Nepheline--Alkali Feldspar Equilibria: I. Experimental Data and Thermodynamic Calculations

Nepheline-alkali feldspar equilibria with alkali chloride aqueoussolutions have been determined for the temperature range 400to 700 °C at 1000 bars pressure. Nepheline-alkali feldsparequilibria with alkali chloride melts have been determined forthe temperature range 800 to 1100 °C at approximately 6bars pressure. (1) NaAlSiO₄ + KCl(aq) = NaCl(aq) + KAlSiO₄ (2) NaAlSiO₄ + KCl(melt) = NaCl(melt) + KAlSiO₄ (3) NaAlSi₃O₈(high) + KCl(aq) = NaCl(aq) + KAlSi₃O₈(San) (4) NaAlSi₃O₈(low) + KCl(aq) = NaCl(aq) + KAlSi₃O₈(Mic) (5) NaAlSi₃O₈(high) + KCl(melt) = NaCl(melt) + KAlSi₃O₄(San) (6) NaAlSi₃O₈(low) + KCl(melt) = NaCl(melt) + KAlSi₃O₈(Mic) From these, two diagrams of phase relationships were derivedfor the following exchange equilibria: (7) NaAlSiO₄ + KAlSi₃O₈(San) = NaAlSi₃O₈(high) + KAlSiO₄; (8) NaAlSiO₄ + KAlSi₃O₈(Mic) = NaAlSi₃O₈(low) + KAlSiO₄. The effect of pressure on these equilibria has been determinedby comparing the experimental data for 1000 and 5000 bars (t= 500 °C) and thermodynamic calculations. It has also beenshown that the effect of excess silica in nepheline solid solutionon the K—Na distribution between nepheline and alkalifeldspar is substantial and opposite to that of temperature.In the high temperature region an increase in silica contentin nepheline of 2 wt. per cent eliminates the effect on theredistribution of a temperature increase of 100 °C. Thesecation exchange data and unit cell data for the crystal phasesare used to calculate thermodynamic mixing properties of nephelinesolid solution and alkali feldspar solid solution for a widerange of temperature and pressure.     

利用钾长石尾矿制备矿物聚合材料的实验研究

以福建沙县田口钾长石尾矿粉体为主要原料，以煅烧高岭石作配料，硅酸钠作结构模板剂，氢氧化钠作激活剂，进行了制备矿物聚合材料的实验研究，实验样品静置固化7－28d，其抗压强度高达19.4-24.9MPa。耐酸性，耐碱性指标均优于相似建材的国家标准。在配料组成中，控制高岭石用量为20％，适当提高硅酸钠的用量和固／液化，有利于提高制品的力学性能。实验表明，材料抗中度随固化时间的延长而叶抛物线式发展，矿物聚合材料的形成过程为：铝硅酸盐固体组分的溶解络合，分散迁移，浓缩聚合，脱水硬化。由铝硅酸盐凝胶相固化而在的基体相，其化学组成与沸石相近，微观结构极可能与蛋白质类似，物理形态上呈三维网状结构，将未溶解的晶质颗粒胶结为坚硬块体，是矿物聚合材料获得良好力学性能的结构基础。     

长石溶解模拟实验研究综述

在综合分析前人研究成果基础上,对长石溶解模拟实验研究进行了综述.研究表明,长石溶解与其成分、结构、反应的温压条件以及流体性质等有关.在相同的温压条件下,3种长石的稳定性依次为:钾长石>钠长石>钙长石,且温度升高可加强长石的溶解能力,促进长石的溶解,而压力的变化对长石的溶解影响不大.长石的溶解速率在酸性区域随pH值增大而减小、在中性区域溶解速率低且受影响小、在碱性区域随pH值增大而增大.有机酸通过提供H+、络合金属元素来提高长石的溶解度.长石的溶蚀速率与颗粒的总表面积大小以及颗粒表面粗糙度有关,总表面积越大,表面越粗糙,则反应速率越快,而且溶液的矿化度越低越有利于长石的溶解.长石的溶解过程由表面反应和扩散反应所控制,描述长石溶蚀机理的模型主要包括:表面反应模型和淋滤层扩散模型.     

