dc.description.abstract | ABSTRACT
Kinetic research of minerals has been a very important area in the research of geology. In this research, three kinetic methods ─ Master Curve Model (MCM), Ozawa method and Avrami Equation method ─ have been used to analyze and predict the thermal decomposition reactions of five evaporite minerals.
The research consists of three parts: First is to prepare the five high-purity synthetic evaporite minerals powders, including gypsum, calcite, chalcanthite, nitratine and hydromagnesite, and to verify their phases and purities by XRD. Second is to conduct a series of thermal decomposition experiments of the powders by TGA at various heating rates and isothermal condition. Third is to analyze the weight loss data by the three kinetic methods. The application limitations of MCM, Ozawa method and Avrami Equation on the study of thermal decomposition reactions will be discussed on the basis of the experimental results.
From the experimental results, constant heating rate experiments show a significant deviation of the data due to the possible temperature-measuring errors inside the Thermal Gravitometry Analyzer. Fortunately, isothermal experiments can effectively reduce the uncertainty of the data and thus derive adequate results. In this research, MCM demonstrates that it is excellent in the prediction of reaction process. The effect of grain size on reaction rate is shown in this work that smaller grain size samples may lead to a higher reaction rate, as a result of the “surface-area effect.” The final part of this research is to propose a new concept of “geothermometer,” which is based on the modeling of the kinetic reactions, and it may become a powerful tool to find out the possible temperature and time conditions of many geological processes.
To sum up, the research contributes in three aspects: First, using three kinetic models to characterize the thermal decomposition reactions and the thermal stability of five evaporate minerals, and most importantly to derive the quantitative relationship of the reaction percentage and the reaction time and temperature. Second, learning the applicability, the limitation and possible error levels of MCM, Ozawa method and Avrami Equation, based on the analysis results. Finally, proposing a new concept of “geothermometer,” and which may be very useful in geologic research. The results of this preliminary study may be extended to other kinetic reactions of various minerals. | en |
dc.relation.reference | 參考文獻
1. V. R. Howes(1962)”The Graphitization of Diamond,” Physics Society, 80, p.648-662.
2. Z. Qiao, J. Li, N. Zhao, C. S. Shi and P. Nash(2006)”Graphitization and microstructure transformation of nanodiamond to onion-like carbon,” Acta Material, 54, p.225-229.
3. A. Reznik, V. Richter and R. Kalish(1998)”The re-arrangement of broken bounds in damaged diamond: graphitization versus annealing back to diamond,” Diamond and Related Materials, 7, p.317-321.
4. 陳英田(2000),數種常見氧化物陶瓷之主導燒結曲線及其應用。國立台灣大學地質科學研究所碩士論文,共112頁。
5. 梁家豪(2003),三種分析反應動力學及燒結資料的新方法。台灣大學地質科學系研究所碩士論文,共159頁。
6. 陳孟霞(2004),主導曲線模型運用在奈米氧化鋁和奈米二氧化鈦陶瓷粉末燒結之研究。台灣大學地質科學系研究所碩士論文,共95頁。
7. Tadeusz M. Peryt(1987)Evaporite basins, Berlin Publishing, New
York, p.188.
8. John K. Warren(1951)Evaporites: sediments, resources, and hydrocarbons, Berlin Publishing, New York, p.1035.
9. T. Buckby, S.Black, M. L. Coleman and M. E. Hodson(2003)”Fe-sulfate-rich evaporative mineral precipitates from the Rio Tino, southwest Spain,” Mineralogical Magzine, 67, p263.
10. J. M. Moore and M. A. Bullock(2006)”Mars-analog brines and evaporate experiments: Implications for sulfates,” Nasa ames research center
11. D. T. Vaniman and S. J. Chipera(2006)”Transformations of Mg- and Ca- sulfate hydrates in Mars regolith,” American Mineralogist, 91, p.1628-1642.
12. R. L. Frost, M. L. Weier and W. Martens(2005)“Thermal decomposition of jarosites of potassium, sodium and lead,” Journal of Thermal analysis and calorimetry, 82, p.115-118.
