MO—SiO2二元体系的熔体结构

本文讨论了MO-SiO_2二元熔体的结构与熔体热力学性质的相互关系。在低x_(sio_2)(X_(sio_2)<0.5)的这类熔体中,SiO_4~(4-)、Si_2O_7~(6-)、Si_3O_(10)~(8-)……及链状聚合物是熔体中的主要阴离子。聚合作用是决定熔体结构的主要机制。高x_(sio_2)(x_(sio_2)≥0.5)的二元熔体中出现环状及三维架状的阴离子聚合物。熔体不混溶性是这类熔体的普遍特征。在聚合模型的基础上,本文讨论了x_(sio_2)>0.5的二元熔体中的桥氧、非桥氧及自由氧离子在熔体中的分配及其与x_(sio_2)的关系。在动力学过程基础上推导出在熔体中服从Poission分布。最后对聚合反应平衡常数与聚合物链长及x_(sio_2)的关系进行了讨论。     

同结线附近AbxAnxDiy系列硅酸盐熔体结构及其结晶相的光谱研究

通过高温熔融，对同结线附近一系列硅酸盐熔体进行淬冷或不同速度冷却，实验获得的样品经过显微拉曼光谱分析，对比研究了AbxAnxDiy系列熔体在不同结线附近熔体结构跨相区变化情况，以及析出晶体对相应熔体结构的继承特点，熔体结构单元相对含量，在相界线两侧有某种程度的突变，熔体结构的变化对熔体的粘度，密度影响不同，拉曼光谱检测显示，硅酸盐玻璃的结构对降温速度变化不敏感，晶体对其相应熔体结构的部分继承作用，可能意味着晶体生长单元与熔体结构单元密切相关。     

溶胶凝胶法制备（Eu^2＋，Dy^3＋）SrAl2O4

采用无机盐溶胶-凝胶法制备了颗粒均匀的形态为针状的(Eu2+,Dy3+)SrAl2O4纳米粉体.通过TG-DTA分析和X射线衍射和扫描电镜分析方法,对样品进行了微观结构和表面形态的表征.研究了纳米(Eu2+,Dy3+)SrAl2O4粉体在不同烧结温度下固相反应过程和成相规律.实验结果表明,当样品的烧结温度为500 ℃时是单一的Sr(NO3)2晶相;750 ℃左右生成了Sr3Al2O6,并伴有少量SrAl2O4晶体;1 100 ℃是生成了结晶度良好的针状纳米(Eu2+,Dy3+)SrAl2O4粉体.通过计算,样品粉体晶粒平均为80～100 nm.该晶体粒度随烧结温度升高而逐渐变大.     

花岗岩—KBF4—Na2MoO4—WO3体系的实验研究及其矿床学意义

为探讨长英质岩浆作用过程中金属成矿元素的地球化学行为及其成矿意义,我们进行了常压下花岗岩－ＫＢＦ３－Ｎａ２ＭｏＯ４－ＷＯ３体系的实验研究。结果表明,高温（１２５０℃）条件下呈均一状态的花岗岩－ＫＢＦ４－ＮａＭｏＯ４－ＷＯ３体系,当温度降低时发生液态不混溶,从中分离出含矿熔体的小液滴,体系中的Ｍｏ（Ｗ）几乎全部富集在这种小液滴中。含矿熔体中极富含Ｃａ、Ｍｇ和Ｐ,而贫Ｓｉ、Ａｌ和Ｋ,Ｈ２Ｏ和Ｆ富集在含矿熔体中。此实验结果表明：长英质岩浆中液态不混溶作用的发生可以使成矿元素Ｗ和Ｍｏ富集到与硅酸盐熔体不混溶的独立的非硅酸盐熔体中。这种熔体在适当的地质条件下继续演化可形成类似镁铁质岩浆演化过程中常出现的岩浆熔离型矿床。本实验结果可能为斑岩矿床的形成机理提供一种新的解释。     

溶胶-凝胶法制备纳米荧光粉Y4Al2O9:Eu3+的初步研究

用溶胶-凝胶法(sol-gel)制备了纳米荧光粉Y4Al2O9: Eu3+,用X射线粉晶衍射对其进行了物相鉴定,表明在900℃已经得到纯相的Y4Al2O9产物,并用透射电镜对其进行形貌和衍射分析,分析结果证明得到的产物为纳米粉末态晶体,产物Y4Al2O9:Eu3+粒径均匀,大致在20～50nm之间,平均粒径为30nm.并用荧光光度计对其荧光光谱进行了研究,光谱表明Eu3+在Y4Al2O9晶格中占据两种不同的位置.用λ =254nm的紫外光激发Y4Al2O9:Eu3+时,产生两条发光谱带,即由于5 D 0→7 F 1的跃迁产生在峰值λ =590nm处的橙色发光带,和5 D 0→7 F 2跃迁在峰值λ =610nm处的红色发光带.     

