V. E. Dreval

Effect of the solvent nature on the rheological properties of concentrated solutions of various polymers

Abstract The paper compares the viscous, high-elastic and viscoelastic properties of solutions in various solvents of four polymers (polyisobutylene, polystyrene, polymethyl methacrylate and acetyl cellulose) differing in chain rigidity and the intensity of molecular interaction, over a wide range of compositions for the linear region of the mechanical behaviour of these systems. For solutions of polyisobutylene and polystyrene, the effect of the nature of the solvent on the viscosity is determined by the inherent viscosity of the solvent and by the fact that solutions under isothermal conditions are not in corresponding states with respect to their glass transition temperatures. The high-elasticity modulus of polyisobutylene and polystyrene solutions is independent of the nature of the solvent and of temperature. This indicates that the fluctuating network of entanglements is insensitive to the nature of the solvent and that the free volume plays the determining role in the behaviour of these solutions. Solutions of acetyl cellulose and polymethyl methacrylate are characterized by a very strong dependence of the viscosity on the nature of the solvent (which cannot be explained by notions valid for solutions of the first two polymers) and also by a change in the high-elasticity modulus with variation in the nature of the solvent and temperature. This proves that the properties of solutions of polar polymers are determined both by the free volume and the density of the fluctuating network, which changes with the solvent and temperature. The shape of the relaxation spectra of solutions of various polydisperse polymers in solvents of different natures is the same, while the specific properties of the solutions are associated with the position of the spectra on the time scale, which determines the fundamental constants of the solutions, viz. the zero shear viscosity and the initial high-elasticity modulus.

Uniaxial extension of linear flexible-chain polymers in an extremely broad range of stresses and strain rates

SummaryThis work summarizes the basic patterns of strainstrength behaviour of linear flexible-chain polymers at uniaxial extension. The boundaries of transition of non-cross-linked polymers under isothermal conditions from the fluid to the high-elastic and leathery states when an axial load is applied are defined. A relationship is established between the parameters of longitudinal and low-amplitude strains. A study is made into the effect of molecular parameters and liquid media on the deformation and rupture of non-cross-linked linear polymers.ZusammenfassungDiese Untersuchung vermittelt einen Überblick über die wesentlichen Züge des Dehnungs- und Festigkeitsverhaltens linearer flexibler Kettenpolymerer bei einachsiger Dehnung. Die Übergangsgrenzen vom flüssigen zum lederartigen und zum hochelastischen Zustand beim Einwirken einer Achsiallast werden für unvernetzte Polymere unter isothermen Bedingungen definiert. Zwischen den Parametern der Dehnbelastung und der periodischen Belastung bei niedriger Amplitude wird eine Beziehung hergestellt. Schließlich wird der Einfluß molekularer Parameter und flüssiger Medien auf die Deformations- und Brucheigenschaften der unvernetzten linearen Polymeren untersucht.

Viscoelastic properties of butadiene-styrene block copolymers

SummaryThe viscous properties of SBS block copolymers (of “Cariflex TR-1102” in this work) have been determined with the rate of shear being varied by 108 times. It has been shown that in the region of low shear rates the polymer behaves as a structured highly concentrated disperse system which exhibits sharply pronounced thixotropy. In the region of high shear rates, the viscous properties of the polybutadiene matrix are of decisive importance. At low values of shear stress the compliance of the SBS block copolymer exceeds that of the polybutadiene matrix almost by a decimal order.At high shear stresses, just as in the case of viscous properties, the elastic behaviour of the SBS block copolymer approaches that of the polybutadiene matrix. Measurements of the dynamic characteristics at frequencies, which vary by a million times, most spectacularly point to the specificity of the viscoelastic properties over a wide temperature range. Under conditions of low temperatures the SBS block copolymer behaves as a rubber, while at temperatures above the glass transition temperature of polystyrene, at low loading intensities (low amplitudes and small deformations) the block copolymer shows low fluidity. This is most clearly seen from the frequency dependence of the loss modulus, especially in comparison with the relation typical of polybutadiene.ZusammenfassungDie viskosen Eigenschaften von SBS-Block-Copolymeren (hier „Cariflex TR-1102“) werden in einem Bereich von acht Zehnerpotenzen der Schergeschwindigkeit untersucht. Es wird gezeigt, daß im Bereich niedriger Schergeschwindigkeiten das Polymer sich wie ein strukturiertes hochkonzentriertes disperses System verhält, das eine ausgeprägte Thixotropie besitzt. Im Bereich hoher Schergeschwindigkeiten sind dagegen die viskosen Eigenschaften der Polybutadien-Matrix von entscheidender Bedeutung. Bei niedrigen Schubspannungswerten übersteigt die Komplianz des SBS-Block-Copolymeren diejenige der Polybutadien-Matrix höchstens um etwa 10%.Bei hohen Schubspannungen nähert sich das elastische Verhalten analog wie bei den viskosen Eigenschaften demjenigen der Polybutadien-Matrix an. Die Messung der dynamischen Charakteristiken über einem Frequenzbereich von sechs Zehnerpotenzen lassen die spezifischen viskoelastischen Eigenschaften in einem weiten Temperaturbereich sehr deutlich erkennen. Bei tiefen Temperaturen verhält sich das Polymer wie ein Gummi, während bei Temperaturen oberhalb der Glasübergangstemperatur des Polystyrols unter geringer Belastung (d.h. kleinen Amplituden bzw. Deformationen) das Polymer eine geringe Fluidität zeigt. Dies erkennt man am deutlichsten an der Frequenzabhängigkeit des Verlustmoduls, insbesondere durch Vergleich mit derjenigen bei Polybutadien.

