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- 저자 : Klaus-Dieter Becker (검색결과 3 건)
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Shi, Jianmin,Becker, Klaus-Dieter The Korean Ceramic Society 2010 한국세라믹학회지 Vol.47 No.1
The kinetics of cation reequilibration have been studied theoretically and experimentally in complex oxides after an external perturbation of equilibrium by temperature jumps. A general kinetic model for cation redistribution amongst non-equivalent sites in complex oxides is derived based on a local homogeneous point defect mechanism involving cation vacancies. Temperature-jump optical relaxation spectroscopy has been established to investigate cation kinetic processes in spinels and olivines. The kinetic model satisfactorily describes the experimental absorbance relaxation kinetics in cobalt containing olivines and in nickel containing spinels. It is found that the kinetics of cation redistribution in complex oxides shows a strong temperature- and composition-dependence. Activation energies for cation redistribution in Co-Mg olivines are found to range between 200 and 220 kJ/mol whereas an energy barrier of about 230 kJ/mol is observed in the case of nickel gallate spinel.
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Jianmin Shi,Klaus-Dieter Becker 한국세라믹학회 2010 한국세라믹학회지 Vol.47 No.1
The kinetics of cation reequilibration have been studied theoretically and experimentally in complex oxides after an external perturbation of equilibrium by temperature jumps. A general kinetic model for cation redistribution amongst non-equivalent sites in complex oxides is derived based on a local homogeneous point defect mechanism involving cation vacancies. Temperature-jump optical relaxation spectroscopy has been established to investigate cation kinetic processes in spinels and olivines. The kinetic model satisfactorily describes the experimental absorbance relaxation kinetics in cobalt containing olivines and in nickel containing spinels. It is found that the kinetics of cation redistribution in complex oxides shows a strong temperature- and compositiondependence. Activation energies for cation redistribution in Co-Mg olivines are found to range between 200 and 220 kJ/mol whereas an energy barrier of about 230 kJ/mol is observed in the case of nickel gallate spinel.
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Oxidation kinetics of nitrogen doped TiO<sub>2−<i>δ</i></sub> thin films
Shi, Jianmin,Lee, Doh-Kwon,Yoo, Han-Ill,Janek, Jü,rgen,Becker, Klaus-Dieter The Royal Society of Chemistry 2012 Physical chemistry chemical physics Vol.14 No.37
<P>The oxidation kinetics of nitrogen doped, oxygen deficient titanium dioxide thin films has been studied in atmospheres of pure oxygen or nitrogen at 500 °C, 550 °C, and 600 °C, respectively, by means of <I>in situ</I> optical spectroscopy. The thin films show high electronic absorbance in the visible and NIR region, accompanied by a red shift of the absorption edge of about 0.4 eV, <I>e.g.</I>, from about 2.9 to 2.5 eV at 600 °C. The time dependent decrease of absorbance due to oxidation is found to follow a parabolic rate law. An activation energy of about 1.96 eV can be obtained from the temperature dependence of the parabolic oxidation rate constant. In the framework of a microscopic oxidation model, this energy barrier is attributed to the diffusion of titanium interstitials in the re-oxidized part of the thin films as a rate-determining process. In addition, an attempt is made to evaluate the kinetics of nitrogen release from the time dependent blue shift of the absorption edge during re-oxidation.</P> <P>Graphic Abstract</P><P>Oxidation kinetics of N-doped TiO<SUB>2−<I>δ</I></SUB> thin film has been studied using optical spectroscopy under <I>in situ</I> conditions, revealing the dominance of Ti<SUP>4+</SUP>-interstitial diffusion. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c2cp42559a'> </P>
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