溶胶—凝胶法制备纳米荧光粉Y4A2O9：Eu^3＋的初步研究

用溶胶－凝胶法（sol-gel)制备了纳米荧光粉Y4Al2O9:Eu^3 ，用X射线粉晶对其进行了物相鉴定，表明在900℃已经得到纯相的Y4Al2O9产物，并用透射电镜对其进行形貌和衍射分析，分析结果证明得到的产物为纳米粉末态晶体，产物Y4Al2O9：Eu^3 粒径均匀，大致在20－50nm之间,平均粒径为30nm。并用荧光光度计对其荧光光谱进行了研究，光谱表明Eu^3 在 Y4Al2O9晶格中占据两种不同的位置。用λ=254nm的紫外光激发了Y4Al2O9：Eu^3 时，产生两条发光谱带，即由于^5D0→^7F1的过产生在峰值λ＝590nm处的橙色发光带，和^5D0→^7F2跃迁在峰值λ＝610nm处的红色光带。     

钠长花岗岩—H2O—HF体系中流体／熔体间氟的分配实验研究

在ｐ＝１００Ｍｐａ,在７７０℃≤ｔ≤８００℃和ＷＦ＝２％－６％条件下进行了钠长花岗岩－Ｈ２Ｏ－ＨＦ体系液相线附近线体／熔体间氟的分配实验。对淬火玻璃的主要元素和氟含量进行了电子探针测定。用质量平衡法计算了流体中的氟含量,所获得的氟的流体／熔体分配系数ＤＦ均不盱１．０随体系氟含量的增加ＤＦ有所增大,表明在花岗岩岩浆一热液体系,氟优先进入熔体相,含氟花岗岗岩结晶晚期流体释放阶段残余熔体仍保保持富氟特征     

Behavior and effects of phosphorus in the system Na2O−K2O−Al2O3−SiO2−P2O5−H2O at 200 MPa(H2O)

The addition of phosphorus to H₂O-saturated and initially subaluminous haplogranitic (Qz–Ab–Or) compositions at 200 MPa(H₂O) promotes expansion of the liquidus field of quartz, a marked decrease of the solidus temperature, increased solubility limits of H₂O in melt at low phosphorus concentrations, and fractionation of melt out of the haplogranite plane (projected along an Or₂₈ isopleth) toward a peralkaline, silica-poor but quartz-saturated minimum composition. The partition coefficient for P₂O₅ between aqueous vapor and melt with an ASI (aluminum saturation index, mol Al/[mol Na+K])=1 is negligible (0.06), and consequently so are the effects of phosphorus on other melt-vapor relations involving major components. Phosphorus becomes more soluble in vapor, however, as the concentration of a NaPO₃ component increases via the fractionation of melt by crystallization of quartz and feldspar. The experimental results here corroborate existing concepts regarding the interaction of phosphorus with alkali aluminosilicate melt: phosphorus has an affinity for alkalis and Al, but not Si. Phosphorus is incorporated into alkali feldspars by the exchange component AlPSi_-2. For subaluminous compositions (ASI=1), the distribution coefficient of phosphorus between alkali feldspar and melt, D[P]Af/m, is 0.3. This value increases to D[P]Af/m=1.0 at a melt ASI value of 1.3. The increase in D[P]Af/m with ASI is expected from the fact that excess Al promotes the AlPSi_-2 exchange. With this experimental data, the P₂O₅ content of feldspars and whole rocks can reveal important facets of crystallization and phosphorus geochemistry in subaluminous to peraluminous granitic systems.     

下地幔温压下(Mg,Fe)SiO3钙钛矿的相稳定性

在69~100 GPa冲击压力(估算温度为2600~4300 K)范围内进行了初始样品为(Mg0.92,Fe0.08)SiO3顽火辉石和MgO+SiO2的冲击压缩回收实验.对回收样品进行的X射线衍射(XRD)分析结果表明:两发顽火辉石回收样品的主相均是单链状结构硅酸盐,而非钙钛矿结构;另外,回收样品中均未观察到氧化物SiO2和(Mg0.92,Fe0.08)O的XRD特征谱线;两发MgO+SiO2回收样品中均观察到SiO2和镁橄榄石(Mg2SiO4)而没有氧化物MgO.实验结果表明:在冲击压缩过程中样品处于钙钛矿结构,在冲击卸载过程中样品发生了由钙钛矿结构向单链状结构的逆转相变;在实验的温压范围内,不可能发生由(Mg0.92,Fe0.08)SiO3向SiO2和(Mg0.92,Fe0.08)O的化学分解相变,顽火辉石的高压相--钙钛矿结构是稳定的.高压加载或卸载过程引起的晶格畸变导致回收样品和原始样品的谱线差异,而高压加载导致钙钛矿型(Mg0.92,Fe0.08)SiO3晶格畸变的可能性更大.     

