埃塞俄比亚染色欧泊的研究

目前,埃塞俄比亚染色欧泊在我国市场上屡见不鲜.本文采用常规宝石学测试手段、光谱分析、吸水实验、浸泡褪色实验和浸泡染色实验等方法对市场上常见的3种颜色的埃塞俄比亚染色欧泊进行了研究.结果表明,这些埃塞俄比亚染色欧泊主要通过浸泡于不同颜色的化学颜料溶液中上色,浸泡过程中往往添加含有羧酸根离子的表面活性剂或颜料超分散剂(如邻苯二甲酸酯),以使颜料颗粒分布更加均匀,这主要是由于埃塞俄比亚欧泊的孔隙度相对较大,对染料的吸附性相对较强.这些埃塞俄比亚染色欧泊的主要特征如下: ① 亚透明至微透明,染橙色和染蓝色样品具有弱至强的变彩,染黑色样品体色以灰蓝色或黄灰色为主,具有强烈的红色、黄色、绿色和蓝色变彩;透射光下照射,染黑色欧泊具有强至弱的红色调以及明显的染剂不均匀富集现象. ② 埃塞俄比亚染色欧泊和其天然欧泊一样吸水性强,吸水后密度、质量均有所增加,透明度增强,变彩可能会有所增强,也可能会有所减弱,染色欧泊密度范围为1.63～1.86 g/cm³,折射率在1.40(点测)左右,与天然欧泊一致,均低于澳大利亚和墨西哥的欧泊. ③ 在高倍显微镜下观察,染色样品颜色分布不均,内部常见色点、色斑、色块或色团分布,在表面部位染剂富集现象更为明显,常见染剂沿着边缘、刮痕或凹坑处富集. ④ 染色欧泊浸泡在不同的溶剂中会使溶剂变色. ⑤ 拉曼光谱表明,染色欧泊出现了很强的荧光背景及弱的热效应峰3 362 cm^-1,拉曼散射峰很弱. ⑥ 紫外可见光分光光谱表明,埃塞俄比亚染色欧泊与天然欧泊的吸收光谱不同.     

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

直至目前,我国相关欧泊的矿藏及其相应的矿物学特征鲜见报道,近期在浙江丽水缙云地区发现的蓝色类欧泊石引起了宝玉石科研工作者的广泛关注,但此矿物的相关研究至今尚未见论述。本文应用X射线荧光光谱(XRF)、场发射扫描电镜(FE-SEM)结合X射线粉晶衍射(XRD)与傅里叶变换红外光谱(FTIR)等多种综合检测技术首次对该类蓝色原矿的矿物学及光学变彩性质进行研究。结果表明:XRF分析显示蓝色原矿的主体化学组成为SiO₂(质量含量95%),仅含极少量的Fe₂O₃与Al₂O₃等杂质。同时,蓝色原矿及其相应的热处理后样品局部区域具有明显的变彩特征,主体的化学组成与其光学特征与天然欧泊的组成及变彩效应类同。XRD分析显示原矿粉体的无机相的晶型为方石英相,衍射峰形锐化,该晶体的结构特征明显相异于天然欧泊即微晶类的蛋白石(Opal-CT)、Opal-C与非晶蛋白石类(Opal-A)。此外,样品的红外光谱与天然欧泊间存在一定的频率位移。鉴于此,初步将该类原矿归属为类欧泊,因蓝色原矿所在地丽水缙云地区属于中生代陆相火山岩的地质,因此进一步将该原矿命名为一类火山岩类的类欧泊石,而有关此类欧泊是否可以归属为广义上的欧泊有待再作商榷。同时基于对蓝色原矿有无变彩效应区域的FE-SEM测试结论,本文初步推测该类矿物的光学变彩特征与原矿表面的“叠瓦状”结构形貌有关。     

