Mechanical relaxation processes in polymers

The various kinetic processes are classified and the place of relaxation effects among them is established. The theoretical basis of mechanical relaxation phenomena in polymers is outlined. The characteristics of relaxation processes associated with molecular mobility are examined with reference to various classes of polymers, in particular, amorphous and crystalline polymers, copolymers, and mechanical mixtures. The characteristics of relaxation processes associated with rearrangement of the supermolecular structures in amorphous and crystalline polymers are considered.This article is a review of mechanical relaxation effects in polymers with particular attention to research conducted in the Problem Laboratory of Polymer Physics of the Moscow Lenin State Pedagogical Institute.Problem Laboratory of Polymer Physics, Lenin Moscow State Pedagogical Institute. Translated from Mekhanika Polimerov, Vol. 5, No. 1, pp. 30–53, January–February, 1969.     

Mechanism of the increase in strength and heat resistance of oriented polymeric materials modified by graft copolymerization with vinyl monomers

The mechanical properties and structures of oriented films and fibers composed of polyethylene, polymethyl methacrylate, and other amorphous and crystalline polymers modified by the synthesis of uniformly distributed graft and block copolymers of methyl methacrylate, acrylonitrile, vinylidene chloride and other monomers have been the subject of a comparative investigation. The effect of the grafted polymers on the molecular mobility, relaxation processes, and solubility of the materials is explained by reference to a universal physical "crosslinking" mechanism. A theory of the interrelation between the structure and physical properties of the materials, the nature of the polymers, and the grafting conditions is developed and used to analyze the experimental data on a broad range of systems.V. I. Lenin Belorussian State University, Minsk. Translated from Mekhanika Polimerov, No. 6, pp. 968–975, November–December, 1973.     

Thermofrictional properties of self-lubricating antifriction plastics

New thermally stable polymers (polyimides, polyarylates, and phenolphthalein-phenolformaldehyde copolymers) were used in a study of the thermofrictional properties of their compositions with molybdenum disulfide. We established the existence of several temperature zones of friction and demonstrated their connection with the changes in the relaxation and autohesion properties of the polymers in these same temperature zones.Institute of Organoelement Compounds, Academy of Sciences of the USSR, Moscow. Translated from Mekhanika Polimerov, No. 3, pp. 481–485, May–June, 1970.     

Behavior of copolymers of styrene with polyester-acrylate in isothermal uniaxial compression

The behavior of a series of three-dimensional copolymers of styrene with polyester-acrylate has been investigated in isothermal uniaxial compression and recuperation. The similarity of the behavior of linear and three-dimensional polymers is noted. It is shown that the behavior of polymer specimens in repeat compression after a recuperation period is determined by the relaxational nature of the recuperation process. A relation has been established between the forced-elastic limit in compression and the structure of certain three-dimensional polymers. The effect of the concentration of initiating system components on the forced-elastic limit in compression is demonstrated.Mekhanika Polimerov, Vol. 3, No. 2, pp. 195–199, 1967     

Increasing the adhesion of polymers to metals by adding substances with conjugation systems

The electron-donor properties of polymers with conjugation systems (PCS) and their capability of forming -complexes with metals is of interest in relation to adhesion. Small amounts (0.01–0.1%) of substances with polyconjugation systems (polydiphenylbutadiene, polyphenylacetylene, and copolymers of naphthalene and anthracene with benzene) increase the adhesion between aluminum and polymers used as electrical insulation coatings (polyesters, polyimides, and their derivatives). With optimum PCS dosage, the resistance to peeling rises by 15–38%.Institute of Chemical Physics, Academy of Sciences of the USSR, Moscow. Translated from Mekhanika Polimerov, No. 2, pp. 365–367, March–April, 1974.     

Relation of the reinforcing action of fillers with molecular motion in polymers

In the case of filled systems based on butadiene-styrene copolymers, it has been shown that the attainment of mobility of kinetic segments in definite temperature regions leads in amorphous polymers to an increase in their strength and reinforcement effect, and also to a change in the morphology of the breakdown surface in these temperature regions. The established regularity has been examined from the point of view of the adhesion theory of reinforcement.Moscow Institute of Meat and Milk Industry. Central Scientific-Research Laboratory of Chemical Packaging Materials, Moscow. Translated from Mekhanika Polimerov, No. 5, pp. 909–911, September–October, 1972.     