低温条件下长石溶解模拟实验研究

为了研究有机酸和无机酸对长石的溶解能力以及不同有机酸对长石溶解能力的差异,笔者等在80℃条件下,在不同pH值（4、6和8）的分别含有盐酸、乙酸和草酸的溶液中,对碱性长石和斜长石进行了溶解模拟实验研究。实验结果表明：酸性(pH=4)和弱酸性(pH=6)条件下,乙酸对两种长石的溶解能力大于草酸,碱性条件(pH=8)下草酸的溶解能力最大,无论在酸性或碱性条件下,有机酸对长石的溶解能力均高于无机酸,酸性(pH=4)条件下,斜长石与碱性长石溶解量差别不大,在弱酸性(pH=6)和碱性(pH=8) 条件下,斜长石的溶解量高于碱性长石。     

A Study of Phase Equilibria in a Metamorphic Iron Formation

The paper is based on a study of minerl assemblages in metamorphiciron formations in northere Quebec. Thirty-four mineral analyseshave been performed, using photometric methods of silicate analysis. Three facies of iron formation are represented, namely, quartz-speculariteiron formation, quartz-magnetite iron formation, and quartz-silicateiron formation. The silicate iron formation is made up mainlyof quartz, ferrohypersthene, ferroaugite, cummingtonite, andcalcite. Arfvedsonite and aegirine-hedenbergite occur in magnetite-richrocks. The analysed coexisting minerals are from the silicate ironformation and from overlying mafic rocks of igneous origin.The analysed assemblages include ferrohypersthene-ferro-augite-cummingtonite,ferrohypersthen-ferroaugite, cummingtonite-ferroaugite, diopside-hornblende,anthophyllite-hornblende, hypersthene-diopside-hornblende-garnet,and olivine-hypersthene-chlorite. The analyses show that (1) the minerals are nearly in equilibriumas shown by parallel tie lines, (2) cummingtonite generallyhas a higher MgO/FeO ratio than coexisting ferrohypersthene,(3) the phase higher in calcium has the higher MgO/FeO ratio,(4) the solubility gap between ferrohypersthene and ferroaugiteis 43 mole percent. The stability relationships of pyroxenes and amphiboles arediscussed in view of the new data. It is shown that FeO-CaO-SiO₂systems often behave differently from MgO-CaO-SiO₂ systems.Hedenbergite is probably not stable in the presence of excessCO₂ in the area. The low variance ferrohypersthene-ferroaugite-cummingtonite-calcite-quartzassemblage indicates that the rocks were closed to H₂O and CO₂.The behaviour of the volatile components is discussed in viewof this fact. The source of the silicate minerals is assumed to be hydrousiron silicates and carbonates. A model of the sequence of chemicalreactions taking place in carbonate-silicate iron formationsduring metamorphism is suggested. ¹Present address: Bolidens Gruvaktiebolag, Boliden, Sweden.     

水热法分解钾长石制备雪硅钙石的实验研究

采用CaO作为助剂,在低温、中压的水热条件下分解钾长石,继而合成一种水合硅酸钙--雪硅钙石,同时得到KOH稀溶液,可用于制备高纯碳酸钾。影响晶化反应的主要因素有n(Ca)/n(Al+Si)、晶化温度、晶化时间、水固比（质量比）、搅拌速度等。讨论了各因素对钾长石分解及雪硅钙石形成的影响,通过X射线粉末衍射、热重-差热分析、扫描电镜等手段对合成产物进行结构性能表征。实验结果表明,以CaO为助剂分解钾长石,同时合成雪硅钙石的工艺方法可行,资源利用率接近100%。实验得到的优化工艺条件为：晶化温度为220～250 ℃,n(Ca)/n(Al+Si)在0.8～1.0之间,晶化时间5～8 h,水固比为20～25,搅拌速度400 r/min。在此条件下,钾长石中K₂O的溶出率达80%以上,同时得到结晶良好的针状雪硅钙石晶体。     

不同温度条件下乙酸对长石溶蚀过程的实验研究

本文报道了不同埋藏温压条件下乙酸对条纹长石溶蚀过程的实验研究。结果证明:１）在条纹长石溶蚀过程中，Ｋ、Ｎａ、Ａｌ优先释放，Ｓｉ是最后释放的元素。２）在相对低温的条件下，长石溶出主要元素的比例远远偏离其化学组成，在相对高温的条件下，则接近其化学组成。３）在条纹长石中.钠长石比钾长石更容易分解。４）温度升高对条纹长石中Ｓｉ的影响最大，其温度效应分别是Ｋ、Ａｌ、Ｎａ的９.２，８.６和５.４倍。５）不同温度区间Ｓｉ，Ａｌ的温度效应存在显著的差别，Ａｌ主要在小于９５℃区间释放，而Ｓｉ主要在大于９５℃区间释放，此时将有约２/３的Ｓｉ不能加入到高岭石中。因而在埋藏成岩过程中，自生ＳｉＯ_２矿物沉淀造成的孔隙封堵作用主要发生在地温大于９５℃的埋深中。６）相对高温高压的实验中获得了蛋白石等自生ＳｉＯ_２矿物的沉淀，进一步证明Ｓｉ主要是在高温区间释放的。     

