高纯石英的研究进展及发展趋势

doi:10.13745/j.esf.sf.2021.8.1

摘要/Abstract

摘要：

石英是一种在地壳上大量分布,有着广泛工业用途和广阔应用前景的矿物。当石英晶体形成演化时,受结晶时环境条件、流体性质、结晶后遭受改造(如变质作用、构造变形和热扰动等)等影响,杂质元素如P、Ti、Ge、Al、B、Be、Ca、Na、K、H、Li等会或多或少存在于石英晶体中,因此在自然界不存在纯SiO₂组分的石英。同时,基于石英的微量元素组成,可以反演石英源区和形成演化过程,并用于研究岩石及矿床成因等科学问题。石英晶体内部杂质元素以类质同象替代、气液包裹体、矿物包裹体(不能按尺度分,应该按照状态划分存在形式)3种形式存在。石英中杂质元素的种类、含量、赋存形式,特别是包裹体特征将直接影响石英资源的品质和工业用途。本文还系统地阐述了石英的发光特性、工艺性能以及高纯石英的质量分类与标准和高纯石英原料来源等方面的内容。在本研究中,通过光学显微镜和激光拉曼测试,初步地查明了苏北张锦庄石英砂和广西姑婆山花岗岩石英中流体包裹体的分布和矿物包裹体的种类,这是开展后续研究的基础。高纯石英是优质石英资源经纯化加工得到的高品质石英原材料,可用于石英玻璃、石英坩埚、半导体、高温灯管、光纤、精密光学、微电子和太阳能等高新技术产业中。研究高纯石英原料的评价体系、理想源岩和形成机制有益于持续性地供给高纯石英原料, 极大地提高了石英原料的工业附加值。

关键词: 高纯石英, 高纯石英原料, 苏北张锦庄石英砂, 广西姑婆山花岗岩

Abstract:

Quartz is widely distributed on the Earth’s surface. It has a broad range of industrial uses and other application prospects. Natural quartz, however, are not entirely SiO₂ but contain other elements more or less, such as P, Ti, Ge, Al, B, Be, Ca, Na, K, H, and Li, affected by the physico-chemical conditions/properties of crystallizing melt or fluid as well as post-crystallization alterations (such as metamorphism, structural deformation, and thermal disturbance). Diagenetic study of quartz based on its trace element compositions plays a part in petrological and metallogenic investigations of mineral deposits. The impurity elements in quartz are in forms of lattice impurities or nano- to macro-scale inclusions, and the impurity type, quantity, and form (specially inclusions) affects the quality and industrial use of quartz directly. Here, topics including the luminescent properties and technical performance of quartz, quality classification and rating standard for high purity quartz, source materials of high purity quartz are systematically reviewed. Also, the distribution of fluid inclusions and types of mineral inclusions in quartz from the Zhangjinzhuang quartz sand (Northern Jiangsu) and Guposhan granite (Guangxi) were determined in this study by optical microscopy observations and laser Raman analysis to provide a basis for subsequent research. High purity quartz of high quality and value is naturally formed (such as crystal) or processed from high quality quartz raw materials. It is an environment-friendly strategic resource used in high-tech industries, such as semiconductor, high-temperature lamp tubing, fiber optics, precision optics, microelectronics, and solar energy. Researches on the evaluation system, ideal source rock and formation mechanism for high purity quartz raw materials are beneficial for ensuring a sustainable supply of high purity quartz raw materials and increasing the added value of quartz products.

Key words: quartz, high purity quartz, high purity quartz raw materials, quartz sand in Zhuangjinzhuang in Northern Jiangsu, Guposhan granite in Guangxi

中图分类号:

杨晓勇, 孙超, 曹荆亚, 施建斌. 高纯石英的研究进展及发展趋势[J]. 地学前缘, 2022, 29(1): 231-244.

YANG Xiaoyong, SUN Chao, CAO Jingya, SHI Jianbin. High purity quartz: Research progress and perspective review[J]. Earth Science Frontiers, 2022, 29(1): 231-244.

图/表 9

图1 石英晶体中典型的类质同象替换 (引自文献[11])

Fig.1 Typical isomorphic substitution in quartz crystal. Adapted from [11].

图2 亚微米级和纳米级包裹体的背散射电子图像 (引自文献[39]) a—Llano流纹岩所含蓝色石英中的亚微米级锐钛矿(ilm)、金红石(rt)和云母(m)包裹体;b—Broken Hill蓝色石英中的亚微米级和纳米级金红石(表现为白色的点状或针状)包裹体。

Fig.2 BSE photos of submicron and nano inclusions. Adapted from [39]. (a) Submicron anatase (ilm), rutile (rt) and mica (m) inclusions in blue quartz from Llano rhyolite; (b) Rutile inclusions in the submicron and nanoscale metre grade (white punctate or needle-like) included in the Broken Hill blue quartz.

