Relation between deformation and rotational isomerism

In uniaxially oriented polyethylene and polyethylene terephthalate films conformational transitions were studied by the absorption IR-spectroscopy method during deformation of the specimens carried to rupture in a wide range of temperatures and with different loading methods. It is shown that upon elongation of the polymers the concentration of trans isomers increases and that of gauche isomers decreases. A linear unique relation is obtained between the number of rotational isomers and magnitude of deformation in the amorphous parts of the investigated polymers. It is hypothesized that the conformational transitions determine the magnitude of deformation of amorphous-crystal-line polymers.A. F. Ioffe Physicotechnical Institute, Academy of Sciences of the USSR, Leningrad. Translated from Mekhanika Polimerov, No. 6, pp. 1077–1080, November–December, 1975.     

Strength properties of oriented amorphous linear polymers in relation to their structure

Tensile tests have been conducted at room temperature on uniaxially oriented films of a number of amorphous linear polymers. It has been shown that the mechanical properties of the oriented polymers in the glassy state are chiefly determined by two parameters of the structure—the degree of orientation of the macromolecule segments and the concentration of stressed chains per unit volume, irrespective of the molecular weight of the polymer and the orientational stretching conditions.Mekhanika Polimerov, Vol. 3, No. 3, pp. 455–460, 1967     

Thermomechanical behavior of liquid-crystal polyesters

We have used the thermomechanical method to investigate the processes of self-elongation and shrinkage in uniaxially oriented liquid-crystal (LC) polyesters (CPET — the copolyester of terephthalic acid, phenylhydroquinone, and p-hydroxybenzoic acid; Ultrax — the copolyester of terephthalic acid, isophthalic acid, and bisphenol) and the injection-molded copolyester of hydroxybenzoic and hydroxynaphthoic acids Vectra A900. A universal tensile tester and a thermomechanical tester were used for the investigations. We studied the deformation behavior for the first and second heating under negligible applied stress. We prepared CPET samples in the form of as-spun and annealed fibers, Vectra samples in the form of cubes cut from the nonoriented part of the molded piece (VI) and from the longitudinally oriented central part (VII), Ultrax samples in the form of strands (noncrystalline UI and crystalline UII). We observed a permanent length increase for the as-spun CPET (Fig. 1) and shrinkage in the glass-transition region for the annealed CPET (Fig. 2) for the first and second heating. Note that the as-spun CPET is a smectic polymer, and the annealed CPET contains smectic and crystalline phases. The thermomechanical curves of VI seem to be typical of any molded polymer (Fig. 3). In contrast, for the oriented VII we see spontaneous elongation upon heating in the direction of orientation, with pronounced transverse shrinkage (Fig. 4). The length increase for the noncrystalline UI is quite considerable for the first heating. We observed both spontaneous elongation below the glass-transition temperature and subsequent shrinkage for crystalline UII for the first heating. All the Ultrax curves are much smoother for the second heating (Fig. 5). Spontaneous elongation upon heating appears to be a characteristic feature of oriented LC polymers, the polymer being either fully oriented or oriented within some part of the sample. Shrinkage of LC polyesters upon heating is also possible, as a result of both processing factors and crystallinity. There are two types of restructurization processes: orientation and crystallization (possible for LC polymers capable of forming a crystalline phase).A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia. Translated from Mekhanika Kompozitnykh Materialov, Vol. 32, No. 1, pp. 98–105, January–February, 1996.     

Uniaxial deformation of partially crystalline oriented polymers (fibers)

The uniaxial deformation of partially crystalline oriented polymers is examined under the following assumptions: the volume of the specimen is constant, deformation is affine, stable and reversible, and the crystallites are only slightly deformable as compared with the deformation of the amorphous part. A general expression is obtained for the applied load as a function of the crystallinity, anisotropy factor, and relative elongation. The following cases are considered: isotropic, completely amorphous specimen; isotropic, partially crystalline specimen; and highly oriented, partially crystalline specimen. The results obtained are compared with experimental data.Mekhanika Polimerov, Vol. 3, No. 1, pp. 24–28, 1967     

Some laws of the elastic properties of oriented fibrous polymers and fibers

The author considers the results of calculations of the limiting values of the elastic properties (modulus of elasticity and load-extension diagram) of the main types of chemical fibers, using a model with "ideal orientation" of the molecules and the derived laws of deformation of polymer chains. A method is proposed for calculating the elastic properties of "ideally oriented" polymers from the velocity of propagation of an elastic deformation pulse and the effective density of the "skeletons" of the polymer chains. Values of the moduli of elasticity of the amorphous regions of the structure of oriented polymers are calculated. The calculated results are compared with experimental data on the elastic properties of fibers.Mekhanika Polimerov, Vol. 2, No. 1, pp. 34–42, 1966Paper read at the XIV All-Union Conference on High-Molecular Compounds, Oriented State.     

Elasticity of the crystal lattice of polyethylene terephthalate

The elasticity of the crystal lattice of polyethylene terephthalate was studied along and across the axes of the polymer molecules. The elastic modulus across the chains depended on the degree of crystallinity and the interplane distances in the directions of thea and b parameters of the unit cell. The nature of the elastic deformation in the crystal lattice was analyzed, and its elastic modulus along and across the axes of the chains was calculated. On loading biaxially oriented amorphous-crystalline polymers with a tensile stress applied in the direction of one of the orientation axes of the polymer, the stresses in the crystallites oriented along and across the external applied force and the amorphous regions in series with them were equal to the stress in the sample averaged over the cross section.Deceased.Translated from Mekhanika Polimerov, No. 6, pp. 982–986, November–December, 1972.     

