Valence photoisomerization of 2H-pyrans

Conclusions 2H-Pyrans under the influence of UV light undergo reversible cleavage of the C-O bond and are isomerized to the corresponding dienones, for which reversible photochemical cis-trans isomerization around the C=C bond is characteristic, and not photochemical cyclization to 2H-pyrans.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 390–394, February, 1981.The authors express their deep gratitude to V. A. Kuz'min for a valuable discussion of the study results.     

Excitation of Bloch oscillations in a lateral semiconductor superlattice under the influence of electromagnetic pulses

The conversion of the carrier frequency of electromagnetic pulses in lateral semiconductor superlattices, associated with the excitation of Bloch oscillations in the superlattice, is studied theoretically. Conditions are found that are necessary for the observation of the radiation of a Bloch oscillator. The energy characteristics of the efficiency of frequency multiplication and the spectral distribution of the radiation transmitted through the superlattice are calculated. It is shown that low-frequency collisions of electrons do not suppress the excitation of Bloch oscillations, which can be observed under the interaction of the superlattice not only with a pulsed, but also with a continuous-wave signal.     

Effect of the solvent nature on the rheological properties of concentrated solutions of various polymers

The paper compares the viscous, high-elastic and viscoelastic properties of solutions in various solvents of four polymers (polyisobutylene, polystyrene, polymethyl methacrylate and acetyl cellulose) differing in chain rigidity and the intensity of molecular interaction, over a wide range of compositions for the linear region of the mechanical behaviour of these systems. For solutions of polyisobutylene and polystyrene, the effect of the nature of the solvent on the viscosity is determined by the inherent viscosity of the solvent and by the fact that solutions under isothermal conditions are not in corresponding states with respect to their glass transition temperatures. The high-elasticity modulus of polyisobutylene and polystyrene solutions is independent of the nature of the solvent and of temperature. This indicates that the fluctuating network of entanglements is insensitive to the nature of the solvent and that the free volume plays the determining role in the behaviour of these solutions. Solutions of acetyl cellulose and polymethyl methacrylate are characterized by a very strong dependence of the viscosity on the nature of the solvent (which cannot be explained by notions valid for solutions of the first two polymers) and also by a change in the high-elasticity modulus with variation in the nature of the solvent and temperature. This proves that the properties of solutions of polar polymers are determined both by the free volume and the density of the fluctuating network, which changes with the solvent and temperature. The shape of the relaxation spectra of solutions of various polydisperse polymers in solvents of different natures is the same, while the specific properties of the solutions are associated with the position of the spectra on the time scale, which determines the fundamental constants of the solutions, viz. the zero shear viscosity and the initial high-elasticity modulus.     

Rheologische Eigenschaften der Gele auf der Basis siliciumorganischer Polymere

Ohne Zusammenfassung     

Microstructure and rheological properties of polybutadienes

The viscosities, rubbery deformations, densities, and their dependence on temperature have been measured for several series of polybutadienes with molecular weights ranging from 5,000 to 400,000 and differing in proportions of cis and trans structures (cis content from 40 to 95%). On the basis of the viscosity measurements the critical molecular weight M_c has been determined, corresponding to a sharp change in the nature of the viscosity versus molecular weight dependence. Rubbery deformations are displayed pronouncedly in specimens with M > M_c and are closely related to the appearance of non-Newtonian flow. The value of M_c depends on the relative content of cis and trans forms. When M > M_c, the initial viscosity is a parameter sensitive to the microstructure of polybutadienes, so that with at a single molecular weight, depending on the ratio of cis and trans units, the viscosity may vary over a more than tenfold range. The glass transition temperature and activation energy of viscous flow rise regularly with increasing trans content in the polymer chain, these parameters becoming independent of the molecular weight for specimens with M > M_c within a series of polybutadienes of equal microtacticity. Thermomechanical investigations of polybutadienes also made it possible to define more accurately the boundaries of the crystallization region and the dependence of the melting point on the microtacticity. The results obtained are discussed on the basis of modern ideas of polymer structure.     

Nonlinear dynamics of free electron terahertz lasers with bragg mirrors based on coupling of traveling and quasi-critical waves

Combination of various modifications of Bragg structures makes it possible to control electromagnetic fluxes in the interaction space, thus ensuring spatial coherence of radiation for high superdimensionality in two transverse coordinates required, which is for the operation of free electron lasers with distributed feedback in the submillimeter range. We propose that coupling between traveling and quasi-critical waves in the input Bragg mirror be used for mode selection in the “narrow” transverse coordinate directed along the normal to the conductors forming a planar waveguide. A traditional Bragg structure coupling copropagating and counterpropagating wave flows can be used as the output mirror.