海泡石中水的红外光谱及其结构稳定性的指示作用

在仔细分析海泡石中水的约外谱图特点的基础上,本文其结构水（ＯＨ）结晶水（ＯＨ２）沸石水（Ｈ２Ｏ）吸收带进行了逐个归属,并对比分析了热液型和沉积型海泡石谱图的差异,通过分析处理海泡石样品红外谱图,发现热处理过程中谱图的变化特征与热相变过程能很好地吻合,论证了海泡石中水的红外光谱具有指示结构稳定性的作用。     

黄色葡萄石的光谱学特征研究

利用傅里叶变换红外光谱仪、拉曼光谱仪和紫外可见光谱仪等测试分析手段,并结合偏光显微镜及常规宝石学方法,对黄色葡萄石样品进行了系统的测试研究。结果表明,黄色葡萄石具有典型的显微交织结构。红外吸收光谱和拉曼光谱显示了硅氧官能团的振动在900-1100cm~(-1)和400~800cm~(-1)波段产生特征吸收峰,同时OH~-的振动产生了3495cm~(-1)红外吸收峰和320cm~(-1)、390cm~(-1)拉曼吸收峰。紫外可见光谱显示,葡萄石具有430nm和580nm的吸收带,推断其黄色调是由Fe~(3+)致色形成的。     

天然变石和提拉法合成变石的红外-拉曼光谱分析

合成变石的晶体结构、化学成分及宝石学特征与天然变石基本一致,常规宝石学检测方法很难区分。实验采用红外光谱仪和拉曼光谱仪测试分析,发现天然变石以2 800cm~(-1)~3 300cm~(-1) O—H伸缩振动和2 362cm~(-1) CO_2伸缩振动为红外特征吸收峰,而提拉法合成变石无此特征吸收;拉曼分析中,638cm~(-1) Be—O弯曲振动为天然变石的特征吸收,674cm~(-1) Be—O伸缩振动、708cm~(-1) Be—O弯曲振动、473cm~(-1) Al—O平移运动为提拉法合成变石的特征吸收;对天然变石与提拉法合成变石拉曼谱932cm~(-1)进行洛伦兹线性拟合,得到天然变石半高宽均在17.0cm~(-1)以上,而提拉法合成变石均在17.0cm~(-1)以下。     

无色-近无色高温高压合成钻石的谱图特征及其鉴别方法

实验室发现大量小颗粒的无色高温高压(HPHT)合成钻石与天然钻石混杂镶嵌在各种饰品中,前人提出荧光和磷光特征是主要的快速区分特征,然而荧光、磷光特征的差异并不能完全将HPHT合成钻石与天然钻石区分开来。本文将常规的宝石学观察分析与多种高精度谱学测试相结合,对五粒不同的无色-近无色HPHT合成钻石样品进行深入研究。结果表明,五粒钻石在紫外可见吸收光谱无270 nm吸收或是只有极弱的270 nm吸收,随着颜色级别的降低,270 nm吸收越明显。红外光谱测试显示,各粒样品中都含有不等量的硼元素。光致发光光谱测试表明,HPHT合成钻石含有与微量N、Ni、Si等相关的晶格缺陷。超短波紫外光源激发下,所有的HPHT合成钻石都有强磷光,在钻石观察仪下可以观测到清晰的八面体和立方体分区特征。显然,不同的合成钻石的特征略有差异,但综合其荧光及磷光特征以及红外、紫外、光致发光光谱特征,可以准确地将无色HPHT合成钻石与对应的天然钻石区分开来。     