Experimental Study of Pyroxene Equilibria in the System CaO--MgO--FeO--SiO2

Subsolidus phase equilibria of pyroxenes in the CaO—MgO—FeO—SiO₂system have been experimentally determined at 30 and 15 kb,and mainly at 1200 °C. While phase relations at 30 kb and1200 °C are characterized only by orthopyroxene and clinopyroxene,at 15 kb and 1200 °C phase relations are complicated bythe appearance of the two-clinopyroxene miscibility gap. Thestability of Ca-free clinopyroxene was demonstrated at 15 kband 1200 °C and higher temperatures, and at 30 kb and 1450°C. The new experimental data were combined with the data from theliterature to yield a generalized phase equilibrium scheme ofpyroxenes in temperature-pressure-composition space. Thoughthe majority of naturally occuring pyroxenes can be understoodin the light of the scheme, there are a few samples not fullyconsistent with it. These are briefly mentioned.     

两株异化铁还原菌与蒙脱石交互作用实验研究

本文选用采自辽宁某矿的天然钠基蒙脱石与两株异化铁还原菌模式菌株Shewanella putrefaciensCN32和She-wanellaoneidensisMR-1,研究了蒙脱石与微生物之间的交互作用。结果表明这两株菌均能还原蒙脱石晶格中的三价铁,使微生物作用于蒙脱石之后的反应体系中二价铁离子浓度明显升高,反应悬浊液颜色由无色变为浅绿色。透射电子显微镜晶格条纹像显示微生物作用后的粘土矿物微结构发生明显变化,其层间距d001值从1.29 nm分别减小为1.06 nm(CN32)和1.02nm(MR-1)。上述结果综合指示这两株异化铁还原菌能够通过还原天然蒙脱石结构中的三价铁促进矿物发生物相转变。     

水热法从钾长石中提取钾、硅、铝的实验研究

通过水热化学反应将钾长石中的钾、硅和铝转变为可溶性组份,具有十分重要的应用价值.本文用单因素实验考察了不同水热反应实验条件对钾长石中钾、硅、铝溶出率的影响,并根据溶出率结果优化了反应条件.单因素实验结果表明:(1)在190℃条件下,随生石灰加入量的逐渐增加,产物中各元素的溶出率有一个先增加后减少的趋势.(2)在相同的生石灰、钾长石比例下,当反应16 h后,产物中各元素的溶出率随反应时间的延长趋于平缓.(3)随反应温度的逐渐增加,产物中各元素的溶出率逐渐增加.     

Mineral Compositions and Equilibria in the Metamorphosed Iron Formation of the Gagnon Region, Quebec, Canada

