利用赤泥制备钙铝榴石微晶玻璃的实验研究

在1300℃下将赤泥和石英砂熔制成基础玻璃,经粉磨、筛选后,通过二次热处理工艺获得了以钙铝榴石为主晶相的微晶玻璃。采用XRD和SEM等研究赤泥和微晶玻璃后表明,赤泥主要由方解石和霰石等钙质成分组成;热处理温度对微晶玻璃性能和钙铝榴石晶体结构的影响较大。优化的制备条件为:核化900℃,1h,晶化1105℃,2h,该条件下所得的微晶玻璃晶相含量较高,晶体发育完整,性能良好,相应的体积密度为2.79g/cm3,显微硬度为6.52。     

利用高铝粉煤灰制备堇青石微晶玻璃的实验研究

以高铝粉煤灰为主要原料，制备了堇青石微晶玻璃。通过差热分析（DTA）和X射线粉末衍射分析（XRD）确定了合适的热处理条件：核化温度807℃，核化时间2h，晶化温度960℃，晶化时间3h。XRD分析显示，制得微晶玻璃的主晶相为堇青石。SEM分析表明，基础玻璃晶化完全，微晶玻璃中微晶体呈不规则柱状、棒状，微晶体长度为5～15μm，长径比为5～10。     

热处理制度对温石棉尾矿微晶玻璃析晶行为的影响

基于热处理制度对微晶玻璃析晶行为的重要影响,研究了核化温度和晶化温度对CaO-MgO-SiO2系温石棉尾矿微晶玻璃析晶行为的影响。通过DTA分析初步确定基础玻璃成核和晶化温度范围;采用X射线衍射和扫描电镜分析微晶玻璃的物相组成和显微形貌。结果表明:随着核化和晶化温度的升高,微晶玻璃样品主晶相由铁橄榄石转变为黄长石,且样品的析晶能力逐渐增强;次晶相镁橄榄石和透辉石逐渐消失。且通过热处理过程使石棉纤维相变为对环境无害的硅酸盐矿物。     

利用高铝粉煤灰制备莫来石微晶玻璃的实验研究

以高铝粉煤灰为主要原料,采用粉末烧结法制备出莫来石微晶玻璃。X射线衍射分析显示,经1350~1550℃热处理后,制得的微晶玻璃的主晶相均为莫来石。扫描电镜分析表明,较高的温度下热处理有利于晶体的生长。微晶玻璃的理化性能如吸水率、气孔率、体积密度、抗折强度和化学稳定性,随热处理温度的不同而发生相应的变化。1500℃热处理2 h制得的微晶玻璃具有优良的理化性能,在工程和结构领域具有潜在的应用前景。     

钾霞石制备体系碱性滤液的利用技术

为处理钾长石水热制备钾霞石所产生的碱性滤液,本文采用水热法,考察了氢氧化铝溶解时间、晶化时间、晶化温度、水碱比对钾霞石产率和白度的影响,并对合成钾霞石物相进行了表征。结果表明,合成钾霞石的最佳条件为,氢氧化铝溶解时间为1.5 h,晶化时间为4 h,晶化温度280℃,水碱比为1.8。XRD结果表明,产物为钾霞石粉体。傅里叶变换红外光谱表明,Al(OH)₃中的Al在水热条件下进入到Si—O骨架中形成了Si—O—Al官能团,从而印证了钾霞石的合成。差热分析结果表明,合成钾霞石具有良好的热稳定性。氮气吸附结果表明,合成钾霞石比表面积为5.18 m²/g,平均孔径为32.98 nm。实现了钾长石水热制备钾霞石所剩碱性滤液的资源化利用,并为钾长石水热制备钾霞石提供了一种母液循环的思路,使水热制备钾霞石工业化成为一种可能。     

黑龙江省五大连池、科洛、二克山火山群富钾火山岩中的浅色矿物

本区富钾火山岩中浅色矿物有碱性长石、白榴石和霞石。碱性长石主要为钠透长石、钙歪长石,少数为钙钠透长石和歪长石,其光性变化与长石的地质时代和长石内部的隐条纹结构有关。白榴石的成分及产出方式主要与岩石中的SiO_2含量有关,SiO_2不饱和程度大的白榴苦橄岩的白榴石贫SiO_2;而SiO_2不饱和程度低的白榴碧玄岩和白榴玄武岩中,白榴石富SiO_2而稍贫K_2O+Na_2O,仅见于过渡相,而中心相由于水压较高和近于平衡的结晶条件,白榴石不能晶出,或先晶出后又与熔体反应形成碱性长石。     