Thermodynamics of liquid-crystalline solutions of hydroxypropyl cellulose in water and ethanol

Phase diagrams were constructed and comprehensive thermodynamic analysis was performed for hydroxypropyl cellulose-water and hydroxypropyl cellulose-ethanol systems with the use of the static sorption, calorimetry, cloud-point, polarization microscopy, and X-ray diffraction analysis techniques and the measurement of transmitted polarized light intensity. The concentration dependences of the enthalpy, entropy, and Gibbs energy of the formation of liquid-crystalline phases in the systems were determined. It was found that the formation of liquid-crystalline solutions of hydroxypropyl cellulose in water is associated with the energy term of interaction between the components and that in ethanol solutions is due to changes in combinatorial entropy.

Transition of polymers from the fluid to the forced high-elastic and leathery states at temperatures above the glass transition temperature

Abstract The transition from the fluid to the forced high-elastic (rubber-like or quasi-vulkanizate) state and then to the leathery state (that is between rubbery and glassy states ∗∗ ) has been systematically studied by increasing stresses and deformation rates, using an uncured high molecular-mass 1, 2-polybutadiene characterized by a rather high glass transition temperature (−18°C). Investigation of polymers in simple shear is possible up to critical stresses corresponding to the transition of fluid polymers to FHES. Uniaxial extension offers wide possibilities for characterizing polymers in FHES and FLS since it covers the range of 4–6 decades of deformation rates over the range of simple shear. The deformability of polymers is limited by their fracture even in FHES, and the fracture process is determined only by recoverable deformation. The failure envelope covering FHES and transition to FLS has been constructed and the long-term durability in the range of 7 decades of time measured. The maximum extensibility corresponding to the transition of the polymer to FLS is determined by the ultimate extensibility of macromolecular coils. Over a wide range of stresses the polymer behaves like a linear viscoelastic body. This makes it possible to correlate the data obtained for uniaxial extension and low-amplitude sinusoidal shear deformation, which is important for the prediction of fracture phenomena by means of the low amplitude non-destructive dynamic method.

Effect of liquid media on the ultimate strength characteristics of viscofluid polymers in uniaxial extension

Abstract The fracture properties and deformation behaviour of a linear amorphous polymer (1,2-polybutadiene) above the glass-transition temperature (−18°C) in liquid media have been studied. In accordance with data published earlier it is found that when fractured above T g polymers behave like cured elastomers. Experiments conducted in low-molecular alcohols at 10°C show that the ultimate strength, durability (time-to-fracture) and development of irrecoverable deformation of viscous flow depend very strongly on the nature of the liquid medium, whereas the development of the elastic component of deformation is independent of the nature of the alcohols. It has been established that the dependence of durability on true fracture stress for the polymer studied is described by a power function. A simple correlation has been found between the surface tension at the polymer-liquid interface and the durability and ultimate strength of the polymers.

