Rubber elasticity stress-strain relations

This consists of experimental measurements of stress-strain relations and analysis of the data in terms of the mathematical theory of elastic continua. Rivlin7-10 was the first to pply the finite (or large) deformation theory to the phenomenologic analysis of rubber elasticity. He correctly pointed out the above-mentioned restrictions on W, and proposed an empirical form... 

Because the strain energy function for rubber is valid at large strains, and yields stress-strain relations which are nonlinear in character, the stresses depend on the square and higher powers of strain, rather than the simple proportionality expected at small strains. A striking example of this feature of large elastic deformations is afforded by the normal stresses tn,(22,133 that are necessary... 

Figure 5 demonstrates the different behaviour resulting from Eqs. (49) and (54) in the case of uniaxial compression. We also tested the elastic potential (Eq. (44)) in the two cases v = 1/2 and v = —1/4 by comparing the corresponding stress-strain relations with biaxial extension experiments which cover relatively small as well as large deformation regions for an isoprene rubber vulcanizate. In the rectan-... 

Let us consider in more detail the elasticity of nematic rubbers, which is at the heart of understanding their specific properties. Consider a weakly crosslinked network with junction points sufficiently well spaced to ensure that the conformational freedom of each chain section is not restricted. We recall that for a conventional isotropic network the stress-strain relation for simple stretching (compression) of a unit cube of material can be derived as [62, 63] ... 

The difference between nematic and isotropic elastomers is simply the molecular shape anisotropy induced by the LC order, as discussed in Sect. 2. The simplest approach to nematic rubber elasticity is an extension of classical molecular mbber elasticity using the so-called neo-classical Gaussian chain model [64] see also Warner and Terentjev [4] for a detailed presentation. Imagine an elastomer formed in the isotropic phase and characterized by a scalar step length Iq. After cooling down to a monodomain nematic state, the chains obtain an anisotropic shape described by the step lengths tensor Ig. For this case the stress-strain relation can be written as ... 

In the field of rubber elasticity both experimentalists and theoreticians have mainly concentrated on the equilibrium stress-strain relation of these materials, i e on the stress as a function of strain at infinite time after the imposition of the strain > This approach is obviously impossible for polymer melts Another complication which has thwarted the comparison of stress-strain relations for networks and melts is that cross-linked networks can be stretched uniaxially more easily, because of their high elasticity, than polymer melts On the other hand, polymer melts can be subjected to large shear strains and networks cannot because of slippage at the shearing surface at relatively low strains These seem to be the main reasons why up to some time ago no experimental results were available to compare the nonlinear viscoelastic behaviour of these two types of material Yet, in the last decade, apparatuses have been built to measure the simple extension properties of polymer melts >. It has thus become possible to compare the stress-strain relation at large uniaxial extension of cross-linked rubbers and polymer melts ... 

From the viewpoint of the mechanics of continua, the stress-strain relationship of a perfectly elastic material is fully described in terms of the strain energy density function W. In fact, this relationship is expressed as a linear combination erf the partial derivatives of W with respect to the three invariants of deformation tensor, /j, /2, and /3. It is the fundamental task for a phenomenologic study of elastic material to determine W as a function of these three independent variables either from molecular theory or by experiment. The present paper has reviewed approaches to this task from biaxial extension experiment and the related data. The results obtained so far demonstrate that the kinetic theory of polymer network does not describe actual behavior of rubber vulcanizates. In particular, contrary to the kinetic theory, the observed derivative bW/bI2 does not vanish. 

Thus, this consideration shows that the thermoelasticity of the majority of the new models is considerably more complex than that of the phantom networks. However, the new models contain temperature-dependent parameters which are difficult to relate to molecular characteristics of a real rubber-elastic body. It is necessary to note that recent analysis by Gottlieb and Gaylord 63> has demonstrated that only the Gaylord tube model and the Flory constrained junction fluctuation model agree well with the experimental data on the uniaxial stress-strain response. On the other hand, their analysis has shown that all of the existing molecular theories cannot satisfactorily describe swelling behaviour with a physically reasonable set of parameters. The thermoelastic behaviour of the new models has not yet been analysed. 

