Strain function, equilibrium

In Eq. (1), a is the equilibrium stress (Nm 2) supported by the swollen specimen a is the stretched specimen length divided by the unstretched length (extension ratio) v2 is the volume fraction of dry protein and p is the density of dry protein. In the common case of tetrafunctional crosslinks, the concentration of network chains n (mol network chains/g polymer) is exactly one-half the concentration of crosslinks, so that n = 2c. The hypothesis that a specimen behaves as if it were an ideal rubber can be confirmed by observing a linear relation with zero intercept between a and the strain function (a — 1/a2) and by establishing a direct proportionality between a and the absolute temperature at constant value of the extension ratio, as stipulated by Eq. (1). 

Here i —> i is a continuous convex function describing the plastic yield condition. The equations (5.7) provide a decomposition of the strain tensor Sij u) into a sum of an elastic part aijuicru and a plastic part ij, and (5.6) are the equilibrium equations. 

The above equations are generally valid for any isotropic material, including critical gels, as long as the strain amplitude y0 is sufficiently small. The material is completely characterized by the relaxation function G(t) and, in case of a solid, an additional equilibrium modulus Ge. 

The equilibrium interconversion between an ethylene phosphite and a bicyclic spirophosphorane is shown to proceed by the insertion of the phosphite into the labile O-H bond of the hydroxyethyl ester. The mechanism is similar to the insertion of carbenes or nitrenes. Energy relationships of reaction intermediates were studied by MO RHF, MP2(full), MP4SDTQ, and DFT calculations. In most cases, they predicted that hydroxyethyl ethylene phosphates were more stable than the strained spirophosphoranes, which is not supported by the experimental evidence. The best correspondence to experimental data was obtained by DFT calculations with Perdew-Wang correlation functions <2003JST35>. 

The method (27) can best be explained with reference to Figure 2. After stretching to 10, the force f is measured as a function of time. The strain is kept constant throughout the entire experiment. At a certain time, the sample is quenched to a temperature well below the glass-transition temperature, Tg, and cross-linked. Then the temperature is raised to the relaxation temperature, and the equilibrium force is determined. A direct comparison of the equilibrium force to the non-equilibrium stress-relaxation force can then be made. The experimental set-up is shown in Figure 4. 

Polar-substituted alkenes where the functionality is not attached to a strained ring are considerably more discriminating in their compatibility with metathesis catalysts and as a rule require relatively high catalyst charges. In the aliphatic series, unsaturated esters have received the most attention. Boelhouwer reported in 1972 the metathesis of the ester methyl oleate and its trans isomer, methyl elaidate, with a homogeneous catalyst based on a 1/1.4 molar combination of WCl6/(CH3)4Sn (23). At 70°C and an ester/W molar ratio of 33, near-thermodynamic equilibrium was attained, and 49 and 52% of the respective esters were converted to equal amounts of 9-octadecene and the dimethyl ester of 9-octadecene-1,18-dioic acid. 

An important, implicit assumption is that the potential energy function holds only if the nuclear displacement from a position of equilibrium is not too large. Hence, highly strained molecules are not the best targets. Whereas the MM calculations give the steric energy distribution within a molecule, which no other computational method can provide, one must be aware that this distribution is correct for the model of the molecule, not necessarily for the molecule itself (110-... 

In search for true equilibrium shapes, a smaller system with a periodic length equal to 100 fl is used to study isolated islands. In Fig. 5, such isolated islands are examined as a function ofmisfit strain, e. All other input conditions are similar to those ofFig. 3. Whene = 0, the island becomes a semi-circle in the infinite-torque condition, whereas a lense shape with a dihedral angle of 120° should be established in the zero-torque condition. Albeit some facetting due to the discrete nature, the shapes are consistent with the Wulff construction. For 8 0, the shapes of e = 0 are used as the initial configurations. As e increases, the... 

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