Rheological properties of concentrated aqueous solutions of anionic and cationic polyelectrolyte mixtures

The rheological properties of aqueous solutions of poly(acrylic acid), poly(diallyldimethyldiammonium chloride), and their mixtures at 25°C have been studied. The concentrated solutions of the mixtures contain 18 wt % of both polymers taken at different ratios. The ratio of cationogenic and anionogenic groups φ varied from 0 to 0.4 is taken as a criterion for selection of mixture composition. An increase in φ, reflecting a more intense formation of polyelectrolyte complexes in solution, is accompanied by a significant rise in the low-frequency loss modulus and, especially, in the storage modulus, as well as by an increase in viscosity over the entire studied range of shear rates. This behavior may be explained by the presence of an additional spatial structure with junctions formed by interacting complementary charged groups. In the general case, the formation of poly(acrylic acid)-poly(diallyldimethyldiammonium chloride) polyelectrolyte complexes is said to take place in solution. The excess of rheological characteristics of mixture solutions over the corresponding characteristics of poly(acrylic acid) solutions is found to be the power function of parameter φ. The additional spatial network derived from polyelectrolyte complexes and occurring in solution is destroyed at lower shear stresses than is the network of intermolecular entanglements. At high shear stresses, orientational effects may cause phase separation of the systems owing to a change in the hydrophilic-hydrophobic balance between complexes of poly(acrylic acid) with poly(diallyldimethyldiammonium chloride) and water.

Viscosity and temperature transitions in dimethylacetamide solutions of polyamidobenzimidazole and its blends with polysulfone

The rheological properties of 5% solutions of a fiber-forming polyamidobenzimidazole in DMAA containing LiCl additives and polyamidobenzimidazole-polysulfone blends in the same solvent have been studied. The total concentration of polymer blends with various component ratios is 5 wt %. At temperatures below ∼110°C, the systems under study behave as non-Newtonian fluids and their viscosity decreases with temperature. At T > 110°C, the temperature dependence of viscosity passes through a minimum. The position of the minimum on the temperature scale decreases with the concentration of polyamidobenzimidazole. This character of a change in viscosity is associated with the phase separation of polyamidobenzimidazole solution that leads to its gelation. The temperature corresponding to the minimum viscosity coincides with the onset temperature of a sharp turbidity of solution during heating. It is suggested that solutions containing up to 5% polyamidobenzimidazole possess an LCST. The addition of up to 50% polysulfone has almost no effect on the temperature of transition but brings about a marked decline in the viscosity of the system.

Rheological and mechanical properties of ABS plastics prepared by bulk polymerization

A series of ABS plastics prepared by bulk polymerization was studied. The test samples contained almost equal amounts of PB but mostly differed in the molecular mass of a styrene-acrylonitrile copolymer. It was shown that the molecular mass of the copolymer strongly affects the rheological and mechanical properties of ABS plastics. An increase in molecular mass leads to a rise not only in the non-Newtonian viscosity of plastics but also in their yield point, storage modulus under periodic steady-state shear flow in the low-frequency plateau region, and impact strength. Quantitative correlations between these rheological and mechanical characteristics of the copolymers and their M w values were established. As opposed to homophase polymer systems, a marked increase in the shear stress has no effect on viscosity in relation to the molecular mass of ABS plastics. In the case of melts, the influence of the M w of the styrene-acrylonitrile copolymer on the rheological behavior of ABS plastics is apparently related to a change in the interaction of PB particles with the copolymer that controls the structural framework of the system. The relationship between the impact strength of the copolymer and its M W may be explained by the fact that the latter parameter influences orientational effects in crazes that arise during steady-state shear flow of ABS plastics in the solid state.

Uniaxial extension and shear in combination with cyclic straining as a promising method for studying the viscoelasticity of polymers over a wide range of stresses and strains atT > T g

Simple relations are found between the fracture strains, the long-term durability and the initial values of parameters characterizing polymer rheology at deformation rates and stresses approaching zero. Fracture regimes are determined by two groups of parameters. One includes critical values of stresses. They are invariant with repect to temperature and molecular weight of the polymers; the values of critical stresses for different polymer compositions differ by a factor of 10 to 20. The second group of critical parameters includes the rates of deformation determined by the initial viscosity. The latter may vary by many orders of magnitude. There exists a universal critical value determining polymer fracture independent of linear macromolecule composition, its molecular weight, the temperature and the way of attaining a given state. This value is the recoverable strain and is equal to 0.5 according to Hencky. There exists a relation between the maximum value of recoverable strain in the transition region from the rubbery to the leathery state and the extensibility of macromolecules for polymers with various molecular weights. Quenching of the polymer near the maximum recoverable strain makes it possible to obtain high strength samples. Overspurt regimes for polymer flow have also been studied. It has been shown that this causes polymer static electrification. Simple and unique dependences of the charge density on temperature and polymer molecular weight have been established.