NaF-Na_(3)PO_(4)-H_(2)O体系相图与热力学模型

NaF–Na_(3)PO_(4)–H_(2)O体系是稀土矿物加工的典型盐水体系,开发氟、磷回收工艺需要该体系的相图和热力学模型支持。利用等温溶解平衡法测定了273.15 K、298.15 K、323.15 K和348.15 K的固液相平衡数据,并基于eNRTL模型框架构建了该体系从最低共熔点到348.15 K的热力学模型。实验结果表明:NaF–Na_(3)PO_(4)–H_(2)O体系存在NaF、Na_(3)PO_(4)·12H_(2)O、Na_(3)PO_(4)·8H_(2)O和复盐NaF·2Na_(3)PO_(4)·19H_(2)O 4个固相物种;其中复盐在各温度均占据三元体系的主要相区,磷酸钠水合物的相区极窄,很难单独成盐,NaF相区相对较大并随温度升高而增大。热力学模型研究较好地表达了NaF–H_(2)O、Na_(3)PO_(4)–H_(2)O体系的多温离子活度系数、溶液渗透系数、二元体系相图,获得了盐水作用参数和6个固相的热力学数据;通过对三元体系多温相图数据的有效表达,获得了盐-盐作用参数和复盐的热力学数据,在此基础上推测了NaF–Na_(3)PO_(4)–H_(2)O体系相图结构,获得了难以实验测定的9个零变量点和9条单变量共饱和线,从而得到了全部固相的平衡相区,并给出了NaF–Na_(3)PO_(4)–H_(2)O体系完整相图,为更复杂体系的热力学表达以及工业应用提供了参考依据。

Thermodynamic modeling and phase diagram prediction of salt lake brine systems.Ⅰ. Aqueous Mg^2+–Ca^2+–Cl^- binary and ternary systems

Salt lake brine is a complex salt-water system under natural environment.Although many models can express the thermodynamic properties and phase equilibrium of electrolyte aqueous solution,the multi-temperature characteristics and predictability are still the goals of model development.In this study,a comprehensive thermodynamic model system is re-established based on the eNRTL model and some improvements:(1) new expression of long-range electrostatic term with symmetrical reference state is proposed to handle the electrolyte solution covering entire concentration range;(2) the temperature dependence of the binary interaction parameters is formulated with a Gibbs Helmholtz expression containing three temperature coefficients,the liquid parameters,which associated with Gibbs energy,enthalpy,and heat capacity contribution;and(3) liquid parameters and solid species data are regressed from properties and solubility data at full temperature range.Together the activity coefficient model,property models and parameters of liquid and solid offer a comprehensive thermodynamic model system for the typical bittern of MgCl2-CaCl2-H2 O binary and ternary systems,and it shows excellent agreement with the literature data for the ternary and binary systems.The successful prediction of complete phase diagram of ternary system shows that the model has the ability to deal with high concentration and high non-idealitv system,and the ability to extrapolate the temperature.

Phase Equilibrium and Phase Diagram of the Ternary System（MgCl2 + MgB2O4 + H2O） at 288 and 298 K

1 Introduction The brines with high concentrations of magnesium and boron resources are widely distributed in the Qaidam Basin of the Qinghai-Tibet plateau,China(Zheng&Tang,1988).Although some works on the ternary system

Primary study of the isothermal phase diagram of the Cu_2O-Al_2O_3-SiO_2 ternary system at 1150℃ in air

The isothermal phase diagram of the Cu2O-Al2O3-SiO2 ternary system at 1150℃ was reported for the samples which were prepared from sol-gel method and quenched by water after being heated at 1150℃ for 12 h. Based on the conventional X-ray powder diffraction （XRD） and in situ high-temperature XRD quantitative analysis,in addition to scanning electron microscopy measurement,the phase identification was achieved. Combining the deduction from the component phase diagrams of the binary systems using the phase equilibrium theorem,the primary isothermal phase diagram was plotted over the composition area Cu2O-mullite-SiO2. In this area,the approximate composition areas of two two-phase regions and one three-phase region,（L2＋Cr）,（L2＋M）,and （L1＋L2＋Tr）,were determined. Moreover,the precise composition areas of both of the three-phase regions （L2＋Cr＋M） and （L2＋M＋A） were determined according to the results of conventional and in situ high-temperature XRD quantitative analysis by Rietveld method.

Phase equilibrium of CaSO_4Ca(OH)_2-H_2O system

In order to provide the theoretical guidance for applying the neutralization method to treatment of heavy metals wastewater with high concentration of sulfate, and to better understand the mechanism of calcium sulfate scale formation, the equilibrium solubility data of CaSOa-Ca（OH）2-H2O system at 298.15 K were theoretically calculated via the Pitzer semi-empirical ion-interaction theory, and determined experimentally by the optical method combining with X-ray diffractometry, and the calculated and determined phase diagrams of CaSOa-Ca（OH）2-H2O system were plotted and compared. Physical definition of each area was studied, and the physical law of characteristic point and line was explained in detail. Adjusting the pH value of neutralization-hydrolysis solution depended on the SO4z- concentration in the system. And interaction characteristics between the solubilities of CaSO4（s）and Ca（OH）2（s）were found out.

