山东蓝宝石的呈色机制及改色试验

利用穆斯堡尔谱分析结果以及前人光谱分析等资料，从铁离子的价态入手，重新确立了山东蓝宝石的呈色机制，确定出致蓝因素与致黑因素。认为Fe^2 与Ti^4 对可见光565nm的吸收是使蓝宝石产生美丽蓝色调的原因，而Fe^3 对可见光442nm的吸收是使蓝宝石呈黑色的原因，并在此基础上进行了以消除Fe^3 、保障并增加Fe^2 和Ti^4 为宗旨的改色实验，取得了较好的效果。     

山东蓝宝石的主要致色因素

山东蓝宝石颜色深暗,与其主要致色元素有着直接关系.对其化学成分进行分析认为:Cr2O3是红色、橙黄色、黄色的主要致色因素.而w(TiO2)低,w(TFeO)高,尤其是Fe3 大于全铁的90%,TFeO/TiO2比值大是山东蓝宝石颜色深暗的主要原因.对其紫外-可见光-近红外吸收光谱进行分析,进一步得出Cr3 离子的d-d电子跃迁、成对Fe3 离子、单Fe3 离子的d-d电子跃迁、Fe2 -Ti4 之间的电荷转移、Fe2 Fe3 之间的电荷转移等是山东蓝宝石致色的本质.代表绝大多数山东蓝宝石颜色的深蓝色蓝宝石,缺失紫外-可见光-近红外吸收光谱的575～711nm吸收带,即缺少Fe2 -Ti4 之间的电荷转移.因此,针对性地选择w(TiO2)高的蓝宝石进行改善,或是设法加入TiO2、减少Fe3 含量、在还原条件下改变其TFeO/TiO2的比值,应是目前山东蓝宝石改色的关键.     

蓝色翡翠的呈色机制探讨

近期广东市场上出现了一种来自缅甸的蓝色翡翠样品,该样品目前未见相关报道。为了确定其定名,通过常规宝石学测试、红外光谱和X射线粉末衍射测试对样品进行分析,表明样品的主要矿物组成为硬玉,质量分数约97．1％,检测鉴定结论为翡翠。为了对蓝色翡翠呈色机制进行研究,通过紫外一可见吸收光谱测试,表明可见光区480nm以后逐渐增强的吸收带是其产生蓝色的原因;采用电子探针进行化学成分测试,表明蓝色的成因与钒离子有关。根据3d过渡金属离子的晶体场理论和翡翠晶体场理论的研究,可以推测：由于翡翠结构中M1位的Al3＋被过渡金属离子钒（V4＋）替代,目l起八面体结构畸变而导致蓝色的产生,因此,蓝色是过渡金属离子钒（v4＋）产生的原生色。     

福建明溪蓝宝石的谱学特征及颜色成因

采用颜色测量、紫外-可见光谱、红外光谱等方法对福建明溪蓝宝石进行的研究表明,明溪蓝宝石颜色蓝中带黄,二色性强。紫外-可见吸收光谱中377,388和451nm吸收带较强。这些吸收带是Fe3 的d－d和Fe3 —Fe3 ,交换相合离子间的电子跃迁引起的。810nm带存在于各色蓝宝石中,强度变化较大,有时伴随有510nm吸收带。它是由Fe2 —Fe3 电荷转移形成的。570nm吸收带只出现在蓝色或绿色的蓝宝石中。结合蓝宝石红外33loom－‘吸收带与宝石颜色之间的关系,笔者将570nm吸收带归属于H、Fe、Ti构成的致色缺陷团。这一研究结果对蓝宝石呈色机理的进一步研究和宝石的合成等具有重要意义。     

山东蓝宝石铁离子的价态及其对色调的影响

山东蓝色蓝宝石的着色是由Ｔｉ４＋离子与Ｆｅ２＋离子合理配比而成，一般控制在Ｔｉ４＋／Ｆｅ２＋＝１的配比范围内。多余的Ｆｅ２＋和其它Ｆｅ３＋离子存在都不利于蓝色蓝宝石正常呈色。通过穆斯堡尔谱和电子顺磁共振谱分析，测定了山东蓝宝石中铁离子的不同价态和浓度。对Ｆｅ２＋和Ｆｅ３＋离子所引起的吸收光谱特征作了研究，查明只有Ｆｅ３＋浓度很高时才产生４７７ｎｍ吸收峰，是致使山东蓝宝石表观上呈深蓝带黑色调的的重要原因。     

