SiO2—Al2O3—Na2O（K2O）系列淬火熔体的高温高压合成及其LRM研究

本文采用合成溶胶凝胶中间体的技术方法,降低了硅酸盐熔体的熔化温度,并在１７５０～１８５０℃和２．０～４．０ＧＰａ条件下合面出９个ＳｉＯ２－Ａｌ２Ｏ３－Ｎａ２Ｏ（Ｋ２Ｏ）系列淬火硅权盐熔体,淬火熔体中Ｎａ（Ｋ）／Ａ１≤１属过铝质硅酸盐熔体,其激光拉曼微探针（ＬＲＭ）研究表明,随压力增大,Ｔ－Ｏｎｂ在高频区（９００～１２００ｃｍ＾－１）的对称和反对称伸缩振动频率明显减小,过铝质熔体中存在六配位铝,且随     

花岗岩+P2O5-H2O体系中W、Sn、Be、Nb、Ta在流体/熔体间分配的实验研究

实验研究了W、Sn、Be、Nb、Ta在不同压力(150 MPa、100MPa和50 MPa)、温度(850℃和800℃)条件下,于水饱和含P过铝质岩浆体系(P2O5分别为0.32%、1.98%、4.91%和7.78%)中流体-熔体间的分配.研究结果显示,W、Sn、Be、Nb、Ta在流体/熔体相间的分配系数Di＜0.1,表明它们强烈分配进入熔体相.W、Nb、Ta在流体/熔体相间的分配显示压力相关性随压力降低而降低.     

一种计算NaAlSi3O8熔体粘度的理论方法

硅酸岩熔体的结构特征是制约熔体粘度的主要因素，熔体结构的变异是其中粘流作用发生的原因，化学成分对熔体粘度的控制是通过改变熔体结构而实现的。ＳｉＯ２熔体中仅存在Ｓｉ－Ｏ键，而ＮａＡｌ－Ｓｉ３Ｏ８熔体中存在Ｓｉ－Ｏ键，Ａｌ－Ｏ键和Ｎａ－Ｏ键，Ｎａ－Ｏ键在熔体结构中通过Ｏ与Ｓｉ－Ｏ键相联结，并且使与之相联的Ｓｉ－Ｏ键的键强变弱。因此，熔体结构单元中与Ｎａ－Ｏ键相联结的Ｓｉ－Ｏ键最易断开，并因此导致流变作用的发生。文中计算了不同温度条件下ＮａＡｌＳｉ３Ｏ８熔体中Ｓｉ－Ｏ键的键强，以ＳｉＯ２熔体中的Ｓｉ－Ｏ键的键强和ＳｉＯ２熔体的粘度为标准，建立了计算了ＮａＡｌＳｉ３Ｏ８熔体粘度的理论模型，依此理论模型求得的熔体粘度在合理的地质温度范围内与实验结果完全吻合     

高压条件下KAlSi3O8熔体中水的溶解机理

应用＾２７Ａｌ、＾２９ＳｉＭＡＳ ＮＭＲ，喇曼和红外光谱技术研究了ＫＡｌＳｉ３Ｏ８溶体中水的溶解机理。在０．１ＭＰａ和２ＧＰａ下由等压淬火熔体制成了无水玻璃。含２．５ｗｔ％的含水玻璃在５和７ＧＰａ压力下等压淬火制成。在２ＧＰａ压力下等压淬火制成含２．５，５．０，和７．５ｗｔ％的含水玻璃。所有含水ＫＡｌＳｉ３Ｏ８玻璃的Ｒａｍａｎ和ＩＲ谱中均在９００ｃｍ＾－１附近出现一谱峰。所有２ＧＰａ含水玻璃９００     

Shear modulus, heat capacity, viscosity and structural relaxation time of Na2O–Al2O3–SiO2 and Na2O–Fe2O3–Al2O3–SiO2 melts

The configurational heat capacity, shear modulus and shear viscosity of a series of Na₂O–Fe₂O₃–Al₂O₃–SiO₂ melts have been determined as a function of composition. A change in composition dependence of each of the physical properties is observed as Na₂O/(Na₂O + Al₂O₃) is decreased, and the peralkaline melts become peraluminous and a new charge-balanced Al-structure appears in the melts. Of special interest are the frequency dependent (1 mHz–1 Hz) measurements of the shear modulus. These forced oscillation measurements determine the lifetimes of Si–O bonds and Na–O bonds in the melt. The lifetime of the Al–O bonds could not, however, be resolved from the mechanical spectrum. Therefore, it appears that the lifetime of Al–O bonds in these melts is similar to that of Si–O bonds with the Al–O relaxation peak being subsumed by the Si–O relaxation peak. The appearance of a new Al-structure in the peraluminous melts also cannot be resolved from the mechanical spectra, although a change in elastic shear modulus is determined as a function of composition. The structural shear-relaxation time of some of these melts is not that which is predicted by the Maxwell equation, but up to 1.5 orders of magnitude faster. Although the configurational heat capacity, density and shear modulus of the melts show a change in trend as a function of composition at the boundary between peralkaline and peraluminous, the deviation in relaxation time from the Maxwell equation occurs in the peralkaline regime. The measured relaxation times for both the very peralkaline melts and the peraluminous melts are identical with the calculated Maxwell relaxation time. As the Maxwell equation was created to describe the timescale of flow of a mono-structure material, a deviation from the prediction would indicate that the structure of the melt is too complex to be described by this simple flow equation. One possibility is that Al-rich channels form and then disappear with decreasing Si/Al, and that the flow is dominated by the lifetime of Si–O bonds in the Al-poor peralkaline melts, and by the lifetime of Al–O bonds in the relatively Si-poor peralkaline and peraluminous melts with a complex flow mechanism occurring in the mid-compositions. This anomalous deviation from the calculated relaxation time appears to be independent of the change in structure expected to occur at the peralkaline/peraluminous boundary due to the lack of charge-balancing cations for the Al-tetrahedra.     