Forty-seven specimens of the Wabush Iron Formation were collectedfrom ten outcrop areas. Twenty-five specimens contain the assemblage(1), quartz+clinopyroxene+calcite with or without orthopyroxene,grunerite, magnetite, ankerite, and siderite. Five specimenscontain assemblage (2), quartz+clinopyroxene+actinolite+calcite+magnetite+hematite,and two contain assemblage (3), quartz+orthopyroxene+actinolite+magnetite+hematite.In three specimens of assemblage (1), graphite occurs in theabsence of magnetite; pyrrhotite and pyrite occur separatelyor together in specimens with assemblage (1). Thirty-nine clinopyroxenes, 38 orthopyroxenes, 18 grunerites,7 actinolites, 16 calcites, 1 ankerite, and 1 siderite wereanalyzed for iron, manganese, and calcium by X-ray emissionspectrography. Magnesium contents were estimated by assumingstoichiometric proportions. Minerals occurring with hematite show low Fe/(Fe+Mg) ratios,and those in the other assemblages show higher values with awide range of variation. In orthopyroxene, Fe/(Fe+ Mg) rangesfrom 0·17 (with hematite) to 0·77. Regularity in the distributions of Fe, Mn, and Ca between pairsof coexisting minerals shows that equilibrium was attained inmost of the rocks studied. This regularity is also accomplishedin the distribution of Mn between calcite and coexisting silicatesas well as between the silicates themselves. Small differencesin the distributions of Ca and Fe depend on both outcrop areaand mineral assemblage. Phase rule considerations suggest that the specimens with dolomite-ankeriteor magnesitesiderite do not represent equilibrium assemblages.Variations in orthopyroxene compositions in assemblages withpyrite or pyrrhotite, or both, and magnetite indicate non-equilibrationof sulfides with silicates. The presence of the oxygen buffer,magnetite+hematite, attests to the immobility of oxygen duringmetamorphism. Within each outcrop area, over which the temperature and pressureare assumed to have been uniform, variations in the compositionsof the silicates in the sub-assemblages quartz+ orthopyroxene+gruneriteand quartz+orthopyroxene+clinopyroxene+calcite indicate gradientsof µ_H2O µ_CO2 and respectively. As characterizedby the composition of orthopyroxene, both gradients are relativelylow along strike, and high across strike. The direction of gradientsacross strike is almost without reversals, which is consistentwith intergranular diffusion of H₂O and CO₂. Phase rule restrictionsfor a majority of assemblages are not in accord with the simultaneousimposition of µ_H2O and µ_CO2 gradients on the rocks,nor the formation of an H₂O-CO₂ fluid phase during metamorphism.     

利用钾长石粉水热合成13X沸石分子筛的实验研究

对综合利用钾长石提钾工艺中的重要高附加值副产品13X沸石分子筛的合成进行了实验研究。对福建沙县的钾长石粉加入配料NaCO3进行焙烧实验，确定培烧的最佳工艺参数为：钾长石粉：NaCO3=1：1．30(摩尔比)，焙烧温度为845℃，焙烧时间为150min；优化的水热合成条件为M2O／SiO2(mo1)=1．50，H2O／M2O(mo1)=40．0，合成时间为8h，晶种加入量为9．0％。对合成样品化学成分分析、X射线物相分析、红外光谱分析、扫描电镜分析表明，合成13X沸石分子筛结晶完好，性能优良．水热反应经由溶解水合反应和聚合浓缩反应两大阶段。     

熔融制样X射线荧光光谱法测定钠长石钾长石中多元素

采用熔融制样X射线荧光光谱法测定钠长石和钾长石中的Na2O、MgO、Al2O3、SiO2、P2O5、K2O、CaO、TiO2、Fe203、Rb、Sr、Y、Zr、Ba14个成分的含量，所得结果与化学分析结果相符，各组分测定33次的仪器RSD为0．10％～4．67％。在试验过程中，对功率为1kW和4kW的两种波长色散型X射线荧光光谱仪的灵敏度和检出限进行了比较，并对仪器的精密度和长期稳定性进行了考察。     

An Experimental Study of the Influence of Oxygen Fugacity on Fe-Ti Oxide Stability, Phase Relations, and Mineral--Melt Equilibria in Ferro-Basaltic Systems

Equilibrium crystallization experiments at atmospheric pressureand over a range of oxygen fugacity (fO₂) have been carriedout on a ferro-basaltic composition similar to liquids proposedto have been parental to much of the exposed portion of theSkaergaard intrusion. Before Fe-Ti oxide saturation the liquidline of descent is little affected by fO₂. However, the appearancetemperatures of the magnetite-ulvspinel solid solution (Mt)and the ilmenite-haematite solid solution (Ilm) depend stronglyon fO₂. Above the fayalite-magnetite-quartz (FMQ) buffer Mtis the first oxide phase to appear on the liquidus, but belowthe FMQ buffer Ilm is the first oxide to crystallize. The appearancetemperature of Mt is 1100C at FMQ and the Mt liquidus slopeis 30C/log fO₂ unit between FMQ–;2 and FMQJ+1. The Ilmliquidus is at 1100C between FMQ and FMQ–2, but movesto lower temperature at higher fO₂ where Mt is the first oxidephase. The results indicate that the ferric iron content ofMt-saturated melts varies linearly with inverse temperature,and that Ilm saturation is closely related to melt TiO₂ content.Mt saturation produces an immediate enrichment of SiO₂ and depletionin FeO^* in the melt phase, whereas Ilm saturation produces similarenrichment in SiO², but inn enrichment may continue for 10Cbelow the ilmenite liquidus. The experimental liquids reacha maximum of 18 wt% FeO^*, at 48 wt% SiO₂ for ilmenite-saturatedmelts at low f_O2, more differentiated melts having lower ironand higher silica. Cotectic proportions, derived from mass balancecalculations, are in good agreement with data from natural samplesand other experimental studies. Olivine resorption is inferredat all fO₂, with the onset of resorption occurring 10C higherthan the appearance of magnetite. The effect of fO₂ on silicatemineral compositions, and partitioning of elements between coexistingmineral-melt pairs, is small. Thermodynamic considerations suggestthat variations of Fe-Mg partitioning between the iron-richolivines, pyroxenes and melts produced in this study may beexplained by known non-idealities of Fe-Mg mixing in the crystallinephases, rather than nonidealities in the coexisting melts. Theseexperiments also provide insights into many features commonto natural tholeiitic series of volcanic and plutonic rocks,and provide experimental data required for modelling of fractionalcrystallization and crystallization closed to oxygen, processeswhich are not easily investigated experimentally. KEY WORDS: ferro-basalt; Fe-Ti oxides; oxygen fugacity; Skaergaard intrusion; iron enrichment ^*Corresponding author. Present address: Bayerisches Geoinstitut, Univerritt Bayreuth, D-95440 Bayreuth, Germany     