Nature and mechanism of friction of rubberlike polymers in different physical states

We have investigated the frictional properties of crosslinked butadiene-nitrile and butadiene-styrene copolymers and natural rubber in friction against polished steel under vacuum conditions in the temperature interval from –200 to +150° C, which embraces the glassy and high-elastic states, as well as the transition region between them. The temperature dependence of polymer friction is characterized by two maxima, a principal and a low-temperature maximum. The principal maximum, observed in the glass transition region, is not associated with the mechanical loss maximum observed in the polymers themselves. The temperature dependence of the force of friction is composed of three parts. In the high-elastic region there is an increase in the force of friction with fall in temperature, in accordance with the molecular-kinetic theory of friction of rubberlike polymers. In this region the nature of friction is associated with mechanical losses in the surface layer of polymer. The mechanical losses inside the polymer itself are unimportant. The deviation from the theoretical curve and the fall in the force of friction below a certain temperature in the transition region are chiefly associated with a decrease in the actual area of contact as the polymer passes into the glassy state. In the glassy region the friction is significantly determined by the mechanical losses in the polymer itself associated with the repeated elastic and forced-elastic deformation of the asperities in the layer of polymer in contact with the rigid surface. Therefore the low-temperature maximum is closely related to the mechanical loss maximum observed in the same temperature region in dynamic tests. Apart from this, the friction maximum is also associated with the increase in the forces of adhesion and the reduction of the actual area of contact at temperatures at which a forced-elastic mechanism of compression of the polymer asperities is not realized.Mekhanika Polimerov, Vol. 3, No. 1, pp. 123–135, 1967     

Influence of structure on the mechanical properties of block copolymers

The variation of the strength characteristics of three-block butadiene-styrene copolymers with the characteristic viscosity has been investigated for polymers of fixed styrene content, as has its variation with the styrene and butadiene content. Measurements were made in the temperature range 20–60°C, at rates of elongation of 5, 50, 250, 500, and 1000 mm/min. It was shown that the relationship between the breaking strength of the block-copolymers and the rate of elongation is analogous to that found for rubber vulcanizates, but has specific features determined by their structure. Values are tabulated for the parameters A and n in the equation giving the relationship between the strength and the rate of elongation under isothermal conditions.     

Description of the mechanical relaxation of highly oriented polymers based on their relaxation spectra

Both the shape and width of the relaxation spectra of polymers with different draw ratios are analyzed in regions of relaxation transitions. The analysis substantiates an empirically ascertained linear law governing the frequency distribution of the dynamic modulus E'(ω) of highly oriented polymers in E' = ln ω coordinates, which corresponds to the uniform distribution of a single relaxation time H(τ) ? const. The possibility of describing the temperature dependence of the modulus of highly oriented polymers within a broad temperature range is demonstrated, where a single relaxation time is used and consideration given to the nonuniform distribution of the energy of fundamental vibrations with respect to oscillatory modes.     

Viscous-elastic properties of amorphous polymers used in the polarization-optical method for investigation of stresses

The present article gives the results of an investigation of the mechanical properties of certain optically sensitive polymers under static and dynamic loading. It is shown that the Kelvin-Voight model can be used to describe the behavior of the materials investigated over limited time intervals corresponding to the duration of static or dynamic experiments.B. E. Vedeneev All-Union Scientific-Research Institute of Hydraulic Engineering, Leningrad. Translated from Mekhanika Polimerov, No. 4, pp. 585–596, July–August, 1972.     

Mechanical behavior of a number of polymers at helium temperatures

An experimental investigation of the mechanical behavior of a number of polymers in the range 4.2–240°K has been made. It has been shown that at helium temperature the Poisson ratio is governed by the free volume. It has been established that the dynamic Young's modulus and shear modulus of these polymers at 4.2°K depend on the chemical structure: their values are determined by the mean distance between neighboring macromolecule chains.     