名义上无水矿物中"水"的原位变温红外光谱研究

名义上无水矿物(nominally anhydrous minerals, 简称NAMs, 如橄榄石、辉石、石榴石、长石等)中以缺陷形式存在的结构水的重要性已经被地球科学界广泛认同,并得到了越来越多的关注。由于对OH振动的高度敏感性,红外光谱方法被广泛用来测量NAMs中"水"的赋存状态、含量以及在晶体结构中的位置。随着傅立叶变换红外光谱仪的不断发展及分析技术的提高,以及红外附件的更新换代,出现了一些新的分析方法。原位变温红外光谱实验就是利用变温红外附件测量样品在不同温度下的红外光谱,通过研究不同温度下红外光谱图的峰形、峰位、峰数等参数的变化,了解温度改变过程中样品所发生的物理、化学变化,且具有实时监测的优点,因此广泛用于含水矿物和玻璃中OH和H₂O的研究。主要包括含水矿物和玻璃的脱水机理及脱水动力学研究,OH和H₂O的红外吸收系数的温度依赖性及不同温度下红外吸收系数的校正等方面。虽然原位变温红外光谱广泛应用于含水矿物和玻璃中水的研究,但是应用于名义上无水矿物还是刚刚起步。NAMs中的H是活动的,高温下H的赋存状态及其在晶体中的位置可能会不同于室温,而地质过程往往都在高温下进行,研究高温下NAMs中的水具有重要的地质学意义。因此,有必要利用原位变温红外光谱实时监测不同温度下NAMs中水的变化。有关NAMs中水的原位变温红外光谱实验早期工作只是观察不同温度下谱图参数的变化并给予一定的解释,以及用此法来确定NAMs中水的赋存状态。受含水矿物和玻璃的研究结果的启发,原位变温红外光谱实验目前也开始用来研究NAMs中水的脱水机理和扩散动力学。此外,利用原位变温红外光谱技术,通过研究不同温度下OH的积分吸收面积可探索NAMs中OH红外吸收系数温度依赖性;通过研究OH峰位随温度移动的幅度与某些化学成分的关系,可给出NAMs中OH的结合机理方面的有用信息。虽然近些年来已经开展了一些工作,取得了一些新的成果,但是总的说来还处在起步阶段,今后针对NAMs的研究重点应该集中在以下三个方面:(1)吸收系数温度依赖性的定量化,(2)脱水机理和动力学的扩展,(3) OH结合机理研究的深入。     

澳大利亚孟席斯祖母绿的光谱学特征

采用红外吸收光谱、拉曼光谱、紫外-可见-近红外吸收光谱等无损分析技术,并结合激光诱导击穿光谱和电子探针对澳大利亚孟席斯祖母绿的光谱特征、成分特征和颜色成因进行了研究。红外光谱分析显示孟席斯祖母绿具有[Si_6O_(18)]基团振动特征,其结构孔道中的Ⅱ型水吸收强于Ⅰ型水;拉曼光谱特征峰主要在323 cm、397 cm~(-1)、685 cm~(-1)和1067 cm~(-1),并可检测到142 cm~(-1)和190 cm~(-1)等弱散射峰;紫外-可见-近红外吸收光谱主要由Cr~(3+)、V~(3+)、Fe~(2+)和Fe~(3+)的吸收组成,其中424 nm和611 nm的吸收由Cr~(3+)和V~(3+)联合作用导致,644 nm、661 nm和682 nm的吸收由Cr~(3+)产生。结合Cr_2O_3含量显著高于V_2O_3的化学成分特征,表明孟席斯祖母绿主要由Cr致色。同时将孟席斯祖母绿与云南祖母绿进行对比分析,为孟席斯祖母绿的宝石学鉴定和质量评价提供依据。     

CCSD超高压变质岩中金红石结构水（OH^-）的傅里叶变换红外光谱测定及其地球动力学意义

名义上无水矿物(NAMs)的结构水研究是认识超高压变质作用(UHPM)过程中流体活动规律的重要手段,并对板块汇聚边缘大陆动力学及水的深部地球循环有重要意义。本文采用傅立叶变换红外光谱(非偏振光)研究了中国大陆科学钻探(CCSD)主孔岩心及其周围地表榴辉岩中副矿物—金红石中的结构水。所有测试样品都在3285 cm~(-1)和3295 cm~(-1)附近产生尖锐的吸收峰,证实“水”以结构羟基(OH~-)的形式赋存于金红石晶格之中。采用最新标定的摩尔吸收系数[38000 L/(mol·cm~2)]计算表明,金红石结构水含量在324×10~(-6)～523×10~(-6)范围内,远较前人有关金红石结构水含量的计算结果为低。同时,结构水分布不均一性在不同样品之间和颗粒内部都有明显表现,指示超高压变质过程中有限的流体活动和快速的板块俯冲—折返过程。     

