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1.
硅酸盐熔体微结构单元的探讨 总被引：4，自引：0，他引：4
为了深入了解熔融硅酸盐的各种性质，综合前人的资料并结合自己的实验结果，对硅酸盐熔体中的微结构单元进行了探讨。熔体中包含5种不同的硅氧四面体(以Qn表示，n为四面体中的桥氧数目)，不同的硅氧键中的电荷分布以及Qn在Raman谱图中的特征位移区有区别，熔态谱和玻璃态谱之间也存在差别，同组成熔体和淬冷玻璃中，同一Qn具有不同的摩尔分数、自由能和无序度，并且熔体中Q4的振动是非Raman活性的。 相似文献
2.
在他的专著《论岩浆熔体的粘度》中提出了计算岩浆熔体的粘度的半经验简易方法.该法与实验测定的精度相比,尚有误差.其方程式是:lg·η＝(a-bK)10~3/4.576T－3.5＋a(P总压-PH_2O)式中,η—粘度(泊);P—压力(MPa);T—温度(K);a= -5.02·10_(-4)MPa,对于“干的”熔体-1.2·10_(-3)MPa,对于不饱和水的熔体K—结构化学参数,熔体的结构比学参数K用下式计算:K=O_(-1)O_0=2(O-2M)/M×100式中,O_-—非桥氧;O~0—桥氧;O—熔体内氧的离子总和;M—成网阳离子(Si~(4+)、Al~(3+)、Fe~(3+)、P~(5+))的离子总和(单位均以moi计).参数K可根据岩石的化学成分计算,例子见《岩浆熔体的粘度》. 相似文献
3.
通过研究硅酸盐熔体的氧平均体积,并与硅酸盐玻璃相对比,提出硅酸盐熔体的体积可分为两部分,即硅-氧骨架部分和阳离子部分,根据氧平均体积变化规律,得出硅-氧骨架部分的体积基本不随温度变化,硅酸盐熔体的体积膨胀主要是由于“氧化物”部分的局部膨胀所致,进一步提出O~(2-)半径基本不变,而主要是阳离子半径变化,并讨论了膨胀的机制。 相似文献
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在流纹质岩浆中,存在两种不混溶的熔体,一种熔体富SiO_2贫FeO,另一种则相反。从熔体结构的角度看,前一种熔体富桥氧,后者则富自由氧。水的解聚作用可以改变流纹质岩浆的结构,即降低它的聚合程度,因此,含水流纹岩浆的粘度低于玄武岩浆的粘度,从而使流纹岩中流纹构造发育。 实际工作中应避免混淆流纹岩与酸性熔结凝灰岩。 相似文献
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在硅酸盐液相不混溶过程中,高电荷密度(HCD)阳离子优先进入较基性的不混溶熔体相中,这与它们在岩浆分离结晶过程中的行为正好相反.根据这个原理,可区分岩石(矿石)是液相不混溶成因还是结晶分异成因.HCD阳离子在两共轭液相中的分配主要由其聚合程度强弱决定.在基性熔体中,非桥氧(NBO)数较多,要求更多的HCD阳离子以求配位.两液相中结晶相的存在会严重影响HCD阳离子的配分性质. 相似文献
8.
热扩散在地质过程中是否发挥重要作用一直存有争议。本文回顾了热扩散的研究历史和现状,重点总结了热扩散驱动的元素和同位素行为规律,并探讨了温度、硅酸盐组分、压力和氧逸度等因素对热扩散行为的影响。已有的研究表明,稳定热梯度下的硅酸盐热扩散效应类似于结晶分异或AFC过程,可以造成轻、重同位素分别在高温端和低温端富集,而主、微量元素的扩散方向则取决于两端化学势的高低和熔体中的电价平衡。从基性岩浆到酸性岩浆,熔体聚合度增大,黏度增加,热扩散速率明显降低,成网元素的热扩散效应减弱,变网元素则反之;水、氟、氯和硫化氢等挥发组分能增加熔体的非桥氧比例,降低熔体聚合度,因而能显著增强硅酸盐熔体中元素和同位素的热扩散效应。在此基础上,本文提出了当前硅酸盐体系热扩散研究中存在的五个亟需解决的问题,即:1)对不同硅酸盐体系的热扩散规律的研究还不够全面;2)对微量元素的热扩散行为认识不足;3)硅酸盐体系热扩散作用的影响因素及尺度还不够明确;4)热扩散作用的地质与地球化学关键识别标志有待确立;5)硅酸盐体系热扩散作用的理论模型有待建立。尽管硅酸盐体系热扩散的研究还存在诸多不足,但越来越多的证据表明,热扩散是地质过程中不容忽视的一种成分分异机制。这种机制会造成岩浆房或岩浆通道中的元素分异和同位素分馏,可能对于一些成分分异的岩石和矿床的形成具有重要的意义。 相似文献
9.
