. The maximum value of anisotropy of elastic properties was noted for a rather low content of LCP (c = 5%). On the contrary, the stress at yield decreases with increasing LCP content. The same was observed for the strain at yield but in both cases an important increase of anisotropy has taken place. Consequently, the total elongation during drawing (strain at break) showed a drastic decrease for blends with higher LCP content (about 60–80 times). The addition of the LCP to polypropylene has led to a stiffness increase (higher elasticity modulus) but simultaneously to a considerable plasticity decrease. As a confirmation of these observations, there served also the creep test where a decrease of the creep compliance (by two times) for LC-rich blends as compared with pure PP was noted.It also should be emphasized that, generally, a smaller effect of LCP content on the elastic deformation was noted than that on the time dependent effects (nonelastic creep deformation).Published in Mekhanika Kompozitnykh Materialov, Vol. 30, No. 4, pp. 442–450, July–August, 1994.     

Polymer flow in cylindrical channels

The author examines the problem of flow of a polymer melt in a cylindrical channel of arbitrary cross section. It is assumed that the polymer is an isotropic viscoelastic medium. All the coefficients of the equation of state obtained for the flow in question are functions of the second invariant of the strain rate tensor only and can be determined experimentally in simple types of flow. A perturbation method is proposed for the solution of specific problems, the Dirichlet problem for Poisson's equation being solved in each perturbation step.Mekhanika Polimerov, Vol. 2, No. 3, pp. 421–428, 1966     

Possible flow mechanisms of polymer solutions and melts

The experimental results on combined parallel stationary flow and linear periodic deformation are analyzed. The correlation limits of the frequency viscoelastic functions and the stationary flow characteristics, determined by the flow mechanisms at different shear rates, are established.Presented at the 5th Symposium on Rheology, Moscow, May, 1970.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR, Riga. Translated from Mekhanika Polimerov, No. 3, pp. 546–549, May–June, 1971.