镁铝榴石中的结构水的研究

通过对34个取自金伯利岩管中的粗晶镁铝榴石及碱性玄武岩中镁铝榴石巨晶样品的红外光谱分析发现,金伯利岩中部分镁铝榴石粗晶含有结构水,但不同颗粒之间含量差异很大,含量较高者约0.07wt%,而所研究的碱性玄武岩中的镁铝榴石不含结构水。分析发现,结构水在同一样品内分布基本均匀。在红外光谱3800—3500cm~(-1)波长范围内,分别记录到三峰谱和单峰谱两种类型,其中位于3570cm~(-1)±的吸收峰峰位明显受镁铝榴石结构中八配位阳离子(Mg~(2+)、Fe~(2+))影响,而六配位阳离子(Cr~(3+)、Al~(3+))的影响不明显。结构水在镁铝榴石晶格中的存在形式是多样的。     

秘鲁蓝色蛋白石矿物学性质及致色机理初探

近年来蓝色蛋白石的研究仅限于矿物成分及致色机理,并未对其化学成分、红外光谱、拉曼光谱等开展较为深入的分析。本文在前人的研究基础上,通过傅里叶变换红外光谱(FTIR)、X射线粉晶衍射(XRD)、电子探针分析(EMPA)、紫外可见分光光谱、拉曼光谱等技术对样品的振动光谱、官能团表征、矿物组成及呈色机理进行研究。研究结果表明:蓝色蛋白石的主要组成矿物为非晶态蛋白石,且振动光谱与天然蛋白石存在一定程度的频率位移。EMPA分析结果显示蓝色蛋白石主要元素为Si和Cu,且紫外可见分光光谱表征为742 nm附近一吸收强度较高的宽谱带。综合电子探针和紫外可见吸收光谱的测试结果得出,蓝色蛋白石的致色元素为Cu,在其内部呈典型平面正方形结构的[Cu~(2+)(H_2O)_4]~(2+),且Cu含量与其蓝色的体色存在一定的正相关性,即随着Cu含量增加蓝色体色更加浓艳。     

埃塞俄比亚欧泊充填处理及鉴定特征研究

埃塞俄比亚WOLLO地区产出的欧泊品种丰富,但火欧泊和水欧泊不稳定,易因外界温度或水分变化形成较多裂纹,严重影响其稳定性及加工性能。因此,本实验对埃塞俄比亚WOLLO地区产出的多裂纹火欧泊、水欧泊样品进行了充填处理,并对充填前、后的样品进行了显微放大观察和红外光谱、相对密度、紫外荧光的测试及分析,总结出了有机充填欧泊的一些鉴定特征。测试及分析结果显示,在2800-3100cm叫范围内红外吸收峰为有机充填欧泊的主要鉴定特征,表面及内部显微充填特征、偏小的相对密度、裂隙处的蠕虫状及空洞缺陷处的斑块状强蓝白色荧光可作为辅助鉴定特征。从样品的充填及测试分析结果可见,埃塞俄比亚WOLLO地区产出欧泊的有机充填方案可行,比较明显的开放裂隙易被充填。     

The geochemistry of gem opals as evidence of their origin

Seventy-seven gem opals from ten countries were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) through a dilution process, in order to establish the nature of the impurities. The results are correlated to the mode of formation and physical properties and are instrumental in establishing the geographical origin of a gem opal. The geochemistry of an opal is shown to be dependant mostly on the host rock, at least for examples from Mexico and Brazil, even if modified by weathering processes. In order of decreasing concentration, the main impurities present are Al, Ca, Fe, K, Na, and Mg (more than 500 ppm). Other noticeable elements in lesser amounts are Ba, followed by Zr, Sr, Rb, U, and Pb. For the first time, geochemistry helps to discriminate some varieties of opals. The Ba content, as well as the chondrite-normalized REE pattern, are the keys to separating sedimentary opals (Ba > 110 ppm, Eu and Ce anomalies) from volcanic opals (Ba < 110 ppm, no Eu or Ce anomaly). The Ca content, and to a lesser extent that of Mg, Al, K and Nb, helps to distinguish gem opals from different volcanic environments. The limited range of concentrations for all elements in precious (play-of-color) compared to common opals, indicates that this variety must have very specific, or more restricted, conditions of formation. We tentatively interpreted the presence of impurities in terms of crystallochemistry, even if opal is a poorly crystallized or amorphous material. The main replacement is the substitution of Si⁴⁺ by Al³⁺ and Fe³⁺. The induced charge imbalance is compensated chiefly by Ca²⁺, Mg²⁺, Mn²⁺, Ba²⁺, K⁺, and Na⁺. In terms of origin of color, greater concentrations of iron induce darker colors (from yellow to “chocolate brown”). This element inhibits luminescence for concentrations above 1000 ppm, whereas already a low content in U (≤ 1 ppm) induces a green luminescence.     