水热交代实验形成的铝黄长石的特征和物理化学条件

通过实验研究和反应平衡的热力学计算,表明铝黄长石是由中基性侵入岩和碳酸盐岩在580-700℃和300×10~5-750×10~5Pa的温度和压力条件下,含氟、氯的碱性(pH=8.0-11.0)介质中接触交代而形成。氧化环境则有利于它的发育和生长。实验所形成的铝黄长石的主要特征是呈四方板状,无色透明,大小约0.001-0.05mm,正延长性,平行消光,多色性不明显,干涉色为一级灰色,一轴晶,负光性。其折光率分别为No=1.657-1.668,Ne=1.655-1.659。它由90-60％的铝黄长百分子和10-40％的镁黄长石所组成,常与钙铁榴石、钙铝榴石和磁铁矿共生。     

一种和田玉仿制品——含氟的硅碱钙石微晶化玻璃的初步研究

针对市场上出现的一种外观酷似和田玉的微晶化玻璃,利用常规宝石学测试手段、扫描电镜分析、X射线粉末衍射分析以及红外光谱分析等测试方法,对该材料样品的宝石学特征、表面微观形貌特征、光谱学特征等进行了研究。结果显示,样品为一种含氟的硅碱钙石微晶化玻璃,它是由以二氧化硅为主要成分的基础玻璃在特定的温度条件下逐渐析晶而成的,其微观结构与和田玉的有一定的差异,可以通过红外光谱和XRD对其进行结论性鉴定与区别。     

硅酸盐体系的化学平衡:(2)反应热力学

通过具体的应用实例,系统介绍了在矿物材料学研究中硅酸盐体系的多相平衡反应热力学的基本原理。对硅酸盐体系的典型多相平衡反应进行了热力学计算,包括:(1)微晶玻璃制备过程中的硅酸盐熔融反应;(2)霞石正长岩和高铝粉煤灰利用技术中的硅酸盐烧结反应;(3)S iO2-CaO-H2O体系和KA lS i3O8-CaO-H2O体系雪硅钙石、硬硅钙石的水热晶化反应;(4)高铝粉煤灰和霞石正长岩烧结产物的溶解反应;(5)Na[A l(OH)4]-A l(OH)3-H2O体系和Na2SO4-Ca(OH)2-H2O体系中α-A l(OH)3和CaSO4.2H2O的析晶反应。研究成果可望对矿物材料制备实验方案设计、工业生产过程优化及改进产品性能提供理论指导,同时为同类材料学研究提供借鉴。     

凹凸棒石水热制备中空六方钾霞石及生长机制

用KOH、酸处理凹凸棒石、硝酸铝为原料在180℃~200℃水热条件下制备中空的钾霞石。经粉末晶体衍射图证实,所制备的晶体与钾霞石的特征峰符合,表明制备物质为钾霞石。由扫描电镜图中,可以看出所制备的六方片状晶体直径约为5μm~10μm,厚度约为500nm,并且片状中间出现了很多的大孔(直径约100nm~1 000nm左右),这在之前的报道中从未出现过。因此,追踪钾霞石的生长机制,发现这种多孔六方钾霞石生长分为三步,第一步,是纳米棒聚集形成放射状微球;第二步微球晶化形成假六方片钾霞石;第三步,假六方片晶体经过奥斯特瓦尔德熟化过程表面再结晶形成中空六方片。这是首次在二维材料上观察到这种奥斯特瓦尔德熟化再结晶的现象。     

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.     

Stability of the assemblage orthopyroxene-sillimanite-quartz in the system MgO-FeO-Fe2O3-Al2O3-SiO2-H2O

The stability of coexisting orthopyroxene, sillimanite and quartz and the composition of orthopyroxene in this assemblage has been determined in the system MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂-H₂O as a function of pressure, mainly at 1,000° C, and at oxygen fugacities defined mostly by the hematite-magnetite buffer. The upper stability of the assemblage is terminated at 17 kbars, 1,000° C, by the reaction opx+Al-silicate gar+qz, proceeding toward lower pressures with increasing Fe/(Fe+Mg) ratio in the system. The lower stability is controlled by the reaction opx+sill+qz cord, which occurs at 11 kbars in the iron-free system but is lowered to 9 kbars with increasing Fe/(Fe+Mg). Spinel solid solutions are stabilized, besides quartz, up to 14 kbars in favour of garnet in the iron-rich part of the system (Fe/(Fe+Mg)0.30). Ferric-ferrous ratios in orthopyroxene are increasing with increasing ferro-magnesian ratio. At least part of the generally observed increase in Al content with Fe²⁺ in orthopyroxene is not due to an increased solubility of the MgAlAlSiO₆ component but rather of a MgFe³⁺AlSiO₆ component. The data permit an estimate of oxygen fugacity from the composition of orthopyroxene in coexistence with sillimanite and quartz.     

