触媒组分对高温高压金刚石大单晶生长及裂纹缺陷的影响

本文利用六面顶压机,在5.6 GPa, 1250—1450℃的高压高温条件下,分别选用FeNiCo和NiMnCo触媒合金开展了金刚石大单晶的生长实验,系统地考察了触媒组分对金刚石单晶裂纹缺陷的影响.首先,通过对两种组分触媒晶体生长实验对比发现,金刚石大单晶裂纹缺陷出现的概率与触媒组分相关联.同NiMnCo触媒相比, FeNiCo触媒生长的金刚石单晶更容易出现生长裂纹.我们认为,这与FeNiCo触媒黏度高、流动性差、碳素输运能力差、生长中晶体比表面积大,进而导致其对生长条件稳定性的要求较高有关.其次,两种触媒极限增重速度和生长时间的关系曲线表明,相同生长时间条件下, NiMnCo触媒生长金刚石单晶的极限增重速度相对较大.再次,扫描电子显微镜测试结果表明,裂纹缺陷的出现与否同晶体表面平整度的高低无必然联系,表面平整度高的金刚石单晶内部也可能存在裂纹缺陷.最后,经对金刚石单晶傅里叶微区红外测试结果进行分析,得出了氮杂质含量的高低与金刚石单晶裂纹缺陷的出现与否无内在关联性的研究结论.     

高温高压下掺硼宝石级金刚石单晶生长特性的研究

本文在5.1—5.6 GPa,1230—1600℃的压力、温度条件下,以FeNiMnCo作为触媒,进行单质硼添加宝石级金刚石单晶的生长研究.借助于有限元法,对触媒内的温度场进行模拟.研究得到了FeNiMnCo-C-B体系下,金刚石单晶生长的P-T相图.该体系下合成金刚石单晶的最低压力、温度条件分别为5.1 GPa,1230℃左右.研究发现,在单晶同一{111}扇区内部,硼元素呈内多外少的分布规律.有限元模拟结果给出,该分布规律是由在晶体生长过程中,{111}扇区的增长速度逐渐减小所致.{111}晶向的晶体生长实验结果表明,硼元素优先从{111}次扇区进入晶体.研究发现,这是该扇区增长速度相对较快,硼元素扩散逃离可用时间短导致的.另外,同磨料级掺硼金刚石单晶生长相比,对于温度梯度法生长掺硼宝石级金刚石单晶,由于晶体的增厚速度较慢,即使硼添加量相对较高,也可以实现表面无凹坑缺陷的优质金刚石单晶的生长.     

Fe3O4纳米粒子的可控制备及其表面改性

四氧化三铁(Fe_3O_4)因在细胞分离、靶向药物、磁共振成像等生物医学领域具有广阔的应用前景而成为研究热点。本文采用溶剂热法合成了Fe_3O_4纳米粒子,并详细研究了反应温度、反应时间和反应前驱体组成对Fe_3O_4结构和形貌的影响。实验结果表明,反应时间对球形纳米颗粒的尺寸影响不大,反应时间为12 h时,球的直径达到了最大,继续延长反应时间,球的尺寸保持不变;200℃容易生成大尺寸的Fe_3O_4纳米粒子;反应物的组成对Fe_3O_4纳米粒子的形貌也有一定的影响,当用水合肼代替乙二胺时,得到的是立方体形状的Fe_3O_4。为了增加Fe_3O_4纳米粒子的化学稳定性、生物相容性和作为药物载体的可能性,我们用St?ber方法在Fe_3O_4纳米粒子的表面包覆了一层SiO_2介孔分子筛,并探索了超声和机械搅拌对核壳结构形貌的影响,还研究了包覆前后样品的磁学性质。     

Dependence of Crystal Quality and β Value on Synthesis Temperature in Growing Gem Diamond Crystals

High quality Ib gem diamond single crystals were synthesized in cubic anvil high-pressure apparatus （SPD- 6 × 1200） under 5.4GPa and 1230℃-1280℃. The （100） face of seed crystal was used as growth face, and Ni70Mn25Co5 alloy was used as solvent/catalyst. The dependence of crystal quality andβ value （the ratio of height to diameter of diamond crystal） on synthesis temperature was studied. When the synthesis temperature is between 1230℃ and 1280℃, theβ value of the synthetic high-quality gem diamond crystals is between 0.4 and 0.6. The results show that when theβ value is between 0.4 and O. 45, the synthetic diamonds are sheet-shape crystals; however, when theβ value is between 0.45 and 0.6, the synthetic diamonds are tower-shape crystals. In addition, when theβ value is less than 0.4, skeleton crystals will appear. When theβ value is more than 0.6, most of the synthetic diamond crystals are inferior crystals.     

Effect of FeS doping on large diamond synthesis in FeNi-C system

The large single-crystal diamond with FeS doping along the(111) face is synthesized from the FeNi–C system by the temperature gradient method(TGM) under high-pressure and high-temperature(HPHT). The effects of different FeS additive content on the shape, color, and quality of diamond are investigated. It is found that the(111) face of diamond is dominated and the(100) face of diamond disappears gradually with the increase of the FeS content. At the same time, the color of the diamond crystal changes from light yellow to gray-green and even gray-yellow. The stripes and pits corrosion on the diamond surface are observed to turn worse. The effects of FeS doping on the shape and surface morphology of diamond crystal are explained by the number of hang bonds in different surfaces of diamond. It can be shown from the test results of the Fourier transform infrared(FTIR) spectrum that there exists an S element in the obtained diamond. The N element content values in different additive amounts of diamond are calculated. The XPS spectrum results demonstrate that our obtained diamond contains S elements that exist in S–C and S–C–O forms in a diamond lattice. This work contributes to the further understanding and research of FeS-doped large single-crystal diamond characterization.     