硅酸盐岩浆的Fe^3＋—Fe^2＋平衡与氧逸度 总被引：2，自引：0，他引：2
铁是硅酸盐岩浆中唯一呈两种价态存在的主要元素.岩浆中Fe~(3+)——Fe~(2+)的平街不仅显著地影响岩浆结晶作用的趋势,而且由于Fe~(3+)和Fe~(2+)在熔体相中具有不同的结构作用,从而影响熔体的性质,如密度和粘度等.氧是岩浆中具有相当化学活动性的组分.岩浆演化过程中氧逸度的变化明显地影响岩浆的结构、流变学性质和化学成分.对岩浆中Fe~(3+)——Fe~(2+)平衡的研究,可以获得有关氧逸度变化的信息,因而具有重要的岩石学意义. 相似文献
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The speciation of water in silicate melts 总被引：1，自引：0，他引：1
Edward Stolper 《Geochimica et cosmochimica acta》1982,46(12):2609-2620
Previous models of water solubility in silicate melts generally assume essentially complete reaction of water molecules to hydroxyl groups. In this paper a new model is proposed that is based on the hypothesis that the observed concentrations of molecular water and hydroxyl groups in hydrous silicate glasses reflect those of the melts from which they were quenched. The new model relates the proportions of molecular water and hydroxyl groups in melts via the following reaction describing the homogeneous equilibrium between melt species: H2Omolecular (melt) + oxygen (melt) = 2OH (melt). An equilibrium constant has been formulated for this reaction and species are assumed to mix ideally. Given an equilibrium constant for this reaction of 0.1–0.3, the proposed model can account for variations in the concentrations of molecular water and hydroxyl groups in melts as functions of the total dissolved water content that are similar to those observed in glasses. The solubility of molecular water in melt is described by the following reaction: H2O (vapor) = H2Omolecular (melt).These reactions describing the homogeneous and heterogeneous equilibria of hydrous silicate melts can account for the following observations: the linearity between fH2O and the square of the mole fraction of dissolved water at low total water contents and deviations from linearity at high total water contents; the difference between the partial molar volume of water in melts at low total water contents and at high total water contents; the similarity between water contents of vapor-saturated melts of significantly different compositions at high pressures versus the dependence on melt composition of water solubility in silicate melts at low pressures; and the variations of viscosity, electrical conductivity, the diffusivity of “water,” the diffusivity of cesium, and phase relationships with the total dissolved water contents of melts.This model is thus consistent with available observations on hydrous melt systems and available data on the species concentrations of hydrous glasses and is easily tested, since measurements of the concentrations of molecular water and hydroxyl groups in silicate glasses quenched from melts equilibrated over a range of conditions and total dissolved water contents are readily obtainable. 相似文献
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The structures of sodium silicate and aluminosilicate glasses quenched from melts at high pressure (6-10 GPa) with varying degrees of polymerization (fractions of nonbridging oxygen) were explored using solid-state NMR [17O and 27Al triple-quantum magic-angle spinning (3QMAS) NMR]. The bond connectivity in melts among four and highly coordinated network polyhedra, such as [4]Al, [5,6]Al, [4]Si, and [5,6]Si, at high pressure is shown to be significantly different from that at ambient pressure. In particular, in the silicate and aluminosilicate melts, the proportion of nonbridging oxygen (NBO) generally decreases with increasing pressure, leading to the formation of new oxygen clusters that include 5- and 6-coordinated Si and Al in addition to 4-coordinated Al and Si, such as [4]Si-O-[5,6]Si, [4]Si-O-[5,6]Al and Na-O-[5,6]Si. While the fractions of [5,6]Al increase with pressure, the magnitude of this increase diminishes with increasing degrees of ambient-pressure polymerization under isobaric conditions. Incorporating the above structural information into models of melt properties reproduces the anomalous pressure-dependence of O2− diffusivity and viscosity often observed in silicate melts. 相似文献
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The average local structure of a rhyolitic composition glass has been determined at 25°C using X-ray radial distribution analysis (RDA) and quasi-crystalline modelling and is best described as similar to that in a stuffed framework composed principally of six-membered rings of Si and Al tetrahedra (basically a stuffed tridymite-like model). Using this model it is possible to calculate a density (2.41 g/cm3) which compares well with the measured density (2.40 g/cm3); a structural model based on four-membered rings (an albite-like model) results in a substantially higher calculated density (2.60 g/cm3). We suggest that the rhyolite glass structural model is appropriate for rhyolitic melts, based on evidence from the recent literature. New viscosity data for an anhydrous rhyolite composition measured between 1200°C and 1500°C are presented and interpreted in terms of our proposed structural model and previous melt structure models for the major normative components of rhyolite. A mechanism for diffusion and viscous flow in framework silicate melts (including rhyolite composition) is proposed on the basis of recent molecular orbital calculations and molecular dynamics simulations of silicate and fluoride melts. 相似文献
16.
