粉色蛋白石中“水”的热变异行为研究
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摘要
粉色蛋白石为蛋白石和坡缕石的矿物集合体,该类蛋白石的矿物组成和谱学特征与传统的具有变彩效应的蛋白石有着明显的差异。采用常温或变温红外光谱、差热分析等分析测试方法,就粉色蛋白石的热变异行为等问题进行了初步探讨与研究。结果表明:粉色蛋白石红外吸收谱带表征了硅氧化物蛋白石和硅酸盐矿物坡缕石的振动特点,其结构水伸缩振动所致的红外吸收谱带主要表征为4000～3000cm~(-1)范围内一组强度不一的红外吸收谱带。结构水、结晶水以及吸附水倍频、合频组合频振动所致的红外吸收谱带主要集中于8000～4000cm~(-1)范围内。随着温度的升高,吸收谱带的相对吸收强度呈下降趋势,吸收峰也出现了不同程度的漂移、分裂或者新增,这说明—OH的结合与Si~(4+)无关,而与坡缕石中的Mg~(2+)、Al~(3+)、Fe~(2+)、Fe~(3+)相关。
The pink opal is a mineral aggregation of opal and palygorskite.The minerals composition and spectral characteristics of the opal have a significant difference with the traditional opal of play of color.The thermal variation behaviors of the pink opal are studied by means of differential thermal analysis and Fourier transform infrared spectroscopy(FTIR)under room temperature or variable temperature.The results show that the infrared absorption band of the pink opal characterizes the vibrational characteristics of silicate minerals palygorskite and silico oxide opal.The infrared absorption band caused by the structural water expansion vibration is mainly characterized by agroup of infrared absorption bands with different intensities in the range of 4000-3000 cm~(-1).The infrared absorption band caused by sum frequency and frequency doubling of vibration frequency of structural water,crystalline water and adsorptive water is mainly concentrated in the range of 8000-4000 cm~(-1).With the increase of temperature,the relative absorption intensity of the absorption band is decreasing,and the absorption peaks also have different degrees of drift,splitting or addition.It shows that the binding of—OH has no relation to Si~(4+),and is related to Mg~(2+),Al~(3+),Fe~(2+) and Fe~(3+) in palygorskite.
The pink opal is a mineral aggregation of opal and palygorskite.The minerals composition and spectral characteristics of the opal have a significant difference with the traditional opal of play of color.The thermal variation behaviors of the pink opal are studied by means of differential thermal analysis and Fourier transform infrared spectroscopy(FTIR)under room temperature or variable temperature.The results show that the infrared absorption band of the pink opal characterizes the vibrational characteristics of silicate minerals palygorskite and silico oxide opal.The infrared absorption band caused by the structural water expansion vibration is mainly characterized by agroup of infrared absorption bands with different intensities in the range of 4000-3000 cm~(-1).The infrared absorption band caused by sum frequency and frequency doubling of vibration frequency of structural water,crystalline water and adsorptive water is mainly concentrated in the range of 8000-4000 cm~(-1).With the increase of temperature,the relative absorption intensity of the absorption band is decreasing,and the absorption peaks also have different degrees of drift,splitting or addition.It shows that the binding of—OH has no relation to Si~(4+),and is related to Mg~(2+),Al~(3+),Fe~(2+) and Fe~(3+) in palygorskite.
引文
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[2]Gaillou E,Fritsch E,Aguilar-Reyes B,et al.Common gem opal:an investigation of micro-to nano-structure[J].American Mineralogist,2008,93(11/12):1865-1873.
[3]Chen T H,Xu X C,Xu H F,et al.Characteristics and significance of opals in palygorskite clay at the boundary between Jiangsu and Anhui provinces[J].Acta Mineralogica Sinica,2005,25(1):81-88.陈天虎,徐晓春,Xu H F,等.苏皖坡缕石粘土中蛋白石特征及其成因意义[J].矿物学报,2005,25(1):81-88.
[4]Qi L J,Yang M Z,Hu Y B,et al.Blue opal from Peru[J].Journal of Gems and Gemmology,2001,3(3):13-16.亓利剑,杨梅珍,胡永兵,等.秘鲁蓝欧泊[J].宝石和宝石学杂志,2001,3(3):13-16.
[5]Zhao H P,Zhang X M,He X M.Prase opal from Tanzania[J].Journal of Gems&Gemmology,2014,16(4):14-21.赵海平,张雪梅,何雪梅.坦桑尼亚绿色蛋白石[J].宝石和宝石学杂志,2014,16(4):14-21.