基于有限元法分析宝石级金刚石的合成腔体温度场

以有限元法为理论分析手段模拟分析了温度梯度法合成宝石级金刚石大单晶的腔体温度场,实现了对宝石级金刚石的合成腔体内各位置温度同时测量.模拟结果表明:在宝石级金刚石合成过程中,其温度分布呈不均匀分布.腔体内高温区分布在样品(碳源+触媒)边缘,低温区分布在籽晶附近.样品腔内热量的传递方式和样品腔内的碳源输运方式相同,均由碳源的两侧向籽晶附近传输.籽晶附近轴向温度梯度大于径向温度梯度,导致单位时间内其轴向生长尺寸大于径向生长尺寸.宝石级金刚石腔体温度场分析的理论模型的成功构建,为新型宝石级金刚石腔体的研制提供了良好的设计基础,对促进优质宝石级金刚石的生长技术具有指导意义.     

Different effect of NiMnCo or FeNiCo on the growth of type-Ⅱa large diamonds with Ti/Cu as nitrogen getter

In order to synthesize high-quality type-Ⅱa large diamond, the selection of catalyst is very important, in addition to the nitrogen getter. In this paper, type-IIa large diamonds are grown under high pressure and high temperature(HPHT) by using the temperature gradient method(TGM), with adopting Ti/Cu as the nitrogen getter in Ni_(70)Mn_(25)Co_5(abbreviated as NiMnCo) or Fe_(55)Ni_(29)Co_(16)(abbreviated FeNiCo) catalyst. The values of nitrogen concentration(N_c) in both synthesized high-quality diamonds are less than 1 ppm, when Ti/Cu(1.6 wt%) is added in the FeNiCo or Ti/Cu(1.8 wt%) is added in the NiMnCo. The difference in solubility of nitrogen between both catalysts at HPHT is the basic reason for the different effect of Ti/Cu on eliminating nitrogen. The nitrogen-removal efficiency of Ti/Cu in the NiMnCo catalyst is less than in the FeNiCo catalyst. Additionally, a high-quality type-Ⅱa large diamond size of 5.0 mm is obtained by reducing the growth rate and keeping the nitrogen concentration of the diamond to be less than 1 ppm, when Ti/Cu(1.6 wt%) is added in the FeNiCo catalyst.     

Dependence of Limited Growth Rate of High-Quality Gem Diamond on Growth Conditions

The growth rate of diamond has been investigated for a long time and researchers have been attempting to enhance the growth rate of high-quality gem diamond infinitely. However, it has been found according to previous research results that the quality of diamond is debased with the increase of growth rate. Thus, under specific conditions, the growth rate of high-quality diamond cannot exceed a limited value that is called the limited growth rate of diamond. We synthesize a series of type Ib gem diamonds by temperature gradient method under high pressure and high temperature （HPHT） using the as-grown {100} face. The dependence of limited growth rate on growth conditions is studied. The results show that the limited growth rate increases when synthetic temperature decreases, also when growth time is prolonged.     

Effects of Al and Ti/Cu on Synthesis of Type-IIa Diamond Crystals in Ni70Mn25Co5-C System at HPHT

High-quality type-Ⅱa gem diamond crystals are successfully synthesized in a NiToMn25Co5-C system by temperature gradient method （TGM） at about 5.5 GPa and 1560 K. Al and Ti/Cu are used as nitrogen getters respectively. While nitrogen getter Al or Ti/Cu is added into the synthesis system, some inclusions and caves tend to be introduced into the crystals. When Al is added into the solvent alloy, we would hardly gain high-quality type-Ⅱa diamond crystals with nitrogen concentration Nc 〈 1 ppm because of the reversible reaction of Al and N at high pressure and high temperature （HPHT）. Piowever, when Ti/Cu is added into the solvent alloy, high-quality type-Ⅱa diamond crystals with Nc 〈 1 ppm can be grown by decreasing the growth rate of diamonds.     

降温工艺对宝石级金刚石单晶品质的影响

在国产六面顶压机上,采用温度梯度法,在5.6 GPa,1200—1400?C的高压高温条件下,裂晶问题频繁出现的合成周期内,围绕裂晶现象开展了Ib型宝石级金刚石单晶的生长研究,系统考察了降温工艺对宝石级金刚石单晶品质的影响.针对宝石级金刚石单晶常见的裂纹缺陷,借助于扫描电子显微镜,分别对优质金刚石单晶和存在裂纹金刚石单晶的表面形貌进行了表征;利用微区傅里叶转换红外光谱测试手段,对上述两类晶体的N杂质含量分别进行了测试,依据测试结果,对裂晶出现的原因进行了分析;分别采用传统断电降温和缓慢降温工艺,考察了晶体生长结束后的降温工艺对宝石级金刚石单晶品质的影响.结果表明,缓慢降温工艺在很大程度上可以有效抑制裂晶问题出现.另外,从宝石级金刚石单晶品质和单晶受到的外应力两个方面着手,分别对裂晶出现的机理和采用缓慢降温工艺有效解决裂晶问题的机理进行了讨论.