Nonmetallic substances show a wide variety of stress-strain diagrams, with each type related to the bonding of the particular material. One type, that for an elastomeric rubber, is shown in Fig. 12. Compared to a metal, the rubber can support much larger strains and only much smaller stresses. It follows Hook s law only as a limit at very small displacements. However, displacement is elastic well outside of this range. 

FIGURE 17.11 The effect of ri (the number of statistical chain elements in a cord between cross-links) on the relation between stress and strain of a polymer gel in elongation. a0 is the force divided by the original cross-sectional area of a cylindrical test piece, v is twice the cross-link density, L is the length, and L0 the original length of the test piece. (After calculations by L. R. G. Treloar. The Physics of Rubber Elasticity. Clarendon, Oxford, 1975.)... 

Tensile properties that are related to fiber stiffness can be used to measure the T of almost all fibers. The elastic modulus, that is, the sl pe of the Hookean region of the fiber stress-strain curve, is a measure of the fiber stiffness and can be used for T determination since, by definition, a glass is stlffer than rubber (Figure 6). Since the transition from a glassy to a rubbery state Involves a reduction in stiffness, the temperature at which the modulus is abruptly lowered is taken as... 

The Vc and Me values for crosslinked polymer networks can also be evaluated from stress-strain diagrams on the basis of theories for the rubber elasticity of polymeric networks. In the relaxed state the polymer chains of an elastomer form random coils. On extension, the chains are stretched out, and their conformational entropy is reduced. When the stress is released, this reduced entropy makes the long polymer chains snap back into their original positions entropy elasticity). Classical statistical models of entropy elasticity affine or phantom network model [39]) derive the following simple relation for the experimentally measured stress cr ... 

It was mentioned earlier that rubber elasticity is related to the high levels of entropy present in the undeformed state. Deformation, therefore, involves application of energy, some of which is necessary to overcome inter- and intramolecular forces, the remainder is stored, but is released on recovery from the deformation. The recovery stress-strain curve, therefore, never coincides with the loading curve, with the loss of energy being known as hysteresis. 

The standard stress-strain curve described in Chapter 3 displays important characteristics for rigid or elastomeric materials. Since elastomeric designs usually do not need high strengths, elongation is important and can be related to flexibility and softness. Elastomers are capable of extreme elastic deformation at low levels of stress. This strain is not proportional to stress (see Figs. 6-26 and 6-27). Like solid plastics, the elastomers become brittle below their Tg, which is in the range of - 20°C ( 4 F) for most rubbers and about -60°C (-75°F) for natural and silicone rubbers. 

Masao Doi and Sam F. Edwards (1986) developed a theory on the basis of de Genne s reptation concept relating the mechanical properties of the concentrated polymer liquids and molar mass. They assumed that reptation was also the predominant mechanism for motion of entangled polymer chains in the absence of a permanent network. Using rubber elasticity theory, Doi and Edwards calculated the stress carried by individual chains in an ensemble of monodisperse entangled linear polymer chains after the application of a step strain. The subsequent relaxation of stress was then calculated under the assumption that reptation was the only mechanism for stress release. This led to an equation for the shear relaxation modulus, G t), in the terminal region. From G(t), the following expressions for the plateau modulus, the zero-shear-rate viscosity and the steady-state recoverable compliance are obtained ... 

The general effect of cross-link density on the elastic modulus of an elastomer is indicated by Eq. 2.3. In their paper Landel and Fedors [189] consider the influence of a time-dependent cross-link density on the shape of the stress-strain curves of silicon, butyl, natural, and fluorinated rubbers. Introducing an additional shift-factor a related to the cross-link density, they were able to represent reduced breaking stresses as a function of reduced time in one common master curve. 

Leonov model This constitutive equation is based on irreversible thermodynamic arguments resulting from the theory of rubber elasticity [5]. Mathematically it relates the stress to the elastic strain stored in the polymer melt as ... 

For a rectangular rubber block, plane strain conditions were imposed in the width direction and the rubber was assumed to be an incompressible elastic solid obeying the simplest nonhnear constitutive relation (neo-Hookean). Hence, the elastic properties could be described by only one elastic constant, the shear modulus jx. The shear stress t 2 is then linearly related to the amount of shear y [1,2] ... 

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