Characterization of NH4-phlogopite (NH4) (Mg3) [AlSi3O10] (OH)2 and ND4-phlogopite (ND4) (Mg3) [AlSi3O10] (OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

 A synthesis technique is described which results in >99% pure NH₄-phlogopite (NH₄) (Mg₃) [AlSi₃O₁₀] (OH)₂ and its deuterium analogue ND₄-phlogopite (ND₄) (Mg₃) [AlSi₃O₁₀] (OD)₂. Both phases are characterised using both IR spectroscopy at 298 and 77 K as well as Rietveld refinement of their X-ray powder diffraction pattern. Both NH₄ ⁺ and ND₄ ⁺ are found to occupy the interlayer site in the phlogopite structure. Absorption bands in the IR caused by either NH₄ ⁺ or ND₄ ⁺ can be explained to a good approximation using T_d symmetry as a basis. Rietveld refinement indicates that either phlogopite synthesis contains several mica polytypes. The principle polytype is the one-layer monoclinic polytype (1M), which possesses the space group symmetry C2/m. The next most common polytype is the two-layer polytype (2M ₁ ) with space group symmetry C2/c. Minor amounts of the trigonal polytype 3T with the space group symmetry P3₁12 were found only in the synthesis run for the ND₄-phlogopite. Electron microprobe analyses indicate that NH₄-phlogopite deviates from the ideal phlogopite composition with respect to variable Si/Al and Mg/Al on both the tetrahedral and octahedral sites, respectively, due to the Tschermaks substitution ^VIMg²⁺+^IVSi⁴⁺↔^VIAl³⁺+^IVAl³⁺ and with respect to vacancies on the interlayer site due to the exchange vector ^XII(NH₄)⁺+^IVAl³⁺↔^XII□+^IVSi⁴⁺. Received: 30 August 1999 / Accepted: 2 October 2000     

Temperature-dependent magnetic susceptibility behaviour of spinelloid and spinel solid solutions in the systems Fe2SiO4–Fe3O4 and (Fe,Mg)2SiO4–Fe3O4

The magnetic behaviour and Curie temperatures (T _C ) of spinelloids and spinels in the Fe₃O₄–Fe₂SiO₄ and Fe₃O₄–(Mg,Fe)₂SiO₄ systems have been determined from magnetic susceptibility (k) measurements in the temperature range –192 to 700 °C. Spinelloid II is ferrimagnetic at room temperature and the k measurements display a characteristic asymmetric hump before reaching a T _C at 190 °C. Spinelloid V from the Mg-free system is paramagnetic at room temperature and hysteresis loops at various low temperatures indicate a ferri- to superparamagnetic transition before reaching the T _{C .} The T _C shows a non-linear variation with composition between –50 and –183 °C with decreasing magnetite component (X _Fe3O₄). The substitution of Mg in spinelloid V further decreases T _C . Spinelloid III is paramagnetic over nearly the total temperature range. Ferrimagnetic models for spinelloid II and spinelloid V are proposed. The T _C of Fe₃O₄–Fe₂SiO₄ spinel solid solutions gradually decrease with increasing Si content. Spinel is ferrimagnetic at least to a composition of X _Fe3O₄=0.20, constraining a ferrimagnetic to antiferromagnetic transition to occur at a composition of X _Fe3O₄<0.20. A contribution of the studied ferrimagnetic phases for crustal anomalies on the Earth can be excluded because they lose their magnetization at relatively low temperatures. However, their relevance for magnetic anomalies on other planets (Mars?), where these high-pressure Fe-rich minerals could survive their exhumation or were formed by impacts, has to be considered.     

