Experimental Studies on Crystal Growth of Anatase under Hydrothermal Conditions
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摘要: 为了解金属离子生长成为热液矿石矿物的过程和机理，使用氟钛酸钾稀溶液在100 MPa和200~400℃条件下开展了一系列等温不等时和等时变温实验.结果显示该热液条件下形成了不同形貌的锐钛矿.随着反应时间和温度的增加，锐钛矿由几十纳米生长至十几微米；10 h以内的晶体生长速度远高于10 h以后，相对高温下的晶体生长速度则高于低温，表明锐钛矿的热液生长与温度、过饱和程度密切相关.综合来看，粒子成核生长、定向附着和奥氏熟化先后控制了热液锐钛矿的生长，而金属在流体中的过饱和程度和溶解-沉淀过程则决定了其生长速度.因而锐钛矿的形态特征可用于指示其形成的温度、世代关系甚至含氟流体的演化历史.Abstract: How metal mineral grows in hydrothermal fluids from a metal ion or metallic compound to the macrocrystals is one of the most fundamental problems in mineralogy and metallogeny. In this study, a series of non-isothermal and non-isochronic hydrolysis experiments of potassium titanium fluoride (K2TiF6) solution were investigated at temperatures from 200 to 400℃ and pressure of 100 MPa. The results show that anatases, with varied morphology, were synthetized in the hydrothermal conditions. With increasing reactive time and temperature, the anatase can grow up from dozens of nanometers to 10 micrometers or more. Remarkably, the anatases that were synthetized within 10 h or at higher temperatures exceeds those over 10 h or at lower temperatures in the rate of growth, which suggests the supersaturation level of Ti and temperature dependence on the crystal morphology, grain size and the rate of growth of the anatase. Generally speaking, classical nucleation and growth, oriented attachment, and Ostwald ripening are involved in the growth of the hydrothermal anatase, in which the supersaturation level of metal in hydrothermal fluids and dissolution-precipitation process are decisive to control the rate of anatase growth. Finally, we consider anatase as a typomorphic mineral that its morphology could be used to decipher the formation temperature, generation relationship of minerals, and even the evolution of F-bearing hydrothermal fluids.
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Key words:
- hydrothermal /
- anatase /
- crystal growth /
- oriented attachment /
- Ostwald ripening /
- crystallography
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图 1 锐钛矿晶体生长实验的设备组装简图
Fig. 1. A sketch of cold-seal vessel for the experiments on the anatase growth
图 2 锐钛矿纳米晶的代表性能谱图
Fig. 2. Representative EDS spectra of synthesized anatase nano-crystals
图 3 不同温度下合成的锐钛矿代表性拉曼图
Fig. 3. Representative Raman spectra of synthesized anatase at different temperatures
图 4 100 MPa和200 ℃条件下不同反应时间获得的锐钛矿晶体的扫描电镜图
a.0.1 h；b.3 h；c.10 h；d.52 h
Fig. 4. Scanning electron micrographs of synthesized anatase nano-crystals at 100 MPa and 200 ℃
图 5 100 MPa和300 ℃、400 ℃条件下合成的锐钛矿扫描电镜图
a.300 ℃和24 h；b.400 ℃和11 h；c, d.400 ℃和24 h
Fig. 5. Scanning electron micrographs of synthetized anatase at 100 MPa and 300 ℃ or 400 ℃
图 6 不同温度和时间条件下锐钛矿晶体的尺寸示意
Fig. 6. Grain size diagram of synthesized anatase at varied reactive times and temperatures
图 7 不同时间尺度下锐钛矿的定向附着生长
Fig. 7. Oriented attachment growth of anatase nano-crystals on the prolonged reactive time
表 1 锐钛矿晶体生长实验的条件和对应的产物特征
Table 1. Run conditions and product characteristics in the anatase growth experiments
序号 初始浓度(mol/L) 压力(MPa) 温度(℃) 运行时间(h) 尺寸(nm) 形貌描述 1 0.02 100 200 0.1 10~80 自形扁平十面体单晶纳米颗、他形-半自形纳米颗 2 0.02 100 200 0.1 15~80 自形扁平十面体单晶纳米颗、他形-半自形纳米颗 3 0.02 100 200 3 30~200 自形截头锥形十面体单晶纳米颗、他形-半自形纳米颗 4 0.02 100 200 3 20~180 自形截头锥形十面体单晶纳米颗、他形-半自形纳米颗 5 0.02 100 200 10 40~500 他形-半自形短柱状纳米晶、不定形纳米颗 6 0.02 100 200 52 60~600 他形-半自形短柱状纳米晶、不定形纳米颗 7 0.04 100 300 12 100~500 自形-半自形多面锥体单晶纳米颗、不定形纳米颗 8 0.04 100 300 24 135~650 自形-半自形多面锥体单晶纳米颗、不定形纳米颗 9 0.04 100 400 11 1 000~11 900 不完整的半自形截头锥形十面体、不定形晶体 10 0.04 100 400 24 2 000~12 100 不完整的半自形截头锥形十面体、不定形晶体 
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