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     

NaAlSi3O8熔体粒子扩散行为压力效应的分子动力学研究

为了研究压力对钠长石成分熔体粒子微观扩散行为的影响，本文用分子动力学方法，探讨了2001．5K温度下，压力由50MPa上升到19862MPa的过程中，熔体的微观结构、粒子自扩散系数随压力的变化规律。研究表明，在升压过程中，低次配位体Al和Si向5次和6次配位体转变，Al的含量在15GPa达到极大值，而Si含量的极大值在20GPa仍未出现。Na的自扩散系数随压力升高单调下降，Al、Si和O的自扩散系数随压力升高先增后减，在8～10GPa左右达到极大值。网架形成粒子自扩散系数的极大值与Al和Si含量的极大值对应的压力点不一致。所有粒子的自扩散系数与它们与O之间键的寿命呈线性负相关。     

硅酸盐熔体结构及水—熔体反应机理

本文对铝硅酸盐熔体结构这一领域的研究成果从以下三个方面作了总结：（１）熔体结构及其物理性质；（２）水－熔体反应机理；（３）熔体结构与压力的关系。熔体结构的变化是熔体粘度、密度、热膨胀性变化乃至粘流发生的根本原因，水与熔体的反应促使熔体粘度降低，不同的水溶解模式的建立是熔体结构研究深入的标志；压力对熔体结构的影响与温度和挥发份对它的影响大致相反，压力的增高使熔体结构产生加密效应，而温度的升高和挥发份     

NiFe2O4—ZnFe2O4尖晶石固溶体中的离子占位

在１＊１０＾５Ｐａ,１４００℃条件下实验合成了不同成分的Ｎｉ（１－ｘ）ＺｎｘＦｅ２Ｏ４尖晶石,并将部分尖晶石在１１００℃和１６１０℃条件下重新平衡。采用粉晶Ｘ射线衍射法测定了尖晶石的晶胞参数。将实测的尖晶石晶胞参数与理论计算值进行对比,结果发现,在温度小于１４００℃时Ｎｉ（１－ｘ）ＺｎｘＦｅ２Ｏ４尖晶石中的四面体主要由Ｚｎ＾２＋、Ｆｅ＾３＋占据,而八面体主要由Ｎｉ＾２＋、Ｆｅ＾３＋占据,但至少当温     

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。     

The molar volume of FeO–MgO–Fe2O3–Cr2O3–Al2O3–TiO2 spinels

We define and calibrate a new model of molar volume as a function of pressure, temperature, ordering state, and composition for spinels in the supersystem (Mg, Fe²⁺)(Al, Cr, Fe³⁺)₂O₄ ? (Mg, Fe²⁺)₂TiO₄. We use 832 X-ray and neutron diffraction measurements performed on spinels at ambient and in situ high-P, T conditions to calibrate end-member equations of state and an excess volume model for this system. The effect on molar volume of cation ordering over the octahedral and tetrahedral sites is captured with linear dependence on Mg²⁺, Al³⁺, and Fe³⁺ site occupancy terms. We allow standard-state volumes and coefficients of thermal expansion of the end members to vary within their uncertainties during extraction of the mixing properties, in order to achieve the best fit. Published equations of state of the various spinel end members are analyzed to obtain optimal values of the bulk modulus and its pressure derivative, for each explicit end member. For any spinel composition in the supersystem, the model molar volume is obtained by adding excess volume and cation order-dependent terms to a linear combination of the five end-member volumes, estimated at pressure and temperature using the high-T Vinet equation of state. The preferred model has a total of 9 excess volume and order-dependent parameters and fits nearly all experiments to within 0.02 J/bar/mol, or better than 0.5 % in volume. The model is compared to the current MELTS spinel model with a demonstration of the impact of the model difference on the estimated spinel-garnet lherzolite transition pressure.     

岩浆熔体结构

关于岩浆熔体结构,即硅酸盐熔体结构的研究,是岩浆岩岩石学的前沿课题.著名美国岩石学家卡麦克尔(I.S.E.Car－michael)教授曾经预言:在今后几年内,它将成为岩浆热力学研究的中心(1983年,私人通讯).     

