高温高压下合成金刚石单晶用新型触媒材料的研究与设计
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摘要
金刚石是集多种优异性能于一体的多功能超硬材料。目前,我国是世界金刚石的主产国,但高端产品稀缺,其主要原因是我国对合成金刚石的触媒材料研究和开发力量薄弱。本工作在国内首次开展了在高于7.0 GPa的压力条件下对合成金刚石单晶用新型触媒材料研究,填补了我国在这一重要领域的空白。获得了以下创新性成果:
1.确定了稳定的金刚石合成技术:首先,通过对传压与保温介质的进一步选择与优化,设计出了在高于7.0GPa,2000℃条件下合成金刚石单晶稳定的材料组装方式;其次,通过对合成工艺进一步改善,得到了适合高质量金刚石单晶合成的成熟工艺。
2.考察了低熔点金属材料合成金刚石的触媒特性:通过在传统触媒体系中添加不同比例的低熔点金属,详细地考察了对合成金刚石的触媒特性的影响。我们发现通过适当比例低熔点金属的添加,金刚石的合成压力与温度条件均得到了明显的降低,金刚石的成核密度和生长速度也可以得到显著提高。
3.考察了触媒材料中的微量杂质元素对合成金刚石的影响:我们在羰基铁粉触媒体系中成功地合成出了高氮含量金刚石单晶,最高氮含量可以达到1438 ppm,金刚石内部氮原子主要以A心与C心形式并存。在羰基镍粉触媒体系中利用膜生长法首次合成出了无色透明的IaB型金刚石晶体,这为揭示天然金刚石的成因提供一种新的可能性。
4.合成出了多种“硼氮”共掺杂的金刚石单晶:目前对“硼碳氮”材料的研究吸引着人们的极大的兴趣,然而到目前为止仍未真正合成出值得信赖的立方相“硼碳氮”晶体。本文中,我们提出并成功合成出了多种优质“硼氮”共掺杂金刚石单晶,这为进一步寻找新型超硬-导电材料提供了新的思路。
5.考察了高温高压下金刚石单晶的生长机制:本文中利用黑色含硼金刚石作为晶种生长黄色的金刚石,为研究金刚石的成核、生长等机理方面的物理问题提供了便利的观察条件。我们通过对金刚石晶体在成核后期的生长方式以及晶形形成过程的一系列研究,为金刚石合成的溶剂理论做了一些有益补充,这为建立新的金刚石合成理论提供了新的实验依据。
The research on catalytic materials for diamond synthesis has been widely performed by many scientists in the world, and notable achievements have been reported during this research process. Recently, foreign researchers found that some non-transition metal materials and compounds show active catalytic effects under much higher pressure and temperature (P-T) conditions, usually higher than 6.0 GPa. The development of these new catalysts is greatly helpful for the synthesis of special diamonds with potential applications in optics and electrics. In some developed countries, the diamond synthesis using the new catalysts has already been well developed. But the synthesis technologies are not open because of the huge commercial value of diamond industry and the difficulties in improving performance of diamond. Thus, the research on the catalytic materials in our country is very necessary and of significance in diamond industry.
Since the limited P-T conditions in the china-type large volume Cubic High-Pressure Apparatus (CHPA) (the maximum pressure ~ 6.0 GPa and temperature ~ 1600℃) prevented further study, we focused on the designing and developing the high-pressure apparatuses and cells for various high pressure and high temperature (HPHT) experimental applications. As well known the maximum pressure of the large volume piston CHPA is mainly determined by the shape of the tungsten carbide anvils, the area ratio between the high-pressure anvils and piston cylinder, and the design of the high-pressure cell. Thus, we have designed several new type of multiple high-pressure anvils and developed the high-pressure cell to obtain much higher P-T conditions ( ~ 7.5 GPa, 2000℃). In this work, we carried out the extensive studies on the new catalysts for the diamond synthesis under the pressure conditions of higher than 7.0 GPa. Most of our studies are as follows:
Firstly, we have designed the stable assembling for diamond synthesis by optimizing the pressure transferring and insulation media, and improved the synthetic technology for the high-quality diamond crystallization.
