Ionization of Acetylacetone in Me2SO—Water Mixtures. Reactivity—Selectivity Principle or Principle of Imperfect Synchronization?

Rate constants for the reversible deprotonation of acetylacetone were measured in carboxylate and amine buffers in water and in 50%, 90% and 95% Me₂SO at 20°C. The Brønsted plot for the carboxylate ions is curved in the Me₂SO—water mixtures, but straight in water. The curvature is in the direction predicted by the Reactivity—Selectivity Principle (RSP). However, the Brønsted plot for the reaction with primary amines is straight in all solvents. This suggests that the curvature observerd with the carboxylate ions is caused by loss of solvation of the base; this loss of solvation is ahead of bond formation in the transition state rather than being a manifestation of the RSP. (Note that all Brønsted plots are based on pK_a values measured in the respective solvents.) The intrinsic rate constant (k₀) for proton transfer increases with the addition of Me₂SO, and more so with the carboxylate buffers than with the amines. This increase in k₀ is attributed to delayed solvation of the developing enolate ion in the transition state; with the carboxylate buffers, an additional factor is the early loss of solvation of the base. The various solvation effects observed in this study can all be understood in the context of the Principle of Imperfect Synchronization (PIS).     

Improved Matrix-Filler Adhesion

Enhanced matrix-filler adhesion is realized after filler treatment with a surface treatment process. The hydrosol/coupling agent treatment was applied to a wide range of inorganic and organic fillers, and adhesion to a variety of matrix resins was improved. Scanning Electron Microscopy (SEM) was used to determine the locus of failure in the filled systems. The locus of failure shows the relative degree of adhesion between the filler and the polymer matrix. Significant improvement in adhesion in humid environments is also observed.     

Effect of Contact Residual Stress Relaxation on Fracture Strength of Indented Soda-Lime Glass

The strength of Vickers-indented soda-lime glass measured in air at room temperature steadily increases with time after indentation, whereas optical retardation steadily decreases in the same interval. Annealing after indentation causes further strength increase and retardation decrease. The results are consistent with Marshall and Lawn's treatment of the slow crack growth of indentation flaws driven by the combined influence of residual contact stress and applied stress. Post-indentation strengthening of indentation flaws can be explained without recourse to flaw blunting.     

Synthesis of Si3N4 with Emphasis on Si-S-N Chemistry

Industrial production of Si₃N₄ from SiCI₄, is increasing. An element rivaling CI in abundance and cheapness with potentially suitable chemistry for this application is sulfur. Thus, Si–S–N chemistry was investigated to determine its usefulness in producing Si₃N₄. Bifunctionality in S, as opposed to mono-functionality in CI, may allow special routes via polymers to become important.     

Segregation of Isovalent Impurity Cations at the Surfaces of MgO and CaO

Enthalpies of segregation for isovalent impurities in magnesium and calcium oxide as a function of surface concentration were calculated by using an atomistic computer simulation method. We have considered Be²⁺, Mg²⁺, Ca²⁺, Ba²⁺, and Ni²⁺, segregating to both (001) and (110) faces. The results obtained can be extrapolated to predict the behavior of other impurities including Mn²⁺, Fe²⁺, and Co²⁺, We find, for example, that Fe²⁺, Mn²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ will concentrate at the (001) surface of MgO, while Ni²⁺ will be depleted. The enthalpy of segregation is found to vary substantially with coverage particularly for the larger impurities. The enthalpy becomes less negative with increasing impurity concentration due to the increasing lattice strain until the surface is nearly saturated. Then additional stabilization is obtained by restructuring of the surface layer. We predict reconstructed surfaces for both the (001) and (110) faces, which contain a high concentration of a larger impurity ion. The enthalpy of segregation shows a maximum at around 50% surface coverage implying a bimodal surface distribution of segregant. The influence of segregation on surface energy suggests two unusual effects. The (001) surface energy of the impure crystal becomes negative for surface concentrations of impurity greater than 10% Ba²⁺ or 75% Sr²⁺ in MgO. This implies a thermodynamic barrier to sintering. At high coverages of Ba²⁺ in MgO the (110) surface becomes more stable than the (001) face suggesting that facetting may occur.     

Knowledge-based understanding of radiology text

A data acquisition tool which will extract pertinent diagnostic information from radiology reports has been designed and implemented. Pertinent diagnostic information is defined as that clinical data which is used by the HELP medical expert system. The program uses a memory-based semantic parsing technique to 'understand' the text. Moreover, the memory structures and lexicon necessary to perform this action are automatically generated from the diagnostic knowledge base by using a special purpose compiler. The result is a system where data extraction from free text is directed by an expert system whose goal is diagnosis.     

The 1987-8 Taulbee Survey report

This report describes the results of a survey completed in December 1988 on the production and employment of PhDs and faculty in PhD-granting computer science/engineering departments during the 1987-8 academic year. All 127 computer science (CS) departments (115 US and 12 Canadian) participated. In addition, 34 departments offering the PhD in computer engineering (CE) were included. Throughout the report. CE statistics are reported separately so that comparisons with previous years can be made for CS. The intent is to merge all statistics for CS and CE after several years     

Semiconductor-insulator structures in the phototargets of vidicons sensitive in the middle infrared region of the spectrum

The kinetics of electronic processes in vidicon phototargets based on semiconductor-insulator structures with a narrow-gap semiconductor is considered taking into account charge drain in the insulator layer and relaxation of the nonequilibrium depletion region in the semiconductor layer. The integration time, threshold sensitivity, and resolution at various intensities of incident radiation are estimated.     

High-load, squeeze action linear bearings with beam deflection

The literature provides little information on high-speed, high-normal-load, plain linear bearings, although the case for two rigid surfaces in relative linear motion can readily be solved by assuming squeeze action resistance. A new genus of internal combustion engines based on the Stiller-Smith mechanism incorporates connecting rods constrained by linear bearings, with the central normal load on the rod restricted by an oil film. A general analysis takes into account the bending of the rod, when the distributed oil film pressure resists the distributed load on the elastic rod. Design charts result that yield the dimensionless velocity at which the rod sinks in the oil as a function of the dimensionless load and the bearing clearance, and predict the deflection of the beam. The rod clearance history simulations for the Stiller-Smith engine compare favourably with computations for the rigid beam, confirming the analysis technique.     

A two-dimensional time-domain finite element formulation for periodic structures

A formulation is presented for a two-dimensional time-domain finite-element method (FEM-TD) that incorporates periodic boundaries. The specifics of the method are shown for scattering problems, but it should be straightforward to extend it to radiation problems. The method solves for a transformed field variable (instead of solving directly for the electric field) in order to easily enable periodic boundary conditions in the time domain. The accuracy and stability of the method is demonstrated by a series of examples where the new formulation is compared with reference solutions. Very accurate results are obtained when the excitation (frequency range) and the geometry are such that no higher order Floquet modes are present. The accuracy is degraded in the presence of higher order modes due to the rather simple absorbing boundary condition that is used with the present formulation. The method is found to be stable even for angles of incidence close to grazing.