The thermal stability of sideronatrite and its decomposition products in the system Na2O–Fe2O3–SO2–H2O

The thermal stability of sideronatrite, ideally Na₂Fe³⁺(SO₄)₂(OH)·3(H₂O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na₃Fe(SO₄)₃ compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe³⁺(SO₄)₂(OH)] _∞ ^2? chains and the formation of an intermediate transient amorphous phase precursor of Na₃Fe(SO₄)₃. (d) for T > 500 °C, the Na₃Fe(SO₄)₃ compound is replaced by the Na-sulfate thenardite, Na₂SO₄, plus Fe-oxides, according to the Na₃Fe³⁺(SO₄)₃ → 3/2 Na₂(SO₄) + 1/2 Fe₂O₃ + SO_x reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.     

海洋N2O的研究进展

N2O在大气中的浓度仅为CO2的浓度的千分之一左右,但在同等浓度的情况下温室效应却是CO2的200~300倍;它在大气层中的光化学产物会与臭氧反应,从而损耗平流层的臭氧。N2O的环境效应引起人们的关注,许多国际气候变化研究项目都把其列入重要研究内容。通过对过去40年的相关研究工作进行综合分析,阐述N2O在海洋中的分布规律和其影响因素、产生的机制、它的海气通量及其影响因素,从而揭示N2O的海洋生物地球化学循环过程以及这一过程对全球氮循环的贡献。     

Formation and properties of hydrosilicate liquids in the systems Na2O-Al2O3-SiO2-H2O and granite-Na2O-SiO2-H2O at 600°C and 1.5 kbar

In order to determine the mechanisms of formation and properties of natural hydrosilicate liquids (HSLs), which are formed during the transition from magmatic to hydrothermal mineral formation in granitic pegmatites and rare-metal granites, the formation of HSLs was experimentally studied in the Na₂O-SiO₂-H₂O, Na₂O-Al₂O₃-SiO₂-H₂O, and Na₂O-K₂O-Li₂O-Al₂O₃-SiO₂-H₂O systems at 600°C and 1.5 kbar. It was shown that the sequential extension of composition does not suppress HSL formation in the systems and expands the stability field of this phase. However, HSLs formed in extended chemical systems have different structure and properties: the addition of alumina induces some compression of the structure of the silicate framework of HSLs, which results in a decrease in water content in this phase and probably hinders the reversibility of its dehydration. It was demonstrated that HSL can be formed by the coagulation of silica present in a silica-oversaturated alkaline aqueous fluid. It was supposed that the HSL formed during this process has a finely dispersed structure. It was argued that anomalous enrichment in some elements in natural HSLs can be due to their sorption by the extensively developed surface of HSL at the moment of its formation.     

Phase Equilibria in the Ternary Systems KBr–K2B4O7–H2O and KCl–K2B4O7–H2O at 373 K

According to the compositions of the underground gasfield brines in the west of Sichuan Basin,the phase equilibria in the ternary systems KBr-K2B4O7-H2O and KCl-K2B4O7-H2O at 373 K were studied using the isothermal dissolution equilibrium method.The solubilities of salts and the densities of saturated solutions in these ternary systems were determined.Using the experimental data,phase diagrams and density-composition diagrams were constructed.The two phase diagrams were simple co-saturation type,each having an invariant point,two univariant curves and two crystallization regions.The equilibrium solid phases in the ternary system KBr-K2B4O7-H2O are potassium bromide （KBr） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）,and those in the ternary system KCl-K2B4O7-H2O are potassium chloride （KCl） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）.Comparisons of the phase diagrams of the two systems at different temperatures show that there is no change in the crystallization phases,but there are changes in the size of the crystallization regions.As temperature increases,the solubility of K2B4O7·4H2O increases rapidly,so the crystallization field of K2B4O7·4H2O becomes smaller.     

Raman study of MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 synthetic series: the effects of Fe2+ and Fe3+ on Raman shifts

Two synthetic series of spinels, MgCr₂O₄–Fe²⁺Cr₂O₄ and MgCr₂O₄–MgFe₂ ³⁺O₄ have been studied by Raman spectroscopy to investigate the effects of Fe²⁺ and Fe³⁺ on their structure. In the first case, where Fe²⁺ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A_1g and E_g toward lower wavenumbers with the increase of the chromite component into the spinel, while the F_2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe³⁺ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe³⁺ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm^?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe³⁺ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm^?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm^?1, when observed, show little or negligible Raman shift.     

Na2CO3-Na2B4O7-H2O三元体系288K相平衡研究

采用等温溶解平衡法研究了三元体系 Na2 CO3- Na2 B4 O7- H2 O 2 88K时的相平衡及平衡液相的主要物化性质 (密度 ,电导率 ,p H)。研究发现 :该三元体系为简单共饱和型 ,无复盐及固溶体形成 ,根据溶解度数据绘制出相图 ,相图中单变量曲线所对应的平衡固相分别为 :Na2 CO3· 10 H2 O,Na2 B4 O7· 10 H2 O。并简要讨论了物化性质的变化规律。