This paper studies the competition between electric and mechanical force fields simultaneously applied to a polar elastomer that can lead to electric breakdown. The analysis of the system, performed assuming that the free energy of the elastomer is simply the addition of polarizing and stretching energies leads to the classical “thermodynamic” (in this case “electromechanical”) stability.
The synthesis of several polyesters from p,p′-bibenzoic acid and diols bearing ether bonds in asymmetric positions is described. The polyesters develop smectic mesophases, the type of which depends on the chemical structure of the spacer. The ether groups and the asymmetry of the spacers stabilize the liquid crystalline order in these polymers. Glass transition and isotropization temperatures, enthalpies, and entropies of the thermotropic polyesters are reported. Comparison of the melting entropies with the conformational entropies of the chains suggests a great disorder in the mesophases of thermotropic polyesters. For some polyesters, the stretched polymer chains do not follow the direction of the fiber axis, an unusual phenomenon that has already been described for some polybibenzoates with aliphatic separators. The influence of the strain rate on the anomalous flow is discussed.
Based on creep and creep‐recovery measurements, the viscoelastic functions [J(t), Jr(t), J′(ω), J″(ω), G′(ω), G″(ω), and L(lnτ)] are presented for solutions of a narrow molecular‐weight‐distribution polystyrene in tri‐m‐tolyl phosphate in the concentration range of 1% to 100% polymer. For concentrations of 25% polymer and above, two maxima are exhibited by the retardation spectrum, L(lnτ). In the neighborhood of each of the maxima the retardation spectra of the more concentrated solutions can be superimposed by translations along both the logL and logτ axes. Reflecting the increasing width of the rubbery plateau with increasing polymer concentration, the dependence of the concentration time‐scale shift factors is greater for the terminal region of response. The response of the solvent is seen at the lower concentrations and it is a less sensitive function of the concentration than that of the polystyrene. This behavior is associated with the previously reported observation of two glass‐transition temperatures in the middle concentration range. For the higher concentrations, both the steady‐state and rubbery‐plateau compliances are inversely proportional to the square of the concentration.
This work reports the permeation of argon through membranes prepared from poly(pentaerythritoltribenzoate acrylate) (PPTBA) (IUPAC name poly[1-(3-benzoyloxy-2,2-dibenzoyloxymethylpropyloxy)-2-propen-1-one]). The permeation measurements were performed in the vicinity of the
glass transition temperature of the membranes (48 °C). The permeation coefficient only shows a slight
dependence on temperature in the glassy state, but it undergoes a sharp increase with temperature in
the rubbery state. The results for the diffusion coefficient do not show a definite temperature dependence
in the glass−rubber transition. As expected, the solubility of the gas in the membrane is higher in the
rubbery state than in the glassy state. The diffusion coefficient was calculated theoretically by using
the Transition-State Approach which assumes that the diffusant path is independent of the structural
relaxations in the polymer matrix. Reasonably good agreement between the simulated and the
experimental values of the diffusion coefficient was obtained in the range of temperatures from 40 to 60
°C in which the measurements were performed.
The viscoelastic behavior of solutions of a narrow molecular weight distribution polystyrene in tri‐m‐toly 1 phosphate has been determined from the glassy to the terminal zones of response. The polymer concentration was varied from one to 100% thereby providing for the first time a complete picture of the influence of a solvent on the time‐dependent response of a polymer.
A computer analysis, governed by human judgment, has been used to extract retardation spectra which can be used to regenerate the reduced recoverable creep compliance curves within the scatter bands of the data. With the resulting retardation spectra, dynamic compliance and moduli curves have been calculated.
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