Synthesis and crystal chemistry of kornerupine in the system MgO-Al2O3-SiO2-B2O3-H2O

Boron-bearing kornerupine was synthesized in the simplest possible model system at fluid pressures and temperatures both within and outside the stability field of boron-free kornerupine. Best conditions for synthesis of single-phase products are 7 kb and 830 °C. Microprobe and wet chemical analyses as well as X-ray studies indicate compositional variations of kornerupines regarding all five constituent components: Increasing B-contents (from 0.37 to 3.32 wt% B₂O₃) are correlated with decreasing OH^? values largely according to the Eq. B³⁺?3 H⁺; the ratio MgO∶Al₂O₃∶SiO₂ varies from 4∶3∶4 in the direction towards 1∶1∶1. Thus kornerupine exhibits an at least ternary range of solid solution in the system studied. Crystallochemically speaking it is significant that, although the Mg∶Al∶Si ratio of kornerupine may remain constant with increasing boron contents, the total number of cations per formula unit increases beyond the ideal number of 14.0 as given by Moore and Bennett (1968). Considering the presence of an additional structural site at (000) it is suggested that the introduction of boron initiates a sequence of substitutions such as $$B^{[4]} \to Si^{[4] } \to A1^{[4]} \to Mg^{[6]} \to \square$$ . The filling of this site, empty in boron-free kornerupine, by Mg is connected with a loss of hydrogen located near this site. Petrologically speaking an exchange reaction relation exists between kornerupine and its coexisting fluid according to the equation Boron-free kornerupine+B₂O₃=boron-kornerupine+H₂O. The molar fractions $$X_{B_2 O_3 } = B_2 O_3 /\left( {B_2 O_3 + H_2 O} \right)$$ of kornerupines exceed those of their coexisting fluids by about one order of magnitude. Fluids with relatively low X_{B 2 O 3} lead to the coexistence of kornerupine with boron-free minerals such as enstatite and sapphirine, fluids with relatively high X_{B 2 O 3} produce the boron-minerals grandidierite, sinhalite, and tourmaline (in the present system without Na!) in addition to kornerupine.     

Das System NaAlSi3O8-BaAl2Si2O8-H2O bei 1 Kbar

The system albite-celsian-water was investigated at isothermal sections of 670, 760, 800, 900, 1000 and 1100° C at 1 Kbar. At temperatures above about 950° C the existence of a solid solution series could be shown. In the condensed part of the 930° C/1 Kbar section the partition of barium between melt and coexisting crystals was measured using an electron probe microanalyzer. The barium content of crystals grown in equilibrium with a melt is always higher than the barium content of the starting composition, so albite-celsian shows an ascending type solid solution series at low total water pressures. In the subsolidus region two types of solvi are existent, which show different ways of phase unmixing. The relatively low barium contents of natural albites are interpreted as being due to geochemical reasons rather than crystalchemical reasons.

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Meinem hochverehrten Lehrer, Herrn Prof. Dr. K. Jasmund, danke ich für sein lebhaftes Interesse während der Durchführung dieser Arbeit und für die kritische Durchsicht des Manuskripts. Mein Dank gilt ferner Herrn Dr. H. A. Seck für die Einarbeitung in die experimentellen Methoden der Hydrothermalsynthese und für kritische Anmerkungen zum Manuskript. Fräulein Dr. M. Corlett danke ich für wertvolle Informationen zur Messung mit der Elektronenstrahl-Mikrosonde.

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Die Untersuchung wurde mit Hilfe von Personal- und Sachmitteln durchgeführt, die Herrn Professor Dr. K. Jasmund von der Deutschen Forschungsgemeinschaft zur Verfügung gestellt worden waren.     

