Heterogeneous Plantinum Nucleation and Crystallization of a Heavy-Metal Fluoride Glass

The effect of controlled heterogeneous nucleation by platinum on the crystallization of a ZrF₄-BaF₂-LaF₃-AlF₃-NaF (ZBLAN) glass was studied. Various levels of platinum were incorporated into this glass by a combination of PtCl₂-doping and melting-atmosphere variation. The effect of doping levels and melting conditions on the incorporation of platinum and the subsequent nucleation of crystals was studied by optical microscopy, scanning electron microscopy, differential scanning calorimetry (DSC), and X-ray diffraction. Increased platinum in the glass resulted in an increased number of nucleation sites for the growth of β-ZrF₄-BaF₂ crystals. Analysis of isothermal and ramp-rate DSC measurements indicated that the crystallization of this glass changed from surface controlled to bulk controlled with an increased number of nuclei. This was confirmed by optical microscopy. In addition, Avrami analysis of the isothermal crystallization data gave an accurate approximation of the number of nuclei in the glass.     

Studies of the polymerization of methacrylic acid via free-radical retrograde precipitation polymerization process

In this paper, we present some new results of our work in a novel polymerization process (called the free-radical retrograde precipitation polymerization, or FRRPP, process) that occurs at temperatures above the lower critical solution temperature. Our polymerization experiments basically involve the methacrylic acid–poly(methacrylic acid)–water system. Experimental results indicate a gradual increase in conversion with time after what seemingly is the onset of phase separation. In an equivalent solution polymerization system, conversion of methacrylic acid reaches almost 100% at a much shorter time than in the FRRPP system. Molecular weights of poly(methacrylic acid) at different times for the FRRPP system are not dramatically different from those obtained in the solution system. However, the FRRPP system yields a relatively narrow molecular weight distribution at a wide range of conversion compared to that obtained in the equivalent solution system. The unique characteristics of the FRRPP process is shown in the asymptotic time behavior of the free-radical concentration compared to the decay behavior in other polymerization systems. © 1996 John Wiley & Sons, Inc.     

Suppression of fuel and air stream diluted methane–air partially premixed flames in normal and microgravity

The effects of fuel and air stream dilution (ASD) with carbon dioxide on the suppression of normal and microgravity laminar methane–air partially premixed coflow jet flames were experimentally and numerically investigated. Experiments were conducted both in our normal-gravity laboratory and at the NASA Glenn Research Center 2.2 s drop tower. Measurements included flame topology and liftoff heights of diluted flames, critical diluent mole fractions for flame blowout, and the radiant heat loss from flames. The flames were also simulated using an axisymmetric unsteady numerical code that utilizes detailed chemistry and transport models. In addition, counterflow flame simulation results were used to examine similitude between the counterflow and coflow flame suppression, and further characterize the effectiveness of fuel stream versus ASD on flame extinction. A smaller relative fuel stream dilution (FSD) extinguishes partially premixed flames (PPFs) with increasing premixing as compared to dilution of the air stream. Conversely, smaller ASD is required to extinguish PPFs as they become less premixed and approach nonpremixed (NP) behavior. Fuel stream diluted PPFs and air stream diluted NP flames extinguish primarily through a reactant dilution effect while fuel stream diluted NP flames and air stream diluted PPF are extinguished primarily by a thermal cooling effect. Normal gravity flames lift off and blow out with a smaller diluent mole fraction than microgravity flames. The difference between the fuel and ASD effectiveness increases as the gravitational acceleration is reduced. Radiation heat losses are observed to increase with increasing diluent mole fraction and decreasing gravity.     

Polarographic adsorption wave characteristics of copper complexes of substituted pyrazoles

Polarographic current—potential curves for cupric ions in the presence of low concentrations of 3-methyl pyrazole and 3,5-dimethyl pyrazole show three distinct reduction steps. The most negative of these shows characteristics of an adsorption post-wave and is attributed to the reduction of an adsorbed layer of the cuprous complex.     

Note on flash and distillation systems

Flash and distillation systems evolving on the equilibrium manifold possess stable steady states when the molar flows and the boundary conditions are fixed and a vapor and liquid phase is present at all times. The results extend the range of validity of a local stability theorem for linear, constant molar overflow systems due to Acrivos and Amundson. The approach to stability analysis is motivated by the tangent plane method developed by Gibbs to open systems as it takes advantage of the negative curvature of the entropy surface to construct a Lyapunov function. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3322–3332, 2013     

Effect of nozzle orifice geometry on spray, combustion, and emission characteristics under diesel engine conditions

