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  • Chemical Engineering  (70)
  • Wiley-Blackwell  (70)
  • 1995-1999  (70)
  • 1995  (70)
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 1874-1888 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A detailed chemical kinetics model comprising 148 reversible elementory reactions for the supercritical water oxidation (SCWO) of methane, methanol, carbon monoxide and hydrogen was developed. Rate constants were taken from previous critical evaluations. The Lindemann model, at times modified with a broadening parameter, was used to account for the effects of pressure on the kinetics of unimolecular reactions. Model predictions were compared with published experimental SCWO kinetics data for 450-650°C and 240-250 atm. The model correctly predicted global reaction orders for all four fuels to within their uncertainties. In addition, the model correctly predicted that the global reaction orders for O2 during methanol and hydrogen oxidation were essentially zero, and that the O2 concentration had the greatest effect on the methane oxidation rate. The pseudo-first-order rate constants predicted by the model were consistently higher than the experimental values, but the global activation energies were predicted correctly for methane oxidation and for CO and H2 oxidation at high temperatures. The model's predictions generally became worse as the temperature decreased toward the critical point of water. A sensitivity analysis revealed that fewer than 20 elementaty reactions largely controlled the oxidation kinetics for the compounds studied. Nearly half of these reactions involved HO2, which is an important free radical for SCWO. Quantitative agreement with the experimental methane conversions was obtained by adjusting the preexponential factors for three elementary reactions within their uncertainties. It could also be obtained by using the JANAF value (0.5 kcal/mol) for the standard heat of formation of HO2, but this value is lower than other recently recommended values.
    Additional Material: 11 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 1005-1009 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Partial specific volumes at 25°C are reported for α-chymotrypsinogen in aqueous solutions containing NaCl, citrate, and/or polyethylene gycol (PEG) over a range of protein concentrations. The concentration dependence of the partial specific volume can be either positive or negative, depending on the solvent. For example, the partial specific volume increases with increasing protein concentration in NaCl/citrate solutions at high salt concentrations, and decreases with increasing protein concentration in solutions containing PEG. Kirkwood-Buff solution theory has been applied to interpret these results, and it was found that the concentration dependence is determined by two factors: (1) the effective or solvent-averaged interactions between protein molecules in solution, and (2) three-body protein - protein - solvent and protein - solvent - solvent interactions. An approach is proposed for the experimental determination of both contributions that involves measuring osmotic pressures and volumetric properties of dilute to concentrated protein solutions.
    Additional Material: 1 Tab.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 1723-1778 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Supercritical fluids posses properties that make them attractive as media for chemical reactions. Conducting chemical reactions at supercritical conditions affords opportunities to manipulate the reaction environment (solvent properties) by manipulating pressure, to enhance the solubilities of reactants and products, to eliminate interphase transport limitations on reaction rates, and to integrate reaction and separation unit operations. Supercritical conditions may be advantageous for reactions involved in fuels processing, biomass conversion, biocatalysis, homogeneous and heterogeneous catalysis, environmental control, polymerization, materials synthesis, and chemical synthesis. Moreover, supercritical fluids can be used profitably in fundamental chemical investigations of intermolecular interactions and their influence on chemical processes. Work on chemical reactions in and with supercritical fluids is reviewed. We discuss both fundamental studies and applications of reactions at supercritical conditions, with focus on work published after 1985.
    Additional Material: 43 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 12-22 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An analytical approach to the problem of steady-state, axisymmetrically disperesed, bubbly flow in pipes based on a zero equation turbulence model is discussed. The formulation incorporates recent experimental observations and introduces the effect of bubble size in a rudimentary way. The two-phase mixture is modeled as a variabledensity single fluid assuming an empirical void distribution family. The turbulent shear stress is formed from the contributions of both the velocity and density variation, and the solution of the resulting Reynolds-type equation yields the velocity profile of the flow. Predicted void fraction and velocity distributions agree well with experimental measurements. The main objective of the model is to predict the friction multiplier with minimal computational effort. The velocity profiles of this model agree reasonably well with experiments. Predictions for the friction multiplier are compared to six known and widely used correlations, as well as to experimental data. All the correlations severely underpredict the friction multiplier in the disperesed bubbly flow regime, while the results of our model agree well with the measurements, within the range of its validity.