[6]Yan J,Hu X C,Fang B,et al.Study on the mineralogical and optical characteristics of blue opal from Lishui investigated by XRF-SEM-XRD-FTIR[J].Rock and Mineral Analysis,2014,33(6):795-801.严俊,胡仙超,方飚,等.应用XRF-SEM-XRD-FTIR等分析测试技术研究丽水蓝色类欧泊(蛋白石)的矿物学与光学特征[J].岩矿测试,2014,33(6):795-801.
[7]Chen H S,Sun Z Y,Shao J C.Investigation on FT-IR spectroscopy for eight different sources of SiO2[J].Bulletin of the Chinese Ceramic Society,2011,30(4):934-937.陈和生,孙振亚,邵景昌.八种不同来源二氧化硅的红外光谱特征研究[J].硅酸盐通报,2011,30(4):934-937.
[8]Zhi Y X,Liao Z T,Zhou Z Y,et al.A resolution to the hydroxy types of nephrite and its near infrared spectroscopy[J].Spectroscopy and Spectral Analysis,2013,33(6):1481-1486.支颖雪,廖宗廷,周征宇,等.软玉中结构水类型和近红外光谱解析[J].光谱学与光谱分析,2013,33(6):1481-1486.
[9]Chen X,Liu X X,Yang S J.The thermal analysis technique and its application in inorganic materials research[J].Journal of Hubei Normal University(Natural Science),2015,35(4):79-87.陈秀云,刘晓霞,杨水金.热分析技术及其在无机材料研究中的应用[J].湖北师范学院学报(自然科学版),2015,35(4):79-87.
[10]Li B,Gao J H,Xu Z H,et al.Application of thermal analysis in materials analysis[J].Analytical Instrumentation,2018(2):77-81.李波,高锦红,许祖昊,等.热分析法在材料分析中的应用新进展[J].分析仪器,2018(2):77-81.
[11]Gionis V.On the structure of palygorskite by midand near-infrared spectroscopy[J].American Mineralogist,2006,91(7):1125-1133.
[12]Suárez M,García-Romero E.FTIR spectroscopic study of palygorskite:influence of the composition of the octahedral sheet[J].Applied Clay Science,2006,31(1/2):154-163.
[13]Lu B Q.The gemological mineralogy and spectroscopy of nephrite cat’s eye and serpentine cat′s eye from Shimian,Sichuan province,southwest of China[D].Shanghai:Shanghai University,2005.卢保奇.四川石棉软玉猫眼和蛇纹石猫眼的宝石矿物学及其谱学研究[D].上海:上海大学,2005.
[14]Xing Y Y,Qi L J,Wang H T.Mineralogical characteristics and colouration mechanism of blue opals from Peru[J].Rock and Mineral Analysis,2017,36(6):608-613.邢莹莹,亓利剑,王海涛.秘鲁蓝色蛋白石矿物学性质及致色机理初探[J].岩矿测试,2017,36(6):608-613.
[15]Han X Z,Wu X,Kang Y,et al.Application of Raman spectroscopy in sapphire inclusion research[J].Laser&Optoelectronics Progress,2016,53(3):033004.韩孝朕,吴晓,康燕,等.拉曼光谱在蓝宝石包体研究中的应用[J].激光与光电子学进展,2016,53(3):033004.
[16]Sun C,Yao X F,Cui J C,et al.Mineral spectrum measurement based on shortwave infrared imaging spectrometer[J].Acta Optica Sinica,2016,36(2):0230001.孙慈,姚雪峰,崔继承,等.基于短波红外成像光谱仪的矿石光谱测量[J].光学学报,2016,36(2):0230001.
[17]Zhu L,Wang LL,Dong X Y,et al.Mid-infrared supercontinuum generation with highly germaniumdoped silica fiber[J].Acta Optica Sinica,2016,36(3):0319001.朱磊,王鹿鹿,董新永,等.基于高掺锗石英光纤的中红外超连续谱产生[J].光学学报,2016,36(3):0319001.
[18]Han K,Chen J,Huang M,et al.Characterization of micron resolution by weak absorption of mid infrared optical elements[J].Chinese Journal of Lasers,2017,44(7):0715001.韩凯,陈坚,黄明,等.中红外光学元件微弱吸收实现微米分辨率的表征[J].中国激光,2017,44(7):0715001.