Compressibility of P2O5-Al2O3-Na2SiO3 melts

The effect of composition and temperature on the relaxed adiabatic bulk modulus of melts in the P₂O₅-Al₂O ₃-Na₂SiO₃ system have been investigated in the temperature range of 1140 to 1450 °C using ultrasonic interferometric methods at frequencies of 3, 5 and 7 MHz. The density of these melts was determined using Pt-double-bob Archimedean densitometry techiques. P₂O₅ is known to dramatically affect the structure and the chemical and physical properties of granitic and pegmatitic melts as a function of the peralkalinity of the melt. The physical results of the structural changes occurring in Na₂O-Al₂O₃-SiO₂ melt upon the addition of P₂O₅ are observed by variations in the properties such as density and compressibility. For the present peralkaline melts, the bulk modulus and density decrease with addition of 15 mol% P₂O₅, and increase with the addition of 15 mol% Al₂O₃. The addition of P₂O₅ to the present melts results in a larger increase in melt compressibility than that observed with increasing polymerization between Na₂SiO₃ and Na₂Si₂O₅ melts. This would suggest that not only is the polymerization of the melt increasing with the addition of P₂O₅ (Mysen et al. 1981; Nelson and Tallant 1984; Gan and Hess 1992), but that the tetrahedrally co-ordinated phosphorus complexes are influencing the bond lengths and energies within the melt structure; resulting in the structure becoming more compressible than expected, although incompressible (Vaughan and Weidner 1987) tetrahedral P₂O₅ polyhedra (Mysen et al. 1981; Gan and Hess 1992; Toplis et al. 1994) are being added to the melt structure.     

Theoretical growth morphology of whewellite CaC2O4·H2O

The morphological theory of Hartman and Perdok (1955, 1956) allows to deduce the character of a growth form {hkl} on the basis of structural data alone. Its application to the structure of whewellite leads to the identification of forms {100}, {010}, {021}, {011}, {12 \(\bar 1\) } and {121} which show during the growth a flat surface profile (flat forms F). These forms occur very frequently in the crystals we grew from pure aqueous solutions at supersaturation β≦1,90. Other forms, {001} and {10 \(\bar 1\) }, possibly show a double character (F or S, where S stays for related faces showing a stepped profile during the growth) according to the bonds assumed within some periodic bond chains (PBCs). Alternative ways of bonding water molecules lead to different structures of the same PBC. The different energy corresponding to these structures may explain the complex morphology of both natural and synthetic crystals grown at high β values.     

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.     

Synthetic dumortierite: its PTX-dependent compositional variations in the system Al2O3-B2O3-SiO2-H2O

Dumortierite, generally simplified as Al₇BSi₃O₁₈, was synthesized in the pure system Al₂O₃–B₂O₃–SiO₂–H₂O (ABSH) using gels with variable Al/Si ratios mixed with H₃BO₃ and H₂O in known proportions as starting materials. Synthesis conditions ranged from 3 to 5 and 15 to 20 kbar fluid pressure at 650° to 880°C. On the basis of analyses, synthetic dumortierite shows relatively narrow homogeneity ranges with regard to Al/Si which, however, vary as a function of pressure: at low pressures (3–5 kbar) Al/Si is 2.77–2.94 versus 2.33–2.55 at high pressures (15–20 kbar). Outside of these homogeneity limits, dumortierite was found to coexist with quartz or corundum, depending on the starting composition. Whereas synthetic dumortierite invaribly contains 1.0 boron atom per formula unit (p.f.u.) based on 18 oxygens, the water contents vary drastically as a function of pressure and temperature (1.32–2.30 wt.% H₂O or 0.85–1.47 H p.f.u.). H₂O is an essential component in dumortierite. Structural formulae based on complete chemical analyses of the dumortierites synthesized reveal that there is invariably an Si-deficiency against the ideal number of 3.0 p.f.u. In the calculation procedure used here, this deficiency is balanced by assuming tetrahedral Al. The remaining Al, taken to occupy the octahedral sites, is always below the ideal number of 7.0 p.f.u. Charge-balancing the structure with the hydrogen found analytically leads to two different mechanisms of H incorporation: (1) 3H⁺ + octahedral vacancy for Al^[6]; (2) H⁺ + tetrahedral Al for Si^[4]. Dumortierite synthesized at high fluid pressure contains little Al^[4] and, thus, little H⁺ of type 2; its hydrogen is predominantly present as type 1. Conversely, dumortierite formed at low fluid pressures is high in Al^[4] and hydrogen type 2. The amounts of hydrogen type 1 in low-pressure dumortierites decrease with rising temperatures of synthesis. Typical structural formulae are: (Al_6.670.33)[Al_0.49Si_2.51–O_13.53(OH)_1.47](BO₃) for a low-pressure product, and (Al_6.680.32)[Al_0.09Si_2.91O_13.94(OH)_1.06](BO₃) for a high-pressure product. Independently of the synthesis conditions, dumortierite was found always to be orthorhombic, with b₀/a₀ deviating slightly, but significantly from the valid for hexagonal lattice geometry. As a function of increasing Al/Si in the synthetic crystals, their a₀, c₀, and V₀ rise, whereas b₀ decreases. Thus b₀/a₀ decreases most sensitively with rising Al/Si and also with growing Al^[4]. More experimentation is required before the compositional variations of dumortierite found here can be applied successfully to geothermobarometry of natural rocks.