13. B. V. L`vov and V. L. Ugolkov(2005)”Kinetics and mechanism of dehydration of kaolinite, muscovite and talc analyzed thermogravimetrically by third-law method,” Journal of Thermal Analysis and Calorimetry, 82, p.15-22.
14. R. L. Frost, M. L. Weier and W. Martens(2005)“Thermal decomposition of liebigite: A high resolution thermalgravimetric and hot-stage raman sectoscopic study,” Journal of Thermal analysis and calorimetry, 82 p.373-381.
15. V. Berbenni, A. Marini and G. Bruni(1998)”Thermogrvimetric study of the dehydration process of α-cyclodextrin: comparison between conventional and high-resolution TGA, ” Journal of thermochimica acta, 322, p.137-151.
16. J. D. Hancock and J. H. Sharp(1972)”Method of comparing solid state kinetic data and its application to the decomposition of kaolinite, brucite and BaCO3,” Journal of the American Ceramic Society, 55, p.74-77.
17. V. Berbenni, C. Milanese, G. Bruni and A. Marini(2005)”Thermal decomposition of Gallium nitrate Ga(NO3)3•XH2O,” Journal of Thermal Analysis and Calorimetry, 82, p.401-407.
18. J. W. Park, S. C. Oh, H. P. Lee, H. T. Kim and K. O.Yoo(2000)”A kinetic analysis of thermal degradation of polymers using a dynamic method,” Polymer Degradation and Stability, 67, p.535-540.
19. B. L. Denq, W. Y. Chiu and K. F. Lin(1997)”Kinetic model of thermal degradation of polymers for nonisothermal process,” Journal of Apllied Polymer Science, 66, p.1855-1868.
20. A. C. Lasaga and R..J. Kirkpatrick(1981)”Rate laws of chemical reactions;transition state theory;the atomic basis of kinetics-defects in minerals,” Chapters 1, 4, 7 in Kinetics of Geochemical Process. Reviews in mineralogy. Mineralogical Society of America., p.398
21. M. A. Carpenter(1991)”Mechanisms and kinetics of Al, Si ordering in anorthite, I: incommensurate structure and domain coarsening,” American Mineralogist, 76, p.1110-1119.
22. M. Avrami(1939)”Kinetics of phase change I,” Journal of chemical physics, 7, p.1103-1112.
23. M. Avrami(1940)”Kinetics of phase change II,” Journal of chemical physics, 8, p.212-224.
24. J. Burke(1965)The kinetics of phase transformations in metals, Pergamon Press., P.226
25. A. Matthews(1980)”Influences of kinetics and mechanism in metamorphism: a study of albite crystallization,” Geochimica et Cosmochimica Acta, 44, p.387-402.
26. W. L. Huang and G. A. Otten(1998)”Oil generation kinetics determined by DAC-FS/IR Pyroysis: Technique development and preliminary results,” Organic Geochemistry, 29[5-7], p.1119-1137.
27. H. E. Kissinger(1957)”Reaction kinetics in differential thermal analysis,” Analytical Chemistry, 29, p.1702-1706.
28. T. Ozawa(1992)”Estimation of activation energy by isoconversion method,” Thermochimica Acta, 203, p.159-165.
29. T. Ozawa(1999)”Thermal analysis-review and prospect,” Thermochimica Acta, 325, p.35-42.
30. Mustafa Gunes and Semin Gunes(2002), ”A direct search method for determination of daem kinetic parameters from nonisothermal TGA data,” Journal of applied mathematics and computation, 130, p.619-628.
31. R. R. Keuleers, J. F. Janssens and H. O. Desseyn(2002),”Comparison of some methods for activation energy determination of thermal decomposition reactions by thermogravimetry,” Journal of thermochimica acta, 385, p.127-142.
32. R. L. Braun and A. K. Burnham(1987)”Analysis of chemical reaction kinetics using a distribution of activation energies and simple models,” Energy and Fuels 1, p.153-161.
33. 鄧茂華(2003)比表面積,實用儀器分析第五章,王明光、王敏昭聯合編著。和記書局發行,p.125-160共692頁。 | zh_TW |