It is reported that many non-transition metal materials and compounds show active catalytic effects under much higher P-T conditions (larger than 1600℃). So it is necessary to improve the synthetic assembling to be used in the higerer P-T conditions. Thus, we have designed and optimized the shape of multiple high-pressure cells in a XKY—6×12MN CHPA to obtain much higher pressures (larger than 7.5 GPa). Under these conditions, we can perform the studies on new catalytic materials. Besides, we successfully designed a reasonable assembling to synthesize diamond under such HPHT conditions.
Secondly, we examined the properties of low-melting metal catalysts and their catalytic effects on the characteristics and performance of the synthetic diamond.
In the diamond industry, how to lower the synthetic temperature of diamond is still topic interests. Some low-melting metals (Zn, Cu, Mg, Al, et al.) and their alloys have attracted much attention. Usually, such metals are stable in the ambient conditions, but active at HPHT. In this work, we have synthesized the diamond crystals in the Fe-Ni-C and Fe-C systems with some low-melting metals additive (ranging from 1 wt.% to 100 wt.%) and their catalytic capability for converting graphite to diamond were also investigated in detail. Based on the analysis of the experimental results, we found that although much higher temperatures are required for these low-melting materials to be used as catalyst, the reaction temperatures can be reduced significantly (~100-150℃) with an appropriate addition of low-melting materials in conventional catalysts. The diamond nucleation and growth rate is also accelerated, which is very favorable for the diamond industry. Besides, we found that with some low-melting metals additive, the nitrogen concentration in the synthetic diamond is very low, thus such catalysts are very suitable for the type-IIb diamond synthesis.
Thirdly, we examined the effects of minor elements in catalysts on the catalytic activities and properties of synthetic diamonds.
In this paper, we studied the growth characteristics of diamond using the carbonyl iron catalyst under HPHT. We successfully synthesized the diamond single crystals with high nitrogen concentration. Our results show that the diamond morphology is not only determined by P-T conditions, but also significantly influenced by the composition of crystallization medium. The stable growth forms are strip and lamellar shapes at relatively low temperatures. On the other hand, the most important achievement is the successful synthesis of Ia-type diamonds for the first time using a new carbonyl nickel catalyst at temperatures of 1500-1800℃and pressures of 6.2-7.0 GPa. We know that most natural diamonds are dominantly Ia-type, containing aggregated nitrogen. Thus, the man made“natural diamond”may be realized employed a certain nitrogen compounds in the carbonyl nickel catalyst in the further work.
Fourthly, we successfully synthesized covalently bonded“BCN”diamond by subjecting graphitic mixtures of C and BN to HPHT conditions.
The X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared (FTIR) spectrometer were used to confirm the chemical composition of“BCN”diamond and atomic-level hybrid qualities. Based on the results, we found two possible reaction routes during diamond crystallization as described below: Firstly, in the system of C0.98(BN)0.02 and C0.9(BN)0.1, the h-BN powders are partially decomposed into B and N atoms. Then, certain C-C pairs are replaced by B-N pairs into the crystal structure during diamond crystallization. However, it is difficult to control the incorporation of B and N atoms for the high growth rate, which leads to the phase separation for the different B/N ratio in the diamond crystal structures. The other route for the diamond crystallization: the mixtures of h-BN and graphite are firstly transformed to some graphitic B-C-N compounds under HPHT treatment, and then the diamond crystallize directly from graphitic B-C-N compounds in C0.5(BN)0.5 system. Thus, both the B-N pairs and the N-C sp3 bondings are also found in the crystal structure. No phase separation in diamond crystals is found in this system and these“BCN”diamond crystals with well morphology are nearly transparent because of the uniform distribution of B and N atoms in the crystal structure.
At last, we explored the growth mechanism of diamond under HPHT conditions, and presented a reasonable nucleation and growth models.
In 1955, Bundy et al. firstly successfully synthesized diamond using metal catalysts and graphite under HPHT. Since then, the research on diamond synthesis and growth mechanism has been widely performed. But during the diamond synthesis process, the formation of diamond shape has not been examined in detail. In this work, we performed extensive studies on the shape-controlled synthesis. To obviously distinguish the seeds from new grown diamonds, we chose boron-doped diamonds, black in color, as seed crystals. We also established the growth model for the diamond grown on several seeds and proposed the possible growth processes by tracking the particular shapes of seeds before and after treated under HPHT conditions. We found the crystal direction and original shape of seed play important roles in the formation of diamond morphology in the early growth stage and the synthetic temperature will further affect the crystal shape in the following growth process. Our current research proposed a new effective way to further establish the diamond growth mechanism under HPHT conditions.