Elastic properties of certain polymer matrices at low temperatures

A study is made of the viscoelastic behavior of the polyimide DFO and polybenzoxasol (PBZ) at low temperatures. Pulsed ultrasound is used to measure ultrasonic velocity in polymers at the frequency f=5 MHz within the temperature interval 4.2–240 K. Data obtained from acoustic measurements is used to calculate the dynamic elastic modulus, shear modulus, compressive bulk modulus, Poisson's ratio, and certain thermophysical characteristics (Debye temperature, specific heat, coefficient of linear expansion, Grünheisen parameter). It is established that the investigated polymers have low dynamic moduli at 4.2 K. Their values change by 18–20% within the temperature range 4.2–240 K. The polymers also have a large free volume at the temperature of liquid helium. The results show that polyimide DFO and PBZ have good service properties at low temperatures.Paper presented at the IX International Conference on the Mechanics of Composite Materials, Riga, October, 1995.Moscow State Academy of Automotive and Tractor Engineering, Russia. Translated from Mekhanika Kompozitmykh Materialov, No. 4, pp. 454–459, July–August, 1996.     

Structure and rheological properties of polymers

The viscoelastic properties of linear flexible-chain polymers with a narrow distribution, for which M > 5M_c (M_c corresponds to the formation of a three-dimensional entanglement network), their mixtures, and concentrated solutions are examined. It is established that under the influence of deformation the polymer may undergo a transition to the rubbery state, which thus defines the limit of its flow state; this transition is also observed in mixtures and concentrated solutions of high-molecular-weight polymers with a narrow distribution. The relative simplicity of the rheological properties of linear high-molecular-weight polymers and their mixtures is determined by the sharpness of the transition to the rubbery state. It has been found that in mixtures of high-molecular-weight polymers the apparent viscosity mechanism associated with a decrease in dissipative losses on transition of the high-molecular-weight components to the rubbery state is dominant; on a broad range of molecular weights (M > M_c), and moreover for polymer solutions, the decrease in entanglement network density under the influence of deformation acquires considerable importance. It is established that the separate effect of the high-molecular-weight components on the viscoelastic properties of their mixtures contradicts the idea of a random network of macromolecular chains. Attention is drawn to the temperature dependence of the viscosity of polymers with a narrow distribution and the dynamic properties of their mixtures. Problems of theoretical and practical interest associated with the particular rheological properties of polymer systems at high deformation rates are defined.     

Viscoelastic parameters of certain polymers in the temperature interval 4.2–240°K

The principal elastic constants of Nylon 6, Nylon 7, Nylon 6.10, Nylon 11, Nylon 12, PVC, PMMA, polystyrene, and polyvinylfluoride have been calculated from data on the velocity of ultrasonic longitudinal and shear waves measured at a frequency of 5 MHz on the temperature interval 4.2–240°K. It is shown that at cryogenic temperatures the dynamic moduli of elasticity are, to a considerable extent, determined by the characteristics of the chemical structure of the polymers. It is suggested that the Poisson's ratios of the polymers depend on their free volume.Scientific-Research Institute of Plastics, Moscow. Translated from Mekhanika Polimerov, No. 4, pp. 604–609, July–August, 1973.     

Comparative analysis of the relaxation spectra of different classes of polymers

The relaxation spectra of different classes of polymers, calculated from successive approximation formulas based on the dynamic and static characteristics at different temperatures, are compared. The effect of the structure of the polymer and the intra- and intermolecular forces on the shape of the relaxation curves is determined.Mekhanika Polimerov, Vol. 4, No. 3, pp. 445–449, 1968     

Effect of the nature of the alkyl group of 2-alkyl-substituted butadienes on the viscoelasticity and strength of polymers obtained by polymerization with butyllithium

The authors have investigated the effect of the substituent in 2-alkyl-substituted butadienes on the viscoelasticity and strength of the polymers obtained by polymerization with butyllithium. It is shown that the dynamic and strength properties of poly-2-alkylbutadienes-1,3 are determined by the nature of the polymerized diene.Mekhanika Polimerov, Vol. 3, No. 4, pp. 596–600, 1967     

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.