Subsolidus phase relation in the Bi_2O_3–Fe_2O_3–La_2O_3 system

Bismuth-containing semiconductor material is a hot topic in photocatalysts because of its effective absorption under the visible light. In this paper, we expect to explore a new bismuth-based photocatalyst by studying the subsolidus phase relations of the Bi2O3-Fe2O3-La2O3 system. The X-ray diffraction data shows that in this ternary system the ternary compound does not exist, while seven binary compounds （including one solid solution series Bi1-xLaxO1.5 with 0.167 〈 x 〈 0.339） are obtained and eight compatibility triangles are determined.

Subsolidus Phase Relations in the ZnO-BaO-V_2O_5 System

The subsolidus phase relations of the ZnO-BaO-V2O5 ternary systems were investigated by means of X-ray diffraction analysis. There are three ternary compounds, nine binary compounds and sixteen 3-phase regions found in this system. The crystal structure of the ternary compound Ba2ZnV2O8 was refined by Rietveld profile fitting method and the powder diffraction pattern is given. A new ternary compound Ba3.4Zn0.8V4O14.2 has been found by the powder diffraction pattern.

Phase Diagram Calculation and Fabrication of Multi-component Zirconia-Based Ceramics

Ceria-yttria co-doped zirconia-based multi-components ceramics, with superfine alumina dispersed in the matrix, possess excellent fracture toughness, strength and thermal stability. However, the mechanical properties and microstructure are strongly dependent on the composition and the fabrication procedure, especially the composition of zirconia containing multi-component ceramics.

Subsolidus Phase Relations in the ZnO-MoO_3-Bi_2O_3 System

The subsolidus phase relations of the ternary system Zn O-Mo O3-Bi2O3 have been investigated by X-ray diffraction（XRD） analyses. The phase diagrams have been constructed. There are eight binary compounds and no ternary compound in the Zn O-Mo O3-Bi2O3 system. This system can be divided into nine three-phase regions. From the phase relations of Zn O-MoO 3-Bi2O3 system, the possible component regions for Zn O single crystal flux growth are Zn O-Zn3Mo2O9-Bi2 Mo O6, Zn O-Bi2 Mo O6-Bi26Mo10O69, Zn O-Bi26Mo10O69-Bi14 MoO 24, and Zn O-Bi14 Mo O24-Bi38 Zn O58.

Measurements of zinc oxide solubility in sodium hydroxide solution from 25 to 100 °C

The solubility of zinc oxide in sodium hydroxide solution was measured in a closed polytetrafluoroethylene vessel from 25 to 100 ℃. The ZnO solubility was determined by employing the method of isothermal solution saturation. The results show that only ZnO solid exists in the equilibrium state in the low concentration alkali regions, and the solubility of zinc oxide is almost invariable with temperature. With the increase of alkali concentration, equilibrium solid turns from ZnO to NaZn（OH）3 suddenly, this mutation is called invariant point. The alkali concentration of the invariant points increases with increasing temperature, but the solubility of NaZn（OH）3 decreases with increasing alkali concentration at the same temperature. At the same Na2O concentration, the higher the temperature is, the higher the solubility of NaZn（OH）3 is.

Al-TiO_2-C体系热力学分析及Al_2O_3-TiC复相陶瓷的燃烧合成

对Al-TiO2 -C燃烧合成体系进行了热力学计算 ,并利用Al-O -N、Ti-O -N、C -O -N三个体系的叠加优势区相图分析了该燃烧合成体系的平衡产物相。结果表明 ,Al -TiO2 -C燃烧合成体系的绝热燃烧温度为 2 398K ,燃烧合成平衡相为Al2 O3和TiC。XRD检测结果与热力学分析结果相吻合 ,说明该燃烧合成反应进行得较为彻底 ,证实热力学分析结果可信。原位生成的Al2 O3和TiC两相分布较均匀 ,燃烧合成产物疏松多孔 ,易于通过球磨方式达到破碎。

Thermodynamics of some ZrO_2-containing ceramics

Thermodynamic assessment in the ternary systems ZrO2 -CeO2 -Y2 O3, ZrO2 -CeO2 -Ce2 03 and the limiting binaries ZrO2 -Y2 O3, ZrO2 -CeO2, CeO2 -Y2 03, ZrO2 -Ce2O3, CeO2 -Ce2O3 as well as the modeling for oxides are reviewed comprehensively. Based on the recent estimations on the YO1.5-CeO2, ZrO2-CeO2 and ZrO2 -YO1.6 systems, isothermal sections at 1273 and 1 973 K of the ternary CeO2- ZrO2-YO1.5system are calculated. In the system of ZrO2-CeO2-Ce2O3, the complex relation between the nonstoichiometry （y） in CeO2-x, the composition of the ZrO2 -CeO2 solid solution and the oxygen partial pressure （Po2 ） for different ZrO2 containing solid solutions CexZr1-xO2-x. are evaluated from 1 473 to 1 773 K. The relation between the degree of Ce^＋4 reduction to Ce.3 under different Po2 in the fluorite CeO2-xy and CexZr1-xOz-x solid solutions at different temperatures can be used as a guide in the development of functional ceramics.