应用钻石观测仪-红外光谱仪-激光诱导击穿光谱仪鉴定无机材料充填翡翠

通过走访翡翠市场得知存在无机材料充填的翡翠,目前与其相关的研究资料较少,对无机材料充填翡翠缺少鉴定依据.本模拟实验使用水玻璃和硅溶胶这两类无机材料对低档翡翠进行充填以了解其鉴定特征.利用常规宝石学测试、钻石观测仪荧光观察、红外光谱分析(FTIR)、激光诱导击穿光谱分析(LIBS)对无机充填翡翠样品进行测试.结果表明:①...     

On the protonation of oxo- and hydroxo-groups of the goethite (α-FeOOH) surface: A FTIR spectroscopic investigation of surface O-H stretching vibrations

The O-H stretching region of goethite particles evaporated at different levels of acidity was investigated by Attenuated Total Reflectance (ATR)-Fourier Transform InfraRed (FTIR) spectroscopy. Two-dimensional IR Correlation Spectroscopy was used to identify correlations between different sets of discrete surface OH stretches and a Multivariate Curve Resolution analysis was used to resolve the predominant spectral components. Two dominant groups of hydroxyls were identified on the basis of their differences in proton affinity. Group I hydroxyls appear as two 3698/3541 and 3660/3490 cm⁻¹ band pairs. Group II hydroxyls are manifested through the 3648 and 3578 cm⁻¹ bands at greater levels of surface proton loading. There is consequently no correlation between O-H stretching frequencies and proton affinity. Groups I and II were assigned to mostly singly- (-OH) and doubly- (μ-OH) coordinated hydroxyls, respectively. Stretches arising from triply-coordinated (μ₃-OH) are proposed to be embedded within the dominant O-H band of bulk goethite. The possibility that these sites contribute to Group I and II hydroxyls should, however, not be entirely dismissed without further investigations.A reexamination of Temperature Programmed Desorption (TPD)-FTIR data of one goethite sample evaporated from alkaline conditions [Boily J.-F., Szanyi J., Felmy A. R. (2006) A combined FTIR and TPD study on the bulk and surface dehydroxylation and decarbonation of synthetic goethite. Geochim. Cosmochim. Acta70, 3613-3624] provided further constraints to this band assignment by providing clues to the network of surface hydrogen bonds. Important cooperative effects between hydrogen-bonded surface hydroxyls are suggested to play a crucial role on the variations of the position and intensity of discrete O-H stretching bands as a function of protonation level and temperature.     

Structural changes of synthetic opal by heat treatment

The structural changes of synthetic opal by heat treatment up to 1,400 °C were investigated using scanning electron microscopy, X-ray diffraction, and Fourier transform infrared and Raman spectroscopies. The results indicate that the dehydration and condensation of silanol in opal are very important factors in the structural evolution of heat-treated synthetic opal. Synthetic opal releases water molecules and silanols by heat treatment up to 400 °C, where the dehydration of silanol may lead to the condensation of a new Si–O–Si network comprising a four-membered ring structure of SiO₄ tetrahedra, even at 400 °C. Above 600 °C, water molecules are lost and the opal surface and internal silanol molecules are completely dehydrated by heat effect, and the medium-temperature range structure of opal may begin to thermally reconstruct to six-membered rings of SiO₄ tetrahedra. Above 1,000 °C, the opal structure almost approaches that of silica glass with an average structure of six-membered rings. Above 1,200 °C, the opal changes to low-cristobalite; however, minor evidence of low-tridymite stacking was evident after heat treatment at 1,400 °C.     

