Vibrations of excited molecules at combination and difference frequencies

In the context of the theory of molecular vibrations, by applying the direct product operation of matrices, an equation for the vibrations of vibrationally excited molecules at combination and difference frequencies is obtained. From the solution of this equation, elements of vibration patterns and expressions that can be used for the study of changes in the molecular structural parameters and the coefficients of kinematic interactions are determined. The formulas obtained are applied to the calculation of the anharmonic electro-optical parameters of the molecules of water H₂O and its two isotopes H₂ ¹⁷O and H₂ ¹⁸O. These calculations are performed in terms of the semiempirical quantum-chemical CNDO/2 method and by numerical differentiation of dipole moment functions by employing a cubic spline approximation.     

Rod–coil block copolymers: An iterative synthetic approach via living free-radical procedures

A modular approach has been developed for the synthesis of rod–coil block copolymers involving the initial preparation of a macroinitiator based on the rod block followed by the growth of the coil segment with living free-radical procedures. The key feature of this strategy is the utilization of an alkoxyamine group from the beginning of the synthesis, which serves as a solubilizing group and ensures that each rod block contains a single initiating fragment. Using this approach permits block copolymers based on insoluble biphenyl ester oligomers to be conveniently prepared with coil segments that range from styrenes to acrylates to 1,3-dienes. The tendency of the rod segments to crystallize is strongly dependent on the weight fraction of the rod segment and the chemical nature of the coil segment. Rod–coil molecules containing at least 25–35 wt % polystyrene or poly(n-butyl acrylate) coil segments show a two-dimensional hexagonal arrangement of rod aggregates, as characterized by transmission electron microscopy and small-angle X-ray scattering. Polyisoprene block copolymers exhibit a lamellar microstructure with short rigid domains in which the rod units lie in an interdigitated smectic C arrangement. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3640–3656, 2003     

On the Definition of Temperature in FPU Systems

It is usually assumed, in classical statistical mechanics, that the temperature should coincide, apart from a suitable constant factor, with the mean kinetic energy of the particles. We show that this is not the case for Fermi–Pasta–Ulam systems, in conditions in which energy equipartition between the modes is not attained. We find that the temperature should be rather identified with the mean value of the energy of the low frequency modes.     

Thickness decrease of a grafted polyelectrolyte membrane exposed to shear flow

The effect of the shear flow on the thickness change of a polyelectrolyte membrane grafted onto a glass substrate was directly investigated with a flow cell combined with a confocal laser scanning microscope. The membrane thickness decreased proportionally to an increase in the shear stress of the flow when the shear rate exceeded a critical value of 1 s^?1. The higher the ionic strength was of the fluid, the greater the thinning effect was. The correlation between the critical shear rate and the relaxation of the polymer in the gel membrane was examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2808–2815, 2003     

Growth of Sb-Bi gradient single crystals

The growth conditions and structural quality of Sb-Bi gradient single crystals with Bi content from 2 to 18 at %, grown by the Czochralski method with solid phase feed, are investigated. Bi distribution in the crystals along their pulling direction are studied by electron probe microanalysis and the change in the interplanar spacing is analyzed by double-crystal X-ray diffraction. It is established that the pulling rate and feed mass affect the Bi distribution in Sb-Bi single crystals.     

Thermal-performance evaluation of coolant passages with staggered arrays of pin fins

Three-dimensional laminar forced convection including steady-periodic transition is investigated up to periodic-chaotic transition in the fully developed region of coolant passages with staggered arrays of pin fins. Comparative examples concern overall pressure losses and heat transfer characteristics of circular, square and elliptical pins made of nickel and copper. In the numerical model, transient conjugate heat transfer is assumed and space periodicities in pressure, velocity components and temperatures are taken into account. In the range of operative conditions investigated, overall friction factors increase almost linearly with the Reynolds number, while the increase of overall Nusselt numbers with the Reynolds number is characterized by two slope changes connected with the onset of streamwise vortices, and the shedding of transverse vortices, respectively. The use of copper, instead of nickel, increases the overall Nusselt number with all shapes, but is particularly beneficial to the elliptical section. Square pins are characterized by the highest values of friction factors, but are also the best performers as far as convection enhancing is concerned. The reverse is true for the elliptical pins which are characterized by the lowest values of friction factors, but are the worst performers as far as convection enhancing is concerned. On the basis of overall performances, the elliptical pins made of copper are the best choice, at least in the upper range of Reynolds numbers investigated.     

On automation of the procedure for crystal structure model refinement

The methods of automation of the procedure for crystal structure model refinement from experimental diffraction data, implemented in the ASTRA program package, are described. Such tools as statistical tests, parameter scanning, and data scanning reduce the time necessary for structural investigation. At strong correlations between parameters, especially when the data set is limited, parameter scanning has an advantage over the full-matrix refinement.     

Fatigue Loading and Life Prediction in Three Fretting Fatigue Fixtures

Three fixtures for conducting laboratory fretting fatigue tests are described and their respective testing methods and the results of the analysis are compared. Each of these fixtures has been used to investigate the effects of various parameters of interest in fretting fatigue. These fixtures include a unique apparatus in which all load applied to the specimen is transferred to the fretting pads, an apparatus similar to many found in the literature where partial load transfer occurs across the pads, and a simplified dovetail fixture in which the clamping load, P, and the shear load, Q, are varied in phase. Select test conditions from prior experiments performed on identical material and resulting in similar lives ranging from one to ten million cycles from these fixtures are identified. The various testing conditions were used to compute the unique stress field for each case. The resulting contact stresses were used to calculate crack initiation based criteria, and to calculate stress intensity factors. The three fixtures were shown to be able to accommodate a range of loads, fretting pad contours, and specimen geometries that produced a variety of stress fields. A crack-initiation-based criterion was shown to predict the failure lives of thinner specimens accurately. The stress intensity factor calculations showed the possibility of a crack arresting for a stress field that decays rapidly and the possibility of a local minimum for K as a function of depth. The fixtures are shown to be complementary in generating data for development of robust fretting fatigue models that use these criteria.     

Modeling and simulation of first and second sound in solids

We investigate the propagation of mechanical and thermal waves in solids at cryogenic temperatures. The latter are known as the second sound phenomenon. It occurs, e.g., in dielectric solids and differs greatly from the classical case in which the heat transport proceeds by diffusion. Since Fourier’s law of heat conduction fails for modeling second sound, we apply a non-classical one. During the last two decades, the non-classical thermoelastodynamic theory of Green and Naghdi enjoys steadily growing research activities.