福建明溪蓝宝石呈色机理研究

明溪蓝宝石呈色是铁，钛，铬等杂质过渡金属离子电子跃迁和电荷转移等因素共同作用的结果，但蓝色的深浅与铁的含量不呈简单的正相关关系，而更多地与铁，钛间含量的配比相关，Al2O3中OH的振动应成为人们关注的蓝宝石呈色影响因素之一。     

山东蓝宝石的呈色机制

本文采用电子探针、顺磁共振、吸收光谱等手段,着重研究了山东蓝宝石的吸收光谱特征,讨论了它的呈色机制,并简单论述了其改色的可能性。20000～10000cm~(-1)范围内的电荷转移跃迁是造成蓝宝石不同色调和颜色的主要原因,Fe~(2+)-Ti~(4+)、Fe~(2+)-Fe~(3+)、Fe~(3+)及O~(2-)-Fe~(3+)等吸收峰(带)的强弱和相对强弱决定了蓝宝石的具体颜色。如何协调这几个吸收峰的吸收强度是蓝宝石改色的关键。     

蓝色刚玉的致色改色理论分析

蓝色刚玉的致色改色理论分析常晓涛郑辙郑海飞（北京大学地质学系，北京１００８７１）关键词蓝宝石致色机理改色实验本文立足于原有蓝宝石的致色改色理论，通过实验及计算，对蓝宝石改色致色进行了基础性的理论研究，提出了杂质离子缺陷致色新认识，并以这一认识为原理，...     

福建明溪蓝宝石矿物学特征及致色机理探讨

利用颜色测量、顺磁共振谱、红外光谱和热谱等方法研究明溪蓝宝石的矿物学特征和结构特性，明溪蓝宝石色深，蓝中带黄，二色性强，分析表明Fe主要以Fe^3 形式存在，Fe^3 的d-d电子跃迁和Fe^2 -Ti^4 、O-Fe境塌菏转移是明溪蓝宝石致色的主要因素；H含量对蓝色的形成有重要作用。     

福建明溪天然蓝宝石在氩气气氛中的改色实验研究

明溪天然蓝宝石主要呈色元素为Fe和Ti，颜色常带有黄、绿或紫色调，颜色不纯正。在温度为1300℃，环境为氩气气氛中进行热处理后，可消除蓝宝石中原来存在的杂色调，使颜色向纯蓝色方向变化。本文还对热处理后蓝宝石的光吸收港及颜色变化机理进行了初步探讨。     

Origin of the color in cobalt-doped quartz

Synthetic Co-doped quartz was grown hydrothermally in steel autoclaves at the Technological Center of Minas Gerais (CETEC), Brazil. The quartz samples, originally yellow in the as-grown state acquired blue coloration after prolonged heat treatment times at 500°C near the alpha–beta transition temperature. UV–VIS–NIR absorption spectroscopy shows the characteristic spectra of Co³⁺ before heat treatment. After heat treatment, the optical absorption spectrum is dominated by two split-triplet bands the first in the near infrared region centered at about 6,700 cm⁻¹ (1,490 nm) and the second in the visible spectral range at about 16,900 cm⁻¹ (590 nm). Both split-triplet bands are typical for Co²⁺ ions in tetrahedral coordination environments. From the absence of electron paramagnetic resonance (EPR) spectra, we conclude that the Co²⁺ found in the optical absorption spectra of the blue quartz is not due to an isolated structural site in the quartz lattice. Instead, the blue color is associated with electronic transitions of Co²⁺ in small inclusions in which the Co site has tetrahedral symmetry. The non-observation of polarization-depend optical absorption spectra is also in agreement with this model. The results for Co²⁺ in quartz are different from Co-bearing spinel and staurolite and other silicates like orthopyroxene, olivine, and beryls. The formation process of the color center is discussed.     

Spectroscopic Features and Coloration of Gem-Quality Green Tsavorite in Major International Deposits and China

