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  • 1
    Digitale Medien
    Digitale Medien
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 377-388 
    ISSN: 0001-1541
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A thermogravimetric analyzer is used to study the synthesis of TiN from Ti powder over a wide range of temperature, conversion and heating rate, and for two Ti precursor powders with different morphologies. Conversions to TiN up to 99% are obtained with negligible oxygen contamination. Nonisothermal initial rate and isothermal data are used in a nonlinear least-squares minimization to determine the most appropriate rate law. The logarithmic rate law offers an excellent agreement between the experimental and calculated conversions to TiN and can predict afterburning, which is an important experimentally observed phenomenon. Due to the form of the logarithmic rate law, the observed activation energy is a function of effective particle size, extent of conversion, and temperature even when the intrinsic activation energy remains constant. This aspect explains discrepancies among activation energies obtained in previous studies. The frequently used sedimentation particle size is a poor measure of the powder reactivity. The BET surface area indicates the powder reactivity much better.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 1235-1250 
    ISSN: 0001-1541
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: The reaction rate in gas-solid systems can be affected by mechanical stresses that arise as the reaction proceeds. Stresses develop due to differences between precursor and product molar volumes and thermal expansion coefficients. Experimental evidence on the interaction of reaction rate and mechanical stress for the Ti/N2 and Ti/O2 systems is provided. A detailed and consistent mathematical model is developed for the reaction taking place at the constrained precursor/product interface. An elastic formulation for the stresses is adopted, and stress generation due to mismatches in linear thermal expansion coefficients and equivalent volume (Pilling-Bedworth ratio) for the precursor and product are considered. The effect of surface energy, which becomes significant for particle sizes below 1 μm, is also included in the model. Both experimentally and theoretically, conditions exist where the mechanical stresses exceed the strength of the material, leading to mechanical breakdown of the product layer, thus causing a discontinuity in the observed reaction rate. The entire processing history, including the reaction, temperature, and pressure profiles, plays an important role in determining the overall reaction kinetics of the powder.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 2614-2624 
    ISSN: 0001-1541
    Schlagwort(e): Chemistry ; Chemical Engineering
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: A detailed model to describe the overall reaction rate of the oxidation of titanium is developed. The mathematical model consists of two facets, the first of which involves a detailed description of species transport that accounts for the formation of charged species. This is augmented by a description of the occurrence of mechanical stress due to a Pilling - Bedworth ratio that differs significantly from I as well as differences between precursor and product thermal expansion coefficients. A self imposed electric field is formed across the oxide layer due to different mobilities of the species considered. This field opposes the transport of electrons and enhances the transport of anion vacancies, thus increasing the overall reaction rate compared to a pure diffusion process, while also ensuring that electrical charge is conserved. Large growth stresses result from the unmatched precursor and product volumes, significantly affecting the overall process. These results show that the incorporation of a consistent treatment of mechanical stress forms a necessay part of any accurate description of the overall behavior of a reacting particle.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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