The rheological approach

There is no general method of dealing with non-linear viscoelastic behaviour, and here we summarize approaches that have been applied with some success in 

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R.HEOLOGY IS THE STUDY OF THE RESPONSE OF MATERIALS to an applied shear stress or strain (I). In other words, rheology is a science of deformation (a typical response of solids to an applied strain, elasticity) and flow (a typical response of a fluid to an applied shear, viscosity). Sometimes, the methods that impose a strain are classified as the plasticity approach, whereas the methods that apply shear rates or shear stresses are termed the rheological approach (2). In this review, we focus on the rheological approach, whereas the plasticity approach is dealt with only briefly. 

The rheological approach to rubber processing allows a better understanding of the flow behaviour of elastomers to be achieved. Obviously the picture is far from being complete and due to their complexity, rubber compounds are exhibiting phenomena not yet completely understood. 

In this approach the reviews concerned the rheology involving the linear viscoelastic behavior of plastics and how such behavior is affected by temperature. Next is to extend this knowledge to the complex behavior of crystalline plastics, and finally illustrate how experimental data were applied to a practical example of the long-time mechanical stability. 

Viscoelasticity of metal This subject provides an introduction on the viscoelasticity of metals that has no bearing or relationship with viscoelastic properties of plastic materials. The aim is to have the reader recognize that the complex thermodynamic foundations of the theory of viscoplasticity exist with metals. There have been developments in the thermodynamic approach to combined treatment of rheologic and plastic phenomena and to construct a thermodynamic theory non-linear viscoplastic material that may be used to describe the behavior of metals under dynamic loads. 

There are three different approaches to a thermodynamic theory of continuum that can be distinguished. These approaches differ from each other by the fundamental postulates on which the theory is based. All of them are characterized by the same fundamental requirement that the results should be obtained without having recourse to statistical or kinetic theories. None of these approaches is concerned with the atomic structure of the material. Therefore, they represent a pure phenomenological approach. The principal postulates of the first approach, usually called the classical thermodynamics of irreversible processes, are documented. The principle of local state is assumed to be valid. The equation of entropy balance is assumed to involve a term expressing the entropy production which can be represented as a sum of products of fluxes and forces. This term is zero for a state of equilibrium and positive for an irreversible process. The fluxes are function of forces, not necessarily linear. However, the reciprocity relations concern only coefficients of the linear terms of the series expansions. Using methods of this approach, a thermodynamic description of elastic, rheologic and plastic materials was obtained. 

Fluids whose behaviour can be approximated by the power-law or Bingham-plastic equation are essentially special cases, and frequently the rheology may be very much more complex so that it may not be possible to fit simple algebraic equations to the flow curves. It is therefore desirable to adopt a more general approach for time-independent fluids in fully-developed flow which is now introduced. For a more detailed treatment and for examples of its application, reference should be made to more specialist sources/14-17) If the shear stress is a function of the shear rate, it is possible to invert the relation to give the shear rate, y = —dux/ds, as a function of the shear stress, where the negative sign is included here because velocity decreases from the pipe centre outwards. 

The rheological properties of a fluid interface may be characterized by four parameters surface shear viscosity and elasticity, and surface dilational viscosity and elasticity. When polymer monolayers are present at such interfaces, viscoelastic behavior has been observed (1,2), but theoretical progress has been slow. The adsorption of amphiphilic polymers at the interface in liquid emulsions stabilizes the particles mainly through osmotic pressure developed upon close approach. This has become known as steric stabilization (3,4.5). In this paper, the dynamic behavior of amphiphilic, hydrophobically modified hydroxyethyl celluloses (HM-HEC), was studied. In previous studies HM-HEC s were found to greatly reduce liquid/liquid interfacial tensions even at very low polymer concentrations, and were extremely effective emulsifiers for organic liquids in water (6). 

Modern coating is performed at very high speeds, and the fastest coating operations at the moment are carried out at speeds approaching 1600 metres per minute. The rheology and flow behaviour of the dispersions at these speeds is therefore of paramount importance in the coating process. 

Rossi et al. [30] evaluated rheologically mucins of different origin with polyacrylic acid and sodium carboxymethyl cellulose. The same group also reported a novel rheological approach based on a stationary viscoelastic test (creep test) to describe the interaction between mucoadhesive polymers and mucins [31,32]. Jabbari et al. [33] used attenuated total-reflection infrared spectroscopy to investigate the ehain interpenetration of polyaciylic acid in the mucin interface. 

Caramella, C M., Rossi, S., and Bonferoni, M.C., A Rheological Approach to Explain the Mucoadhesive Behavior of Polymer Hydrogels. In Bioadhesive Drug Delivery Systems (E. Mathiowitz, D.E. Chickering, III, and C.-M. Lehr, eds.), Marcel Dekker, Inc., New York, 1999, pp. 25-65. 

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