Tsavorite green colored by Cr3+/V3+ has been traditionally found and mined in Tanzania, Kenya and Madagascar in the Neoproterozoic Mozambique metamorphic belt (NMMB), and recently be found in Sanjiang, Litang, Sichuan, China. The differences of the chemical formula, spectroscopic features, as well as the concentrations of the V2O3 and Cr2O3 in the tsavorite crystals collected from major international deposits and Sanjiang, China have been investigated using EPMA, XRF, UV-VIS spectrometers, FTIR, Raman scattering microscopy, DiamondView TM techniques. It was found that the chemical formulas of African tsavorite and Chinese tsavorite are Ca3(Al,V)2[SiO4]3 and Ca3(Al,Cr)2[SiO4]3, respectively, indicating that tsavorite is a solid solution between dominant grossular and minor goldmanite and uvarovite. Two broad bands centered at 430 nm and 605 nm were the main absorption features in the tsavorite samples, which attribute to the absorption of Cr3+ and/or V3+ ions in the lattice. The green coloration is caused by Cr3+ and/or V3+ ions resulting in the absorption of purple and red components of the visible light. Absorptions caused of Fe3+ and Fe2+ ions could add the bluish color component in some of tsavorite samples. The intensity of green color is proportional to the concentrations of V2O3 and Cr2O3. The basic gemological properties, such as refractive index in the investigated samples were presented, and the definition and chemical and spectroscopic properties of tsavorite are discussed.     

Spectroscopic characterisation and crystal field calculations of varicoloured kyanites from Loliondo, Tanzania

Orange, ochre-coloured, light green and dark blue varieties of kyanite, ideally Al₂SiO₅, from Loliondo, Tanzania, have been characterised by electron microprobe analysis and polarised infrared and optical absorption spectroscopy. All colour varieties show elevated Fe contents of 0.39 to 1.31 wt.% FeO, but Ti contents only in the range of the EMP detection limit. Orange and ochre-coloured crystals have Mn contents of 0.23 and 0.06 wt.% MnO, respectively, the dark blue kyanite contains 0.28 wt.% Cr₂O₃, while the light green sample is nearly free from transition metal cations other than Fe. Polarised infrared spectra reveal OH defect concentrations of 3 to 17 wt.ppm H₂O with structural OH defects partially replacing the O_B (O2) oxygen atoms. Polarised optical absorption spectra show that the colour of all four varieties is governed by crystal field d-d transitions of trivalent cations, i.e. Fe³⁺ (all samples), Mn³⁺ (orange and ochre) and Cr³⁺ (blue kyanite), replacing Al in sixfold coordinated triclinic sites of the kyanite structure. Intervalence charge transfer, the prevalent colour-inducing mechanism in ‘usual’ (Cr-poor) blue kyanites, seems to play a very minor, if any, role in the present samples. Crystal field calculations in both a ‘classic’ tetragonal and in the semiempirical Superposition Model approach, accompanied by distance- and angle-least-squares refinements, indicate that Fe³⁺ preferably occupies the Al4 site, Cr³⁺ prefers the Al1 and Al2 sites, and Mn³⁺ predominantly enters the Al1 site. In each case specific local relaxation effects were observed according to the crystal chemical preferences of these transition metal cations. Furthermore, the high values obtained in the calculations for the interelectronic repulsion parameter Racah B correspond to a high ionic contribution to Me³⁺–O bonding in the kyanite structure. In the particular case of the blue sample, band positions specifically related to the high Racah B value enable this ‘unusual’ type of blue colouration of kyanite solely due to Cr³⁺ cations.     

河北省任丘市浅层地下水化学特征及形成机制

浅层地下水是任丘市重要的水资源之一,为研究其水化学特征及其形成机制,本文在实地调查取样分析化验的基础上,以水文地球化学理论为指导,借助多元数理统计的方法,从多个角度揭示了研究区浅层地下水的形成演化过程:①通过离散分析,认为研究区各主要离子变异系数较大,说明研究区浅层地下水受人为影响明显,水化学特征复杂.②通过相关分析,...     

海南蓬莱蓝宝石的光致发光谱学特征及意义

从光致发光光谱角度探讨了海南蓬莱蓝宝石的呈色机理.结果发现:与蓝宝石吸收光谱的500～700 nm吸收宽带相比,在500～720 nm发光波段内存在566.8 nm锐峰、600 nm左右肩峰和Cr~(3+)的694.2 nm特征峰.600 nm肩峰与其吸收峰镜像对称,566.8 nm处锐峰的产生原因复杂.600 nm肩峰可能与Fe~(2+)-Fe~(2+)离子对的电子跃迁有关;566.8 nm锐峰因532 nm激光激发Fe~(2+)-Ti~(4+)或Fe~(2+)-Fe~(3+)间的电荷迁移带,通过晶格造成Si~(4+)、Mg~(2+)等微量杂质离子敏化而产生.光致发光谱中呈现更多谱峰,能呈现离子跃迁时不同离子间发生的相互作用,为500～700 nm吸收宽带由不同致色机制的叠加给出了直接证明,是一种能全面地研究宝石矿物中致色元素能级结构的有效方法.