Unified equation of state based on the lattice fluid theory for phase equilibria of complex mixtures part I. Molecular thermodynamic framework

Consistent calculation of fugacities of fluid mixtures remains as one of the most important subjects in contemporary molecular thermodynamics. In practice, equations of state (EOSs) and g^E-models have been used. However, most EOSs are erroneous for condensed phases at high densities and g^E-models are inapplicable for pressuresensitive systems. Recently to remedy the shortcomings in both approaches, there has been a surge of new g^E-EOS mixing rules. By equating any set of EOS and g^E-models, the limitations in both approaches could be resolved significantly. However, the self-consistency in the underlying concept of those mixing rules remains controversial. During the last several years, the present authors proposed a new lattice-fluid EOS and its simplification relevant to phase equilibrium calculations. Without employing any g^E-EOS mixing rule and with only two parameters for a pure component and one adjustable interaction energy parameter for a binary mixture, results obtained to date demonstrated that the EOSs are quantitatively applicable to a great variety of phase equilibrium properties of mixtures, especially, for complex and/or macromolecular systems. In the present article we summarize the EOSs and extended the applications to liquid-liquid Equilibria. In part I, we discussed briefly the molecular thermodynamic aspects of general derivation of the EOS and a brief discussion of applying the EOSs to pure fluids while the illustrative application to various real mixture systems is discussed in part II.     

Production of a TiN film with nanoscale particle size by a combined method of plasma-alloy reaction and spray deposition

On leave from: Honda Research and Development Co., Ltd, Wako 351-01, Japan.     

Effects of a Nd—Fe—B magnetic filler on the crystallization of poly(phenylene sulfide)

The crystallization of poly(phenylene sulfide) (PPS) in a polymer–magnetic Nd—Fe—B powder suspension was studied. Isothermal crystallization behavior was analyzed by way of differential scanning calorimetry, and the kinetics were described via the Avrami equation. The Avrami parameters and the crystallization times were strongly affected by both the particle size and the presence of a coupling agent coated on the filler particles. The small Nd—Fe—B particles exhibited long induction and half‐times, whereas the large particles tended to have short crystallization times. Particles ranging from 38 to 150 μ appeared to have similar crystallization times and to have no significant change in the value of Avrami index with melt crystallization temperature. As a result of these analyses, the dynamic mechanical properties were determined to correlate the fundamental polymer crystallization characteristics and the physical properties of the PPS binder. The enhancement of the wetting of the filler to the binder was promoted through the coupling agent, as confirmed by dynamic mechanical testing performed on the samples. The storage modulus typically decreased because of the presence of the uncoated small particles. Conversely, the loss modulus was enhanced because of the presence of the coated small particles in the PPS binder. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1091–1102, 2002     

Passive least-squares-type estimation algorithm for direct adaptive control

The standard least squares (LS) estimation algorithm is modified in such a way that it becomes passive. Therefore the scope of application of the LS algorithm is extended to those adaptive schemes whose convergence proof is based on passivity. The passive version of LS is presented in both continuous and discrete time.     

New substrates of papain, based on the conserved sequence of natural inhibitors of the cystatin family

A discontinuous borate/formate buffer system is presented for horizontal polyacrylamide gel electrophoresis of DNA fragments. The resolution potential of the system could be altered by changing the total monomer concentration (5-9%T), the concentration of the crosslinker piperazine diacrylamide (2-5%CPDA), as well as the concentration of formate in the gel (40-120 mM), the leading ion of the buffer system. The separation of DNA fragments would be improved by increasing the migration distance from 22 to 28 cm. This discontinuous polyacrylamide gel electrophoresis system proved highly reproducible.     

Determination of carbon black fillers in vulcanizates of natural rubber by metathesis degradation

A method for the determination of carbon black fillers in peroxide vulcanizates or sulfur vulcanizates of natural rubber (NR, cis-1,4-polyisoprene) by metathesis degradation with 1-octene was developed using the catalyst WCl₆? (C₂H₅)₃Al₂Cl₃. The carbon black was separated from the reaction mixture by centrifuging and determined by weighing. In this connection, investigations were also performed with the catalyst WCl₆? C₂H₅Al₂Cl₃ which was less suitable for filler determination. The rate of degradation of crosslinked NR with (E)-4-octene was measured. Metathesis reactions of 2-methyl-2-pentene (low-molecular-weight model compound of NR) with 7-tetradecene showed the importance of double bond shift for the degradation of NR.     

Kinetics of zinc oxide formation from zinc sulfide by reaction with lime in the presence of water vapor

A novel reaction scheme for transforming certain metal sulfides to the corresponding oxides has been developed. In this process, steam oxidizes the sulfide into the oxide, and the hydrogen sulfide produced reacts with lime to form calcium sulfide and regenerate steam. There is no net consumption or generation of gaseous species. Thus, the overall reaction can be carried out in a closed system as far as the gas phase is concerned. This eliminates the possibility of emitting hydrogen sulfide out of the reactor. Only certain metal sulfides are thermodynamically amenable to this treatment. In this paper, the reaction of ZnS to ZnO by this scheme is described, together with a detailed formulation of the rate equation for the overall reaction based on the kinetics of the component gas-solid reactions. Although the present work was done with CaO, other suitable oxides may be used in its place. A further potential application of this process is to the selective oxidation of certain sulfide(s) from complex sulfide ores as a treatment prior to the separation of minerals.     

A 4-MB on-chip L2 cache for a 90-nm 1.6-GHz 64-bit microprocessor

A 4-MB L2 data cache was implemented for a 64-bit 1.6-GHz SPARC(r) RISC microprocessor. Static sense amplifiers were used in the SRAM arrays and for global data repeaters, resulting in robust and flexible timing operation. Elimination of the global clock grid over the SRAM array saves power, enabled by combining the clock information with array select signals. Redundancy was implemented flexibly, with shift circuits outside the main data array for area efficiency. The chip integrates 315 million transistors and uses an 8-metal-layer 90-nm CMOS process.     

Single fundamental mode photonic crystal vertical cavity laser with improved output power

The single fundamental mode output power of photonic crystal vertical cavity lasers is improved by varying sizes of oxide apertures and defect lasing apertures. A maximum output power of 3.1 mW in the fundamental mode has been achieved with a new fabrication process that involves only focused ion beam etching to create holes in selectively oxidised VCSELs.