Modulus contributions from

Networks with tri- and tetra-functional cross-links produced by end-linking of short strands give moduli which are more in accord with the new theory if quantitative reaction can be assumed (3...13) However, the data on polydimethylsiloxane networks, may equally well be analyzed in terms of modulus contributions from chemical cross-links and chain entangling, both, if imperfect reaction is taken into account (J 4). Absence of a modulus contribution from chain entangling has therefore not been demonstrated by end-linked networks. 

Figure 3. Modulus contributions from chemical cross-links (Cx, filled triangles) and from chain entangling (Gx, unfilled symbols) plotted against the extension ratio during cross-linking, A0, for 1,2-polybutadiene. Key O, GN, equibiaxial extension , G.v, pure shear A, Gx, simple extension Gx°, pseudo-equilibrium rubber plateau modulus for a polybutadiene with a similar microstructure. See Ref. 10.

Thus, the simplified Two-Network experiment shows by a direct comparison of forces at constant length that the trapped entangled structure of a well cross-linked elastomer contributes to the equilibrium modulus by an amount that is approximately equal to the rubber plateau modulus. The modulus contribution from the trapped entangled structure will be less for lower molecular weights and especially at low degrees of cross-linking (14). 

Thus, in the coarse carbon black-fiUed mbber, the modulus increases according to the Guth equation with filler content, because the contribution from the GH layer (1% of the diameter) will disappear... 

The dimensionless constants b and 2 were introduced by Leikin [78] they account for the fact that contributions from each monolayer to the bending modulus and the surface tension can differ for the two modes considered. Such effects are probably small so that bi bj I [78]. We note that the electrical potential enters Eqs. (69) and (70) only through the parameter z. 

According to the arguments based on the constrained-junction model, the term Gch should equate to the phantom network modulus onto which contributions from entanglements are added. 

Since the excellent work of Moore and Watson (6, who cross-linked natural rubber with t-butylperoxide, most workers have assumed that physical cross-links contribute to the equilibrium elastic properties of cross-linked elastomers. This idea seems to be fully confirmed in work by Graessley and co-workers who used the Langley method on radiation cross-linked polybutadiene (.7) and ethylene-propylene copolymer (8) to study trapped entanglements. Two-network results on 1,2-polybutadiene (9.10) also indicate that the equilibrium elastic contribution from chain entangling at high degrees of cross-linking is quantitatively equal to the pseudoequilibrium rubber plateau modulus (1 1.) of the uncross-linked polymer. 

A8. The Helmholtz elastic free energy relation of the composite network contains a separate term for each of the two networks as in eq. 5. However, the precise mathematical form of the strain dependence is not critical at small deformations. Although all the assumptions seem to be reasonably fulfilled, a simpler method, which would require fewer assumptions, would obviously be desirable. A simpler method can be used if we just want to compare the equilibrium contribution from chain engangling in the cross-linked polymer to the stress-relaxation modulus of the uncross-linked polymer. The new method is described in Part 3. 

The two-network method has been carefully examined. All the previous two-network results were obtained in simple extension for which the Gaussian composite network theory was found to be inadequate. Results obtained on composite networks of 1,2-polybutadiene for three different types of strain, namely equibiaxial extension, pure shear, and simple extension, are discussed in the present paper. The Gaussian composite network elastic free energy relation is found to be adequate in equibiaxial extension and possibly pure shear. Extrapolation to zero strain gives the same result for all three types of strain The contribution from chain entangling at elastic equilibrium is found to be approximately equal to the pseudo-equilibrium rubber plateau modulus and about three times larger than the contribution from chemical cross-links. 

The continuous function II( n T) [often simply given the symbol H(r) as in this chapter) is the continuous relaxation spectrum. Although called, by long-standing custom, a spectrum of relaxation times, it can be seen that H is in reality a distribution of modulus contributions, or a modulus spectrum, over the real time scale from 0 to < or over the logarithmic time scale from - to +. ... 

Since the two effects work in parallel in ordinary networks, it is necessary to know the concentration of effective cross-links and to have a molecular theory which correctly relates the modulus to the concentration of cross-links. The contribution from chain entangling is then found as the difference between the observed and the calculated modulus. This seems to be an almost hopeless task unless the network structure is very simple and the contribution from chain entangling is large. 

The first term again represents drag in steady motion at the instantaneous velocity, with Cd an empirical function of Re as in Chapter 5. The other terms represent contributions from added mass and history, with empirical coefficients, Aa and Ah, to account for differences from creeping flow. From measurements of the drag on a sphere executing simple harmonic motion in a liquid, Aa and Ah appeared to depend only on the acceleration modulus according to ... 

From the calculation in (7), the softer PEB region was shown to have maximum adhesive force in nature with the calculated modulus in the range of 15 1 MPa (Table 2). The harder PS domains found to have modulus in the range of 24 1 MPa in the SEBS/clay nanocomposite. The non attractive clay regions generally did not fit the JKR model. This was the reason for obtaining much less modulus than that of the literature values for clays in the GPa range. The discussion infers that the bulk modulus of the SEBS/clay nanocomposite (26 1 MPa as shown in Table 2) was dictated by the contribution from PS domains in the matrix. 

Modulus data on crosslinked systems would seem to offer the most direct method for studying entanglement effects. Certainly, from the standpoint of molecular modeling, the advantages of equilibrium properties are clear. However, the structural characterization of networks has proven to be very difficult, and without such characterization it is almost impossible to separate entanglement contributions from those of the chemical crosslinks alone. Recent work suggests, however, that these problems are not insurmountable, and some quantitative results are beginning to appear. 

T = 140 °C. Here, during solidification, the H increase from 140 °C down to about 100 °C is the result of a double contribution of (a) the crystallization of the fraction of molten crystals and (b) the thermal contraction of the nonpolar phase crystals. The hysteresis behavior is also found in other mechanical properties (dynamic modulus) derived from micromechanical spectroscopy [66, 67], where it is shown that the hysteresis cycle shifts to lower temperatures if the samples are irradiated with electrons. It has also been pointed out that the samples remain in the paraelectric phase, when cooling, if the irradiation dose is larger than 100 Mrad. 

This equation, also as equation (6.49) gives description of the frequency dependency of dynamic modulus at low frequencies (the terminal zone). Both in equation (6.49) and (9.35), the second terms present the contribution from the orientational relaxation branch, while the first ones present the contribution from the conformational relaxation due to the different mechanisms diffusive and reptational. 

The contribution from the first term (reptation branch) has the same order of magnitude as the contribution from the second term at very high frequencies. However, one has to take into account that, due to distribution of relaxation times, the limit value of the first term is reached at higher frequencies than the limit value of the second term. At lower frequencies the plateau value of the dynamic modulus is determined by the second term and coincides with expression (6.52). 

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