Relaxation processes in oriented amorphous and crystalline polymers

Studies were made of the experimental data on the relaxation processes leading to the preferential molecular disorientation and uniaxially drawn amorphous and crystalline polymers.A. F. Ioffe Physicotechnical Institute, Academy of Sciences of the USSR, Leningrad. Translated from Mekhanika Polimerov, No. 5, pp. 787–792, September–October, 1972.     

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.     

Instability of the crystallites in oriented polymers under load

Large-angle x-ray diffraction and infrared spectroscopy have been used to investigate the behavior of the crystalline zones in oriented polymers under load. It is shown that under the influence of a load applied along the axis of orientation the crystallites are partially destroyed, the more so the greater the applied stress. For different polymers the destruction of the crystallites is the greater the weaker the intermolecular bonds. The stability of the crystallites is improved by orientation.A. F. Ioffe Physicotechnical Institute, Academy of Sciences of the USSR, Leningrad. Translated from Mekhanika Polimerov, No. 3, pp. 516–520, May–June, 1976.     

Changes in the structure of polymeric materials in a magnetic field

It is shown that the action of a magnetic field leads to a change in the supermolecular structure of crystalline polymers. The creation of an oriented state in amorphous thermoplastics and thermosets is accompanied by an increase in their hardness and the homogeneity of the structural state.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR, Riga. Translated from Mekhanika Polimerov, No. 4, pp. 737–739, July–August, 1973.     

Study of a polyethylene terephthalate film by an acoustic method

The effect of orientation on the acoustic properties of a polyethylene terephthalate film is examined. In a crystallized, uniaxially oriented film the velocity of ultrasound measured along the orientation axis is lower than in an amorphous oriented film, while the velocity of ultrasound measured at angles of over 35° to the direction of orientation rises after crystallization. Evidently the supramolecular organization of the polyethylene terephthalate film before and after heat treatment is quite different.Scientific-Research Institute of Plastics, Moscow. Voronezh Branch of the Experimental Design Office of Automation. Translated from Mekhanika Polimerov, No. 4, pp. 759–761, July–August, 1972.     

Effect of the deformation of the film -substrate system on the physicochemical properties of films and their adhesion strength

It was shown that the mechanism of deformation of films of rigid crosslinked polymers (polyester, polyester imide, polyester cyanurate) is appreciably different from the deformation mechanism of free films: a forced highly elastic deformation takes place, sometimes even at an early stage, while the free films deform reversibly up to rupture. Explanations have been suggested for the characteristic features of deformation of films studied on a substrate. The forced highly elastic deformation process is related to the effect of orienting reinforcement of films. An increase in the adhesion strength in the film-substrate system during the deformation has been shown, and an explanation of this effect has been proposed.V. I. Lenin All-Union Electrotechnical Institute, Moscow. Translated from Mekhanika Polimerov, Vol. 9, No. 3, pp. 526–530, May, 1973.     

Effect of hydrostatic pressure on the tensile strength of polymer materials

The effect of hydrostatic pressure on the tensile strength of amorphous, crystalline, and thermosetting polymers has been investigated. The maximum hydrostatic pressure was 2000 kgf/cm². The surfaces of some specimens were protected from the ambient medium (oil). The tests showed that hydrostatic pressure improves the strength or high-elastic limit and Young's modulus of all the materials investigated. In the case of brittle materials, the increase in strength is greater if the surface is protected, whereupon the plasticity is also improved. Hydrostatic pressure produces important changes in the deformation behavior of crystalline polymers.Mekhanika Polimerov, Vol. 3, No. 6, pp. 1043–1047, 1967     

Lamellar structure and plasticity micromechanisms in bulk crystalline polymers. Communication 2

Conclusions 1. It has been experimentally established that the deformation of crystalline polymers is accompanied by the shear transitions between lamellar crystals of different orientations characteristic of martensitic structures.2. It is concluded that the reversibility of the large deformations of linear polymers is martensitic in nature.For communication 1 see [1].E. O. Paton Electrowelding Institute, Academy of Sciences of the Ukrainian SSR, Kiev. Translated from Mekhanika Polimerov, No. 6, pp. 963–969, November–December, 1976.     

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.     

Conformational transitions associated with the deformation of oriented polyethylene fibers

It is shown that, as the elastic deformation of the polymer increases, the number of gauche isomers in oriented polyethylene fibers decreases linearly.A. F. Ioffe Physicotechnical Institute, Academy of Sciences of the USSR, Leningrad. Translated from Mekhanika Polimerov, No. 1, pp. 170–172, January–February, 1970.     

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.     

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.     

Relation between the elastic deformation of oriented specimens of crystalline polymers and the "large-period" deformation

Illustrative calculations for a specific model of the supermolecular organization of an oriented crystalline polymer are presented as an explanation of the fact that the "large-period" deformation may exceed the macrodeformation of the specimen.Institute of High-Molecular-Weight Compounds, Academy of Sciences of the USSR, Leningrad. Translated from Mekhanika Polimerov, No. 4, pp. 579–583, July–August, 1973.     

Volume strains of polymers under short-time loading

The effect of the magnitude of the stress, the type of stress, and the previous loading history on the nonlinear deformation characteristics, the lateral strain coefficient, and the volume strains of two crystalline polymers has been investigated.Institute of Polymer Mechanics, Academy of Sciences of the Latvian SSR, Riga. Translated from Mekhanika Polimerov, No. 5, pp. 828–833, September–October, 1974.