Sung Keun Lee 《Geochimica et cosmochimica acta》2005,69(14):3695-3710
Recent development and advances in solid state NMR, together with theoretical analyses using quantum-chemical calculations and statistical mechanical modeling, have allowed us to estimate and quantify the detailed distributions of cations and anions in model silicate glasses and melts with varying pressure, temperature and composition. How these microscopic, atomic-scale distributions in the melts from NMR and simulations affect the thermodynamic and transport properties relevant to magmatic processes has been extensively explored recently. Here, based on these previous studies, we present a classification scheme to quantify the various aspects of disorder in covalent oxide glasses and melts on scales of less than 1 nm. The scheme includes contributions from both chemical and topological disorder. Chemical disorder can further be divided into [1] connectivity, which quantifies the extent of mixing among framework units (often parameterized by the degree of Al avoidance or phase separation) and the extent of polymerization (mixing between framework and nonframework cations), and [2] nonframework disorder, which denotes the distribution of network-modifying or charge-balancing cations. Topological disorder includes the distribution of bond lengths and angles. We use this framework of disorder quantification to summarize recent progress on the structures of silicate melts and glasses, mainly obtained from 2D triple quantum magic-angle spinning (3QMAS) NMR, as functions of temperature, pressure, and composition.Most glasses and melts studied show a tendency for chemical ordering in connectivity, nonframework disorder and topological disorder at ambient and high pressure. The chemical ordering in framework disorder, a manifestation of energetics in the melts and glasses, contributes to the total negative deviation of activity of oxides from ideal solution in silicate melts (reduced activity). While no definite evidence of clustering among nonframework cations was found, these cations tend to form dissimilar pairs upon mixing with other types of network modifying cations. Topological disorder in silicate glasses and melts tends to increase with increasing pressure, as suggested by increasing bond angle and length distribution, while the chemical order seems to be maintained with pressure. We calculate key macroscopic properties, including the activity coefficient of silica and viscosity, based on the quantitative estimation of the extent of disorder from solid-state NMR, in particular 17O 3QMAS NMR. Structural ordering in melts may strongly affect the composition of partial melts in equilibrium with solids, increasing the silica composition of partial melts as a result. With increasing chemical order, the configurational entropy decreases, which can be correlated to an increase in viscosity of melts. 相似文献
17.
锡在花岗质熔体和流体中的性质及分配行为研究进展 总被引：2，自引：0，他引：2
元素在流/熔体间的交换、分配过程是岩浆热液矿床形成的重要环节，作为与岩浆活动有密切成因联系的典型矿种之一，锡在花岗质熔体和流体中的存在形式、分配行为及其影响因素是认识其成矿机理的关键。锡在花岗质熔体和流体中的分配特征不仅受温度、压力、氧逸度等条件的制约，流体组成和熔体的NBO/T（非桥氧键/桥氧键）、碱含量、AlK/Al(总碱与铝含量比)也是制约锡分配行为的重要因素；挥发分F、Cl对锡在流体、熔体中的地球化学行为影响尤为明显。 相似文献
18.