1.确定了稳定的金刚石合成技术:首先,通过对传压与保温介质的进一步选择与优化,设计出了在高于7.0GPa,2000℃条件下合成金刚石单晶稳定的材料组装方式;其次,通过对合成工艺进一步改善,得到了适合高质量金刚石单晶合成的成熟工艺。
2.考察了低熔点金属材料合成金刚石的触媒特性:通过在传统触媒体系中添加不同比例的低熔点金属,详细地考察了对合成金刚石的触媒特性的影响。我们发现通过适当比例低熔点金属的添加,金刚石的合成压力与温度条件均得到了明显的降低,金刚石的成核密度和生长速度也可以得到显著提高。
3.考察了触媒材料中的微量杂质元素对合成金刚石的影响:我们在羰基铁粉触媒体系中成功地合成出了高氮含量金刚石单晶,最高氮含量可以达到1438 ppm,金刚石内部氮原子主要以A心与C心形式并存。在羰基镍粉触媒体系中利用膜生长法首次合成出了无色透明的IaB型金刚石晶体,这为揭示天然金刚石的成因提供一种新的可能性。
4.合成出了多种“硼氮”共掺杂的金刚石单晶:目前对“硼碳氮”材料的研究吸引着人们的极大的兴趣,然而到目前为止仍未真正合成出值得信赖的立方相“硼碳氮”晶体。本文中,我们提出并成功合成出了多种优质“硼氮”共掺杂金刚石单晶,这为进一步寻找新型超硬-导电材料提供了新的思路。
5.考察了高温高压下金刚石单晶的生长机制:本文中利用黑色含硼金刚石作为晶种生长黄色的金刚石,为研究金刚石的成核、生长等机理方面的物理问题提供了便利的观察条件。我们通过对金刚石晶体在成核后期的生长方式以及晶形形成过程的一系列研究,为金刚石合成的溶剂理论做了一些有益补充,这为建立新的金刚石合成理论提供了新的实验依据。
The research on catalytic materials for diamond synthesis has been widely performed by many scientists in the world, and notable achievements have been reported during this research process. Recently, foreign researchers found that some non-transition metal materials and compounds show active catalytic effects under much higher pressure and temperature (P-T) conditions, usually higher than 6.0 GPa. The development of these new catalysts is greatly helpful for the synthesis of special diamonds with potential applications in optics and electrics. In some developed countries, the diamond synthesis using the new catalysts has already been well developed. But the synthesis technologies are not open because of the huge commercial value of diamond industry and the difficulties in improving performance of diamond. Thus, the research on the catalytic materials in our country is very necessary and of significance in diamond industry.
Since the limited P-T conditions in the china-type large volume Cubic High-Pressure Apparatus (CHPA) (the maximum pressure ~ 6.0 GPa and temperature ~ 1600℃) prevented further study, we focused on the designing and developing the high-pressure apparatuses and cells for various high pressure and high temperature (HPHT) experimental applications. As well known the maximum pressure of the large volume piston CHPA is mainly determined by the shape of the tungsten carbide anvils, the area ratio between the high-pressure anvils and piston cylinder, and the design of the high-pressure cell. Thus, we have designed several new type of multiple high-pressure anvils and developed the high-pressure cell to obtain much higher P-T conditions ( ~ 7.5 GPa, 2000℃). In this work, we carried out the extensive studies on the new catalysts for the diamond synthesis under the pressure conditions of higher than 7.0 GPa. Most of our studies are as follows:
Firstly, we have designed the stable assembling for diamond synthesis by optimizing the pressure transferring and insulation media, and improved the synthetic technology for the high-quality diamond crystallization.
It is reported that many non-transition metal materials and compounds show active catalytic effects under much higher P-T conditions (larger than 1600℃). So it is necessary to improve the synthetic assembling to be used in the higerer P-T conditions. Thus, we have designed and optimized the shape of multiple high-pressure cells in a XKY—6×12MN CHPA to obtain much higher pressures (larger than 7.5 GPa). Under these conditions, we can perform the studies on new catalytic materials. Besides, we successfully designed a reasonable assembling to synthesize diamond under such HPHT conditions.
