高压物理学报

高温高压触媒法金刚石生长的热力学分析

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许斌 ¹ , 李丽 ² , 田彬 ³ , 范小红 ¹ , 冯立明 ¹

高压物理学报 | 2009,23(3): 189-195

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高压物理学报 | 2009 , 23 (3) : 189 -195

高温高压触媒法金刚石生长的热力学分析

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许斌¹, 李丽², 田彬³, 范小红¹, 冯立明¹

作者信息

^1.山东建筑大学材料科学与工程学院，山东济南　250101

^2.河北工程大学机电学院，河北邯郸　056038

^3.山东大学材料科学与工程学院，山东济南　250061

作者简介:

许斌（1957—），男，博士，教授，主要从事超硬材料研究. E-mail：xubin@sdjzu.edu.cn

Thermodynamic Analysis of Diamond Growth with Catalyst at HPHT

Bin XU¹, Li LI², Bin TIAN³, Xiao-Hong FAN¹, Li-Ming FENG¹

Affiliations

^1.School of Materials Science & Engineering, Shandong Jianzhu University, Jinan 250101, China

^2.School of Machinery & Electron, Hebei University of Engineering, Handan 056038, China

^3.School of Materials Science & Engineering, Shandong University, Jinan 250061, China

出版时间: 2009-06-15

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摘要

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利用热力学中经典的ΔG<0判定法，探讨了Fe基触媒合成金刚石晶体生长中的碳源问题，在计算中考虑了各物相的体积随温度和压力的变化。结果表明：在金刚石形成之前，就有大量Fe₃C形成，而在触媒法合成金刚石的温度和压力范围内，Fe₃C⇒C（金刚石）+3γ-Fe反应自由能和石墨⇒金刚石相变自由能均为负值，但前者比后者的绝对值更大，这说明前者更容易发生。因此，从热力学角度看，Fe₃C的形成降低了石墨转变为金刚石所要越过的势垒，使用Fe基触媒合成金刚石单晶的生长来源于Fe₃C的分解而不是石墨的直接转化。同时推导出在1 200 K以上石墨-金刚石的平衡p-T关系：p_eq（GPa）=1.036+0.002 36T（K），与F. P. Bundy的平衡线非常接近，证明了本热力学计算方法的可行性。

关键词

高温高压 / 金刚石生长 / 触媒 / 碳源 / 热力学

Abstract

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The diamond growth with Fe-based catalyst at high pressure and high temperature (HPHT) was analyzed with the determinant method of ΔG<0 in thermodynamics theory, and the changes of volume with temperature and pressure were involved in the calculation. The results show that the Fe₃C phases have been formed before diamond nucleation; at the temperature and pressure range of the diamond synthesis with catalyst, the Gibbs free energies of Fe₃C⇒C (diamond) +3γ-Fe and graphite⇒diamond are all negative, but the former's absolute value is much larger than the latter's, which means the former will take place more easily. Therefore, from the viewpoint of thermodynamics the formation of Fe₃C reduces the potential energy of the transformation from graphite to diamond, and the diamond crystal growth with Fe based catalyst comes from the decomposition of Fe₃C instead of the direct transformation from graphite. Moreover, the p-T (Pressure-Temperature) equilibrium of p_eq (GPa)=1.036+0.002 36T (K) was gained, which was closer to that presented by F. P. Bundy. Thereby the thermodynamic calculation used in this paper is feasible.

Key words

HPHT / diamond growth / catalyst / carbon source / thermodynamics

引用本文

许斌, 李丽, 田彬, 范小红, 冯立明. 高温高压触媒法金刚石生长的热力学分析. 高压物理学报, 2009 , 23 (3) : 189 -195 .

Bin XU, Li LI, Bin TIAN, Xiao-Hong FAN, Li-Ming FENG. Thermodynamic Analysis of Diamond Growth with Catalyst at HPHT[J]. Chinese Journal of High Pressure Physics, 2009 , 23 (3) : 189 -195 .

基金

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国家自然科学基金(50772060)
山东省自然科学基金(Y2007F11)

参考文献

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2009年第23卷第3期

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接收时间：2008-08-11
首发时间：2026-10-30
出版时间：2009-06-15

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出版历史

收稿日期：2008-08-11
修回日期：2009-01-20

基金

国家自然科学基金(50772060)

山东省自然科学基金(Y2007F11)

作者信息

^1.山东建筑大学材料科学与工程学院，山东济南　250101

^2.河北工程大学机电学院，河北邯郸　056038

^3.山东大学材料科学与工程学院，山东济南　250061

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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