Peculiarities of the oxygen isotope ratio in precious opals

This paper presents the results of the δ¹⁸O study of the precious opals from Primor’e (Raduzhnoe deposit), Australia, and Ethiopia and the modern opals from the hydrotherms of the Mendeleev Volcano (Kunashir Island, Kuril Islands). It is established that the oxygen isotope ratio in opals may serve as a criterion for the estimation of their formation temperature. The low-temperature sedimentary opals are relatively enriched in the heavy oxygen isotope independently of the sedimentary or volcanic host rocks. Examples are the Australian and Slovakian opals of the A-type. The hydrothermal opals are enriched in the light oxygen isotope, which depends on the precipitation temperature. The higher the temperature, the lighter the oxygen isotope ratio of the precipitating opal is and the closer it is to that of the hydrothermal fluid.     

Coordination of boron in nominally boron-free rock forming silicates: Evidence for incorporation of BO3 groups in clinopyroxene

To explore mechanisms of B-incorporation in common chain silicates we have investigated synthetic diopside samples produced under boron-saturated conditions by ¹¹B and ²⁹Si magic-angle spinning (MAS) NMR and single-crystal NRA, FTIR, EMP and XRD/SREF techniques. Our samples contain 0.14-0.65 wt.% B₂O₃. NMR reveals that B is predominantly present in trigonal coordination in the clinopyroxene structure. This observation is supported by vibrational bands characteristic for B-O stretching in BO₃ groups in the range 1250-1400 cm⁻¹ in polarised single crystal FTIR-spectra. Single crystal structure refinements suggest that boron replaces Si at the T site. Combined, these results suggest that boron replacement for Si at the T-site leads to disruption of one of the T-O bonds of the nominal clinopyroxene structure resulting in replacement of SiO₄ tetrahedra by BO₃ groups. Our results show that high concentrations of boron can be incorporated in the nominally boron-free diopside. Elevated B-concentrations in the present calcic clinopyroxenes are accompanied by modifications of the diopside crystal structure involving the breaking of one T-O bond and simultaneous formation of vacancies at the octahedral M2 site. These structural modifications destabilize the structure and constitute thereby limiting factors for incorporating higher boron concentrations in diopside.     

安徽马鞍山磷铝石宝石矿物学特征研究

近年来在安徽马鞍山地区所在的绿松石矿体附近,相继发现一种绿色、半透明的磷铝石,部分达到宝石级别。本文采用电子探针、X射线粉晶衍射仪、扫描电镜、傅里叶变换红外光谱仪、紫外可见光谱仪等测试技术,对该地区磷铝石的化学成分、矿物成分、微观结构和光谱特征进行对比验证和综合分析,研究其水的赋存形式,进而对磷铝石的呈色机制作了深入探讨。电子探针分析显示该地区磷铝石的化学成分主要以Al、P元素组成,含微量的Fe、V元素。X射线粉晶衍射与红外吸收光谱分析表明主要矿物为磷铝石,基本不含有其他杂质矿物;磷铝石是一种水合磷酸盐矿物,含有结晶水以及少量结构水的矿物,且结晶水与结构水多与Al3+(Fe3+)相结合的形式存在。偏光显微镜和扫描电镜观察显示磷铝石整体以鳞片状集合体产出,微观上多以短柱状及板片状堆积,单个晶体显示斜方晶系结晶生长习性。紫外可见吸收光谱中639 nm处吸收谱峰由Fe3+与V3+联合所致,300、423、864 nm处吸收峰由Fe3+所致,说明Fe3+与V3+的共同作用是马鞍山地区磷铝石呈现绿色的主要原因。本研究对于认识该类磷铝石的宝石矿物学性质以及颜色成因具有一定意义。