Diesel engine performance and emissions are strongly coupled with fuel atomization and spray processes, which in turn are strongly influenced by injector flow dynamics. Modern engines employ micro-orifices with different orifice designs. It is critical to characterize the effects of various designs on engine performance and emissions. In this study, a recently developed primary breakup model (KH-ACT), which accounts for the effects of cavitation and turbulence generated inside the injector nozzle is incorporated into a CFD software CONVERGE for comprehensive engine simulations. The effects of orifice geometry on inner nozzle flow, spray, and combustion processes are examined by coupling the injector flow and spray simulations. Results indicate that conicity and hydrogrinding reduce cavitation and turbulence inside the nozzle orifice, which slows down primary breakup, increasing spray penetration, and reducing dispersion. Consequently, with conical and hydroground nozzles, the vaporization rate and fuel air mixing are reduced, and ignition occurs further downstream. The flame lift-off lengths are the highest and lowest for the hydroground and conical nozzles, respectively. This can be related to the rate of fuel injection, which is higher for the hydroground nozzle, leading to richer mixtures and lower flame base speeds. A modified flame index is employed to resolve the flame structure, which indicates a dual combustion mode. For the conical nozzle, the relative role of rich premixed combustion is enhanced and that of diffusion combustion reduced compared to the other two nozzles. In contrast, for the hydroground nozzle, the role of rich premixed combustion is reduced and that of non-premixed combustion is enhanced. Consequently, the amount of soot produced is the highest for the conical nozzle, while the amount of NO_x produced is the highest for the hydroground nozzle, indicating the classical tradeoff between them.     

Explicit equations for laminar flow of herschel–bulkley fluids

There are three typical problems encountered in pipe flows: unknown friction factor, unknown flow rate, and unknown diameter problems. A major problem in determining the solution to these flow problems occurs due to the implicit nature of the Darcy–Weisbach friction factor. Though explicit equations for flow of Newtonian fluids and Power Law fluids are available, no such usable equations exist for Herschel–Bulkley fluids. In this paper, explicit equations have been given for flow of Herschel–Bulkley fluids in the laminar regime.     

First X-ray structure of discrete anion [HgBr5]: Synthesis, characterization and single crystal X-ray structure determination of [Co(NH3)6][HgBr5]

A new cobalt(III) complex salt, [Co(NH₃)₆][HgBr₅](1) was crystallized from a solution of hexaamminecobalt(III)bromide and potassium tetrabromomercurate(II) in aqueous medium in 1:1 molar ratio. This complex salt has been characterized by elemental analyses, spectroscopic techniques (e.g. UV/Visible, IR), solubility product and conductance measurements. The complex salt crystallizes in Orthorhombic crystal system with space group Pnma. Single crystal X-ray structure determination revealed the presence of discrete ions: [Co(NH₃)₆]³⁺ cation and a new anion [HgBr₅]³⁻. This is the first structural report of a complex salt containing this new anion. The structure consists of stacks of cations and anions demonstrating supramolecular arrangements through N–HBr hydrogen-bond interactions. The crystal lattice is stabilized by these non-covalent interactions besides electrostatic interaction.     

Effects of Doping Trivalent Ions in Bismuth Borate Glasses

Bismuth borate glasses from the system: 40Bi₂O₃–59B₂O₃–1Tv₂O₃ (where Tv=Al, Y, Nd, Sm, and Eu) and three glasses of composition: 40Bi₂O₃–60B₂O₃, 37.5Bi₂O₃–62.5B₂O₃ and 38Bi₂O₃–60B₂O₃–2Al₂O₃ were prepared by melt quenching and characterized by density, UV-visible absorption spectroscopy and differential thermal analysis (DTA) studies. Bismuth borate glasses exhibit a very strong optical absorption band just below their absorption edge. Glasses were devitrified by heat treatment at temperatures above their glass transition temperatures and the crystalline phases produced in them were characterized by Fourier transform infrared (FTIR) absorption spectroscopy and X-ray diffraction (XRD). Bi₃B₅O₁₂ was found to be the most abundant phase in all devitrified samples. DTA studies on glasses and FTIR and XRD analysis on crystallized samples revealed that very small amounts of trivalent ion doping causes significant changes in the devitrification properties of bismuth borate glasses; rare-earth ions promote the formation of metastable BiBO₃–I and BiBO₃–II phases during glass crystallization.     

Minimum Cost Systems with Specified Reliability

A method is presented for allocating reliability to each unit of a system with a view to minimizing the system cost. The practical utility of this method, as well as other methods, depends heavily on the availability of cost-reliability data for the 1 constituent units. Unfortunately, for most components such data are not readily available. There is a need for manufacturers and users to make these data available to reliability theoreticians so that the derived results are usefully applied to practical systems. So far, very little seems to have been done in this direction.