Secondly, we examined the properties of low-melting metal catalysts and their catalytic effects on the characteristics and performance of the synthetic diamond.
In the diamond industry, how to lower the synthetic temperature of diamond is still topic interests. Some low-melting metals (Zn, Cu, Mg, Al, et al.) and their alloys have attracted much attention. Usually, such metals are stable in the ambient conditions, but active at HPHT. In this work, we have synthesized the diamond crystals in the Fe-Ni-C and Fe-C systems with some low-melting metals additive (ranging from 1 wt.% to 100 wt.%) and their catalytic capability for converting graphite to diamond were also investigated in detail. Based on the analysis of the experimental results, we found that although much higher temperatures are required for these low-melting materials to be used as catalyst, the reaction temperatures can be reduced significantly (~100-150℃) with an appropriate addition of low-melting materials in conventional catalysts. The diamond nucleation and growth rate is also accelerated, which is very favorable for the diamond industry. Besides, we found that with some low-melting metals additive, the nitrogen concentration in the synthetic diamond is very low, thus such catalysts are very suitable for the type-IIb diamond synthesis.
Thirdly, we examined the effects of minor elements in catalysts on the catalytic activities and properties of synthetic diamonds.
In this paper, we studied the growth characteristics of diamond using the carbonyl iron catalyst under HPHT. We successfully synthesized the diamond single crystals with high nitrogen concentration. Our results show that the diamond morphology is not only determined by P-T conditions, but also significantly influenced by the composition of crystallization medium. The stable growth forms are strip and lamellar shapes at relatively low temperatures. On the other hand, the most important achievement is the successful synthesis of Ia-type diamonds for the first time using a new carbonyl nickel catalyst at temperatures of 1500-1800℃and pressures of 6.2-7.0 GPa. We know that most natural diamonds are dominantly Ia-type, containing aggregated nitrogen. Thus, the man made“natural diamond”may be realized employed a certain nitrogen compounds in the carbonyl nickel catalyst in the further work.
Fourthly, we successfully synthesized covalently bonded“BCN”diamond by subjecting graphitic mixtures of C and BN to HPHT conditions.
The X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared (FTIR) spectrometer were used to confirm the chemical composition of“BCN”diamond and atomic-level hybrid qualities. Based on the results, we found two possible reaction routes during diamond crystallization as described below: Firstly, in the system of C0.98(BN)0.02 and C0.9(BN)0.1, the h-BN powders are partially decomposed into B and N atoms. Then, certain C-C pairs are replaced by B-N pairs into the crystal structure during diamond crystallization. However, it is difficult to control the incorporation of B and N atoms for the high growth rate, which leads to the phase separation for the different B/N ratio in the diamond crystal structures. The other route for the diamond crystallization: the mixtures of h-BN and graphite are firstly transformed to some graphitic B-C-N compounds under HPHT treatment, and then the diamond crystallize directly from graphitic B-C-N compounds in C0.5(BN)0.5 system. Thus, both the B-N pairs and the N-C sp3 bondings are also found in the crystal structure. No phase separation in diamond crystals is found in this system and these“BCN”diamond crystals with well morphology are nearly transparent because of the uniform distribution of B and N atoms in the crystal structure.
At last, we explored the growth mechanism of diamond under HPHT conditions, and presented a reasonable nucleation and growth models.
In 1955, Bundy et al. firstly successfully synthesized diamond using metal catalysts and graphite under HPHT. Since then, the research on diamond synthesis and growth mechanism has been widely performed. But during the diamond synthesis process, the formation of diamond shape has not been examined in detail. In this work, we performed extensive studies on the shape-controlled synthesis. To obviously distinguish the seeds from new grown diamonds, we chose boron-doped diamonds, black in color, as seed crystals. We also established the growth model for the diamond grown on several seeds and proposed the possible growth processes by tracking the particular shapes of seeds before and after treated under HPHT conditions. We found the crystal direction and original shape of seed play important roles in the formation of diamond morphology in the early growth stage and the synthetic temperature will further affect the crystal shape in the following growth process. Our current research proposed a new effective way to further establish the diamond growth mechanism under HPHT conditions.
引文
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