图3 石英中的流体包裹体 a-d—广西姑婆山花岗岩中石英所含的典型的流体包裹体; e-g—苏北张锦庄石英砂中石英所含的典型的流体包裹体。所有照片比例尺同图g所示标尺。

Fig.3 Fluid inclusions in quartz. a-d—Typical fluid inclusions in quartz from the Guposhan granite in Guangxi; e-g—Typical fluid inclusions in quartz from Zhangjinzhuang quartz sand, Northern Jiangsu Province. Photographic scales as shown in picture g.

图4 石英中的一些矿物包裹体及其激光拉曼光谱分析 a—广西姑婆山花岗岩中石英所含的磷灰石包裹体;b—苏北张锦庄石英砂中石英所含的方解石包裹体;c—苏北张锦庄石英砂中石英所含的微斜长石包裹体;d—苏北张锦庄石英砂中石英所含的金红石包裹体。

Fig.4 Microphotographs and Roman spectra of representative mineral inclusions in quartz. a—Apatite inclusions contained in quartz from the Guposhan granite in Guangxi; b—Calcite inclusions in quartz from Zhangjinzhuang quartz sand, Northern Jiangsu; c—Microplagioclase inclusion in quartz from Zhangjinzhuang quartz sand, Northern Jiangsu province; d—Rutile inclusions in quartz from Zhangjinzhuang quartz sand, Northern Jiangsu Province.

图5 石英品质分类(根据杂质总量)、价格范围和作为矿床开采所需的最小规模量 (据文献[25]修改)

Fig.5 Quality classification (according to total impurities) and price range of quartz, and minimum size of quartz deposit required for mining. Modified after [25].

图6 基于石英中Al和Ti含量的石英品质判断标准 (据文献[26]修改)

Fig.6 Judgment criteria of quartz quality based on the contents of Al and Ti in quartz. Modified after [26].

图7 石英元素丰度范围(灰色的条带)和平均值以及 IOTA标准石英和高纯石英推荐的元素含量上限 (据文献[27]修改)

Fig.7 Abundance range (grey bars) and average abundance (upper line) of elements in natural quartz, and the suggested maximum abundance of elements in high purity quartz (middle line) and in IOTA standard quartz (lower line). Modified after [27].

表1 高纯石英原料评价指标 (根据文献[28]修改)

Table 1 Assessment indexes for high purity quartz raw materials. Modified after [28].

等级	$化学成分 w (Si O 2) / %$	$平均嵌布粒度 d (Qz) / mm$	脉石矿物种类	包裹体特征		晶格杂质
a	>99.9	>5	0种	气液相	已破坏	纯净
b	99.5~99.9	2~5	1种	占主要	稀疏分布	星染状类质同象
c	99.0~99.5	0.2~2	2种	部分	密集分布	杂质出溶现象
d	<99.0	<0.2	>3种	固相矿物占主要部分		明显石英环带结构

表1 高纯石英原料评价指标 (根据文献[28]修改)

Table 1 Assessment indexes for high purity quartz raw materials. Modified after [28].

等级	$化学成分 w (Si O 2) / %$	$平均嵌布粒度 d (Qz) / mm$	脉石矿物种类	包裹体特征		晶格杂质
a	>99.9	>5	0种	气液相	已破坏	纯净
b	99.5~99.9	2~5	1种	占主要	稀疏分布	星染状类质同象
c	99.0~99.5	0.2~2	2种	部分	密集分布	杂质出溶现象
d	<99.0	<0.2	>3种	固相矿物占主要部分		明显石英环带结构

表2 不同成因石英原材料的性质和首选利用领域 (据文献[30]修改)

Table 2 Properties and preferred applications of quartz raw materials of different origins. Modified after [30].

石英成因	石英类型	属性	首选应用领域
岩浆/岩浆后成因	白岗岩石英	化学纯	高纯石英材料、光学、高温灯管、半导体、太阳能级Si
	伟晶岩	化学纯,晶体高度有序	光学和压电石英
	热液石英		石英合成、半导体、太阳能级Si、Si合金、玻璃
变质成因	石英岩	SiO₂含量可达>98%	难熔材料、Si材料、Si合金
变质成因	变质石英脉	化学纯	石英合成
沉积成因	石英砂	化学纯	玻璃和铸造工业、方石英、石英粉、Si玻璃、SiC
	石英砾石	化学纯	Si材料、Si合金、建筑工业
	沉积石英岩	化学纯,隐晶质SiO₂	难熔材料

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