Production of Bauxite Certified Reference Material (BARC-B1201) for Nine Property Values (Al2O3, Fe2O3, SiO2, TiO2, V2O5, MnO,Cr2O3, MgO and LOI) Traceable to SI Units

The National Centre for Compositional Characterisation of Materials (NCCCM) / Bhabha Atomic Research Centre (BARC) and National Aluminium Company Limited (NALCO), India have produced an Indian origin bauxite certified reference material (CRM), referred to as BARC-B1201, certified for major (Al₂O₃, Fe₂O₃, SiO₂, TiO₂, loss on ignition - LOI) and trace contents (V₂O₅, MnO, Cr₂O₃, MgO). Characterisation was undertaken by strict adherence to ISO Guides. A method previously developed and validated in our laboratory, using single step bauxite dissolution and subsequent quantitation (of Al₂O₃, Fe₂O₃, SiO₂, TiO₂, V₂O_5, MnO, Cr₂O₃ and MgO) by ICP-AES (SSBD ICP-AES) was used for homogeneity studies and an inter-laboratory comparison exercise (ILCE) of the candidate CRM. LOI was determined by thermo-gravimetric analysis. Property values were assigned after an ILCE with participation from seventeen reputed government and private sector laboratories in India. The CRM was certified for nine property values: Al₂O₃, Fe₂O₃, SiO₂, TiO₂, V₂O_5, MnO, Cr₂O₃, MgO and LOI, which are traceable to SI units.     

High-pressure transitions and thermochemistry of MGeO3 (M=Mg, Zn and Sr) and Sr-silicates: systematics in enthalpies of formation of A2+B4+O3 perovskites

Phase transitions in MgGeO₃ and ZnGeO₃ were examined up to 26 GPa and 2,073 K to determine ilmenite–perovskite transition boundaries. In both systems, the perovskite phases were converted to lithium niobate structure on release of pressure. The ilmenite–perovskite boundaries have negative slopes and are expressed as P(GPa)=38.4–0.0082T(K) and P(GPa)=27.4−0.0032T(K), respectively, for MgGeO₃ and ZnGeO₃. Enthalpies of SrGeO₃ polymorphs were measured by high-temperature calorimetry. The enthalpies of SrGeO₃ pseudowollasonite–walstromite and walstromite–perovskite transitions at 298 K were determined to be 6.0±8.6 and 48.9±5.8 kJ/mol, respectively. The calculated transition boundaries of SrGeO₃, using the measured enthalpy data, were consistent with the boundaries determined by previous high-pressure experiments. Enthalpy of formation (ΔH _f°) of SrGeO₃ perovskite from the constituent oxides at 298 K was determined to be −73.6±5.6 kJ/mol by calorimetric measurements. Thermodynamic analysis of the ilmenite–perovskite transition boundaries in MgGeO₃ and ZnGeO₃ and the boundary of formation of SrSiO₃ perovskite provided transition enthalpies that were used to estimate enthalpies of formation of the perovskites. The ΔH _f° of MgGeO₃, ZnGeO₃ and SrSiO₃ perovskites from constituent oxides were 10.2±4.5, 33.8±7.2 and −3.0±2.2 kJ/mol, respectively. The present data on enthalpies of formation of the above high-pressure perovskites were combined with published data for A²⁺B⁴⁺O₃ perovskites stable at both atmospheric and high pressures to explore the relationship between ΔH _f° and ionic radii of eightfold coordinated A²⁺ (R _A) and sixfold coordinated B⁴⁺ (R _B) cations. The results show that enthalpy of formation of A²⁺B⁴⁺O₃ perovskite increases with decreasing R _A and R _B. The relationship between the enthalpy of formation and tolerance factor ( R _o: O²⁻ radius) is not straightforward; however, a linear relationship was found between the enthalpy of formation and the sum of squares of deviations of A²⁺ and B⁴⁺ radii from ideal sizes in the perovskite structure. A diagram showing enthalpy of formation of perovskite as a function of A²⁺ and B⁴⁺ radii indicates a systematic change with equienthalpy curves. These relationships of ΔH _f° with R _A and R _B can be used to estimate enthalpies of formation of perovskites, which have not yet been synthesized.     

A Single Step Acid Assisted Microwave Digestion Method for the Complete Dissolution of Bauxite and Quantitation of its Composition (Al2O3, Fe2O3, SiO2, TiO2, Cr2O3, MgO,MnO and V2O5) by ICP-AES