铁矿石物相中磁性铁测试方法的改进

在传统的铁矿石物相分析中,磁性铁用盐酸溶解,有的样品溶解不完全,故而造成各单项加和低于全铁分析结果.笔者通过试验,发现用硫磷混酸或残渣碱熔能很好地分解磁性铁,使单项加和与全铁分析结果一致.     

高铁钾长石粉体合成13X型分子筛的晶化过程

利用高铁钾长石粉体水热合成13X型分子筛,对晶化过程进行表征,确定了晶化过程的诱导期、晶化期和沸石生长速率。结果显示,与低铁合成体系对比,高铁合成体系中反应物料的陈化期及晶化早期反应产物的红外结构、化学组成更接近于13X型分子筛的红外结构和化学组成,即反应物更易于向13X型分子筛结构转变;13X型分子筛开始形成的时间更早,晶化过程的诱导期和晶化期时间缩短。与低铁合成体系一样,高铁体系水热合成13X型分子筛,晶体成核与生长主要发生在凝胶相内部,是凝胶结构逐步趋于有序化的过程。     

痕量铁和锰的化学发光检测

评述了国内外有关铁、锰的化学发光分析进展。从发光体系、操作方式、最佳条件、干扰离子、检测限等各个方面对化学发光法测定铁、锰及其它们与其它组分同时测定中的应用进行分类评述。     

示波极谱法测定铁矿石中微量砷

报道了H2SO4－Te(Ⅳ）－NH4I体系极谱法测定铁矿石中的微量砷。试验表明，采用HNO3、HCl混合酸分解试样，溶液中大量铁不需分离，在测定体系中Fe^3 允许存在量为6mg。方法经部级标样分析验证，结果与推荐值相符，6次测定的相对标准偏差小于14％。     

钾长石分解反应热力学与过程评价

综述了添加各种助剂分解钾长石的研究进展。对不同体系中钾长石分解反应的G ibbs自由能和能耗计算,综合考虑一次性资源、能源消耗量和烧结过程的环境相容性、产品方案等因素,结果表明:只有以石灰石、碳酸钠为配料的工艺路线具有实际工业应用价值;而唯有以碳酸钠为配料时,钾长石原料烧结过程才具有一次性资源消耗量最少、能耗最低、温室气体CO2排放量最小、且可生产高附加值产品、实现完全清洁生产等优点。因此,选择以碳酸钠为配料分解钾长石的技术路线,具有良好的工业化应用前景。     

红色长石的宝石学特征研究

近几年在国内外珠宝市场上出现了一种红色透明长石,其天然性引起了广泛的争议。采用常规的宝石学方法、LA—ICP—MS以及紫外-可见分光光度计等测试仪器研究了该红色长石样品的宝石学特征、化学成分及紫外-可见吸收光谱,旨在探讨其致色原因。结果表明,该红色长石样品属于中长石;与黄色长石样品相比,其化学成分中Cu的质量分数为739×10^-6～801×10^-6,远远高于黄色长石的（1．07×10^-6）,而其它微量元素的质量分数则无明显的差别,故认为Cu可能与其呈红色有关;紫外-可见吸收光谱结果显示,该红色长石样品在可见光区的吸收带主要位于566nm处,推测其可能与Cu对可见光的吸收有关。