The thermodynamic, structural and transport properties of natural silicate melts under pressure are investigated by molecular dynamics simulation with the help of a force field recently introduced by us [Guillot B. and Sator N. (2007) A computer simulation study of natural silicate melts. Part I: low pressure properties. Geochim. Cosmochim. Acta71, 1249-1265]. It is shown that the simulation reproduces accurately the bulk moduli of a large variety of silicate liquids as evaluated from ultrasonic studies. The equations of state (EOS) of the simulated melts are in good agreement with the density data on mid-ocean ridge basalt, komatiite, peridotite and fayalite as obtained either by sink/float experiments or by shock-wave compression. From the structural point of view it is shown that the population of [5]Al and [6]Al species increases rapidly upon initial compression (0-50 kbar) whereas for Si these highly coordinated species are found in a significant abundance (>5%) only above ∼50 kbar for [5]Si and ∼100-150 kbar for [6]Si. This increase of the coordination of network formers is not the only response of the melt structure to the densification: there is also a large redistribution of the T-O-T (T = Si, Al) bond angles with the pressure and noticeably upon initial compression in rhyolitic and basaltic liquids. Furthermore, a detailed analysis of the population of bridging oxygens (BO) and nonbridging oxygens (NBO) points out that the polymerization of the melt generally increases when the pressure increases, the magnitude of this polymerization enhancement being all the more important that the melt is depolymerized at low pressure. The role of triclusters (threefold coordinated oxygens to network former cations) is particularly emphasized in acidic and basaltic liquids. The pressure-induced redistribution of the oxygen atoms through the melt structure is also stressed. Finally, the simulation predicts a nonmonotonic behavior of the diffusivity of network former ions when the pressure increases, a feature with depends on the melt composition. This could have a counterpart in the electrical conductivity at sufficiently high temperature when the viscosity of the liquid is low. 相似文献
19.
Akio Suzuki Eiji Ohtani Hidenori Terasaki Ken-ichi Funakoshi 《Physics and Chemistry of Minerals》2005,32(2):140-145
In situ X-ray viscometry of the silicate melts was carried out at high pressure and at high temperature. The viscosity of the silicate melts in the diopside(Di)–jadeite(Jd) system was determined in the pressure range from 1.88 GPa to 7.9 GPa and in the temperature range from 2,003 K to 2,173 K. The viscosity of the Di 25%–Jd 75% melt decreases continuously to 5.0 GPa, whereas the viscosity of the Di 50%–Jd 50% melt increases over 3.5 GPa. The viscosity of the Di50%–Jd 50% melt reaches a minimum around 3.5 GPa. Since the amounts of silicon in the two melts are the same, the difference in the pressure dependence of the viscosity may be controlled by another network-forming element, i.e., aluminum. The difference in the pressure dependence of the viscosities in the melts with two intermediate compositions in the Di–Jd system is estimated to be due to the difference in the melt structures at high pressures and high temperatures. 相似文献
20.
Diffusion of water was experimentally investigated for melts of albitic (Ab) and quartz-orthoclasic (Qz29Or71, in wt %) compositions with water contents in the range of 0 to 8.5 wt % at temperatures of 1100 to 1200 °C and at pressures
of 1.0 and 5.0 kbar. Apparent chemical diffusion coefficients of water (D
water) were determined from concentration-distance profiles measured by FTIR microspectroscopy. Under the same P-T condition and water content the diffusivity of water in albitic, quartz-orthoclasic and haplogranitic (Qz28Ab38 Or34, Nowak and Behrens, this issue) melts is identical within experimental error. Comparison to data published in literature
indicates that anhydrous composition only has little influence on the mobility of water in polymerized melts but that the
degree of polymerization has a large effect. For instance, Dwater is almost identical for haplogranitic and rhyolitic melts with 0.5–3.5 wt % water at 850 °C but it is two orders of magnitude
higher in basaltic than in haplogranitic melts with 0.2–0.5 wt % water at 1300 °C. Based on the new water diffusivity data,
recently published in situ near-infrared spectroscopic data (Nowak 1995; Nowak and Behrens 1995), and viscosity data (Schulze et al. 1996) for hydrous
haplogranitic melts current models for water diffusion in silicate melts are critically reviewed. The NIR spectroscopy has
indicated isolated OH groups, pairs of OH groups and H2O molecules as hydrous species in polymerized silicate melts. A significant contribution of isolated OH groups to the transport
of water is excluded for water contents above 10 ppm by comparison of viscosity and water diffusion data and by inspection
of concentration profiles from trace water diffusion. Spectroscopic measurements have indicated that the interconversion of
H2O molecules and OH pairs is relatively fast in silicate glasses and melts even at low temperature and it is inferred that
this reaction is an active step for migration of water. However, direct jumps of H2O molecules from one cavity within the silicate network to another one can not be excluded. Thus, we favour a model in which
water migrates by the interconversion reaction and, possibly, small sequences of direct jumps of H2O molecules. In this model, immobilization of water results from dissociation of the OH pairs. Assuming that the frequency
of the interconversion reaction is faster than that of diffusive jumps, OH pairs and water molecules can be treated as a single
diffusing species having an effective diffusion coefficient . The shape of curves of Dwater versus water content implies that increases with water content. The change from linear to exponential dependence of Dwater between 2 and 3 wt % water is attributed to the influence of the dissociation reaction at low water content and to the modification
of the melt structure by incorporation of OH groups.
Received: 26 March 1996 / Accepted: 23 August 1996 相似文献