    Additional Material: 3 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 151-156 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Thermal diffusivity of high density polyethylene (HDPE) was studied over a wide range of temperatures (25 to 200°C) by melting powdered HDPE in a cylindrical mold at several pressures (101.3 to 5065 KPa gage) and recording the temperature profiles at several radial positions. The energy equation was solved numerically for cylindrical geometry. The thermal diffusivity of HDPE was fit as a function of temperature, porosity, and pressure.
    Additional Material: 8 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1282-1289 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The creep behavior of polymers depends on the physical age of the material at the time of stress application. Creep curves shift to longer times for more highly aged material and, in poly(vinyl chloride), (PVC), this can be modeled by an empirical equation in which the magnitude of an effective mean retardation time parameter is dependent upon, and increases with, the age of the polymer. Creep compliances for PVC also depend on the magnitude of the applied stress when this exceeds about 4 MPa. This nonlinear behavior is caused, at short creep times, by a reduction in the value for the retardation time parameter on application of the creep stress. Specimens appear therefore to be initially de-aged by elevated stresses. Subsequently, this parameter increases with creep time implying that physical aging has been reactivated, but the rate of increase also depends on the stress level. These influences of elevated stresses can be described by an extension of the creep model, and parametric expressions have been derived which relate creep compliance values to time, stress, and the age of the polymer. It is shown how the parameters can be determined from a short series of creep experiments and thus how creep deformations can be calculated over wide ranges of time, stress, and age.
    Additional Material: 10 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Brookfield, Conn. : Wiley-Blackwell
    Polymer Composites 16 (1995), S. 319-324 
    ISSN: 0272-8397
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: This paper deals with the conductivity of binary polymer composites filled with an electronically conductive material. A “dynamic cluster model” is offered to describe the conductivity of such polymer composites in the highly filled region, i.e. above the percolation threshold. The model is based on the following assumptions: 1a modification of the basic statistical percolation equation, i.e. σ (ϕ-ϕc)t, where t = 1.6 to 1.9, should be applied for all systems in the highly filled region, although application is limited to the range ϕ = ϕc + Δϕ, Δϕ ⇒ 0 in the strict statistical percolation approach;2the most important modifications with respect to the basic equation of the statistical percolation theory are (a) the use of a constant teff, including a constant part t1 (resembling “t” in the basic statistical percolation approach) and a variable part t2 (depending on the filler concentration ϕ of the specific mixture) and(b) the definition of ϕc as the filler concentration where a perfect three-dimensional network of the conductive phase has been established. This idea has been adopted from the bond-percolation approach of Aharoni;3the resulting equation should include parameters of specific polymer composites.The generalized equation σ = f(ϕ) is used to calculate the maximum possible conductivity of a certain mixture as well as the dependence of σ on the filler content.
    Additional Material: 6 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Brookfield, Conn. : Wiley-Blackwell
    Journal of Vinyl and Additive Technology 1 (1995), S. 71-75 
    ISSN: 0193-7197
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In designing for stiffness of polymer products, one of the most common questions asked by design engineers is: “What are the effects of time and temperature on the modulus values listed on the product data sheet?” This paper outlines our approach to provide answers for glass reinforced Fiberloc® vinyl composites. Static and dynamic mechanical techniques and time-temperature superposition principles were used to predict modulus as a function of both temperature and time under load. The predictions are being verified by long-term creep tests at several temperatures.
    Additional Material: 8 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 445-445 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 658-665 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The reactive ion etching kinetics of InP studied uses BCl3/Ar and BCl3/Ar/O2 as etchants. High-temperature etching using BCl3 and Ar increases the etch rate negligibly. However, the addition of 30% oxygen in the gas feed increases etch rates by a factor of 10,000 up to 1.5 micron/min at wafer temperatures of 250°C. X-ray photoelectron spectroscopy analysis reveals that oxygen removes the boron species adsorbing on the InP surface by scavenging the boron to form volatile boron oxides. To study the gas-phase chemistry, optical emission spectroscopy is used to monitor atomic chlorine intensity at different gas mixtures. The chlorine intensity shows a Gaussian-type dependence with oxygen addition, which is similar to the etch rate dependence. Two regimes of etching found are: at temperatures below 150°C, the etching is limited by the removal of indium chlorides; above 180°C, the etching is reaction-limited. The surface morphology shows that the etch profile becomes rougher as a result of increased chemical etching. At high power densities (0.21 W/cm2) and intermediate temperatures (150°C), near vertical wall shapes are obtained. A kinetic model for the high-temperature etching is developed, as well as a rate law based on the InCl formation reaction. The rate law compares favorably with experimental etch rate results.
    Additional Material: 11 Ill.
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