An acid assisted microwave-based method for the complete dissolution of bauxite using mixture of H₂SO₄, H₃PO₄ and HF acids in a single step was developed for the determination of various analytes (Al₂O₃, Fe₂O₃, SiO₂, TiO₂, Cr₂O₃, MgO, MnO and V₂O₅) using ICP-AES. The method was validated with respect to ruggedness, linearity, trueness, precision, limit of detection (LOD), limit of quantification (LOQ), working range and measurement uncertainties by analysing a bauxite reference material (Alcan BXT-12) and four certified reference materials (IPT-131, BXBA-4, NIST SRM 600, NIST SRM 697). The expanded uncertainties obtained for Al₂O₃ (40.0%), Fe₂O₃ (17.0%), SiO₂ (20.3%), TiO₂ (1.31%), Cr₂O₃ (0.024%), MgO (0.05), MnO (0.013), and V₂O₅ (0.60%), were 0.80, 0.40, 0.50, 0.033, 0.0008, 0.002, 0.0007 and 0.002 respectively, which are fit for the intended use to characterise bauxite. The developed method was also evaluated through participation in an interlaboratory comparison exercise organised by the Jawaharlal Nehru Aluminium Research Development and Design Centre (JNARDDC), Nagpur, India, using bauxite sample (BXT-JNA), with satisfactory z-scores achieved.     

Calculation of partial melting equilibria in the system Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O (NCKFMASH)

A thermodynamic model for haplogranitic melts in the system Na₂O–CaO–K₂O–Al₂O₃–SiO₂–H₂O (NCKASH) is extended by the addition of FeO and MgO, with the data for the additional end‐members of the liquid incorporated in the Holland & Powell (1998) internally consistent thermodynamic dataset. The resulting dataset, with the software thermocalc , is then used to calculate melting relationships for metapelitic rock compositions. The main forms for this are P–T and T–X pseudosections calculated for particular rock compositions and composition ranges. The relationships in these full‐system pseudosections are controlled by the low‐variance equilibria in subsystems of NCKFMASH. In particular, the solidus relationships are controlled by the solidus relationships in NKASH, and the ferromagnesian mineral relationships are controlled by those in KFMASH. However, calculations in NCKFMASH allow the relationships between the common metapelitic minerals and silicate melt to be determined. In particular, the production of silicate melt and melt loss from such rocks allow observations to be made about the processes involved in producing granulite facies rocks, particularly relating to open‐system behaviour of rocks under high‐grade conditions.     

Crystal-chemical and energetic systematics of wadeite-type phases A2BSi3O9 (A = K, Cs; B = Si, Ti, Zr)

Wadeite K₂ZrSi₃O₉ and its analogues K₂TiSi₃O₉ and Cs₂ZrSi₃O₉, synthesized by high-temperature solid-state sintering, have been investigated using powder X-ray diffraction coupled with Rietveld analysis and high-temperature oxide melt solution calorimetry. The crystal chemistry and energetics of these phases, together with K₂Si^VISi₃ ^IVO₉, a high-pressure wadeite analogue containing both tetrahedral and octahedral Si, are discussed in term of ionic substitutions. As the size of the octahedral framework cation increases, Si⁴⁺ → Ti⁴⁺ → Zr⁴⁺, the cell parameter c increases at a much higher rate than a. In contrast, increasing the interstitial alkali cation size (K⁺ → Cs⁺) results in a higher rate of increase in a compared with c. This behavior can be attributed to framework distortion around the interstitial cation. The enthalpies of formation from the constituent oxides (ΔH_f,ox⁰) and from the elements (ΔH_f,el⁰) have been determined from drop-solution calorimetry into 2PbO·B₂O₃ solvent at 975 K. The obtained values (in kJ/mol) are as follows: ΔH_f,ox⁰ (K₂TiSi₃O₉) = −355.8 ± 3.0, ΔH_f,el⁰ (K₂TiSi₃O₉) = −4395.1 ± 4.8, ΔH_f,ox⁰ (K₂ZrSi₃O₉) = −374.3 ± 3.3, ΔH_f,el⁰ (K₂ZrSi₃O₉) = −4569.9 ± 5.0, ΔH_f,ox⁰ (Cs₂ZrSi₃O₉) = −396.6 ± 4.4, and ΔH_f,el⁰ (Cs₂ZrSi₃O₉) = −4575.0 ± 5.5. The enthalpies of formation for K₂Si^VISi₃ ^IVO₉ were calculated from its drop-solution enthalpy of an earlier study (Akaogi et al. 2004), and the obtained ΔH_f,ox⁰ (K₂SiSi₃O₉) = −319.7 ± 3.4 and ΔH_f,el⁰ (K₂SiSi₃O₉) = −4288.7 ± 5.1 kJ/mol. With increasing the size of the octahedral framework cation or of the interstitial alkali cation, the formation enthalpies become more exothermic. This trend is consistent with the general behavior of increasing energetic stability with decreasing ionic potential (z/r) seen in many oxide and silicate systems. Further, increasing the size of the octahedral framework cation appears to induce more rapid increase in stability than increasing the interstitial alkali cation size, suggesting that framework cations play a more dominant role in wadeite stability.