Phase Relations in Si-Al-Y-O-C Systems

The present work investigated the phase relations in SiC-Al2O3-Y2O3-SiO2 (Si-Al-Y-O-C) system. As a continuation of our previous works, the purpose of this study is to understand the high temperature reaction behaviors of SiO2 in the system and its effect on the phase relations of the valuable system of SiC-Al2O3-Y2O3. The phase compositions of six solid-state reacted samples with different components of Y2O3:Al2O3:SiC:SiO2 were analyzed by XRD. The phase relations of the systems were determined. The subsolidus phase diagrams of ternary Al2O3-SiC-SiO2 system and the tentative phase diagram of an extended quaternary Y2O3-Al2O3-SiC-SiO2 system were presented latter involving several coexisting regions of four phases. The high temperature reaction behavior of SiO2 in the system and its effect on the phase relations of system were discussed.

斑岩铜矿蚀变分带与成矿机制:玉龙矿床水-岩反应热力学平衡模拟例析

蚀变分带和成矿机制的准确厘定是建立斑岩成矿模型与找矿预测的关键。本文以新生代金沙江-哀牢山成矿带的玉龙斑岩铜矿为例,通过质量作用定律(LMA)和吉布斯自由能最小化模型(GEM),构建含矿热液与斑岩侵入体的pH-f O 2相图和动态传输模型,以揭示蚀变分带成因和金属成矿机制。LMA与GEM结果显示初始成矿流体pH值为4.7,logf_(O2)=-23.0(ΔFMQ=+2.7),且溶解Cu含量为1138×10^(-6),Mo为1.2×10^(-6)。研究表明,当该酸性及强氧化性流体流入二长花岗斑岩体时,在温度为450~360℃范围内,代表钾硅酸盐化蚀变的钾长石、黑云母、硬石膏、赤铁矿和磁铁矿的矿物逐渐沉淀,且与钾硅酸盐化蚀变相关流体具有较高pH值(5.0~7.0)和氧逸度(ΔFMQ=+2.9~+3.6)特征;当温度在360~320℃范围时,代表青磐岩化蚀变阶段的典型矿物如绿帘石、铁绿泥石和斜绿泥石等逐渐形成,流体pH值(5.0~6.4)和氧逸度(ΔFMQ=+1.1)均有所下降;当温度进一步从320℃下降到200℃时,流体pH值(5.0~5.7)进一步小幅下降,而氧逸度则(ΔFMQ=+1.7)略有回升,在此期间,绢云母和方解石等开始沉淀并形成典型的绢英岩化蚀变。此外,以HMoO_(4)^(-)和MoO_(4)^(2-)为载体的Mo在狭窄高温区间(450~370℃)内沉淀,而以CuCl(CuCl_(4)^(3-)、CuCl_(2)^(-)、CuCl)为主要载体的Cu则在在中、高温(450~300℃)范围中沉淀。通过利用LMA反演及GEM正演相结合定量化地刻画了玉龙斑岩铜矿水岩反应过程,由此揭示了斑岩矿床蚀变分带是逐渐冷却的单一岩浆热液与斑岩体不断反应的结果,且不同温度窗口对应着钾硅酸盐化(450~360℃)、青磐岩化(360~320℃)和绢英岩化(320~200℃)蚀变矿物的形成,故含矿流体温度的快速下降可能是玉龙铜矿蚀变叠加的重要因素。此外,Cu、Mo络合离子溶解度对温度变化的差异响应,导致了Mo矿化主要发育于靠近斑岩体的高温区域,而Cu则以网脉状-浸染状叠加到Mo矿化之上,并广泛分布于斑岩体周边的高-中温区域。

二氯苯同分异构体及1,2,4-三氯苯体系固液平衡测定

本文利用差式扫描量热法,测定了邻二氯苯/间二氯苯、间二氯苯/对二氯苯、1,2,4-三氯苯/邻二氯苯、1,2,4-三氯苯/间二氯苯和1、2、4-三氯苯/对二氯苯等5个二元物系的固液平衡关系,并按以下方程进行了数据拟合: T=Tm*[1+sum from j=1 to n aj（x1-x1*）j]式中,Tm*为纯物质的熔点,x1*为Tm*下组分1的摩尔分率,aj为拟合系数。通过按不同比例配制的邻、间、对二氯苯以及1,2,4-三氯苯拟二元相图,测出了下列物系三元固液平衡温度-组成关系:邻二氯苯/间二氯苯/对二氯苯、邻二氯苯/对二氯苯/1,2,4-三氯苯和邻二氯苯/间二氯苯/1,2,4-三氯苯。

Three-segment control theory of MgO/Al2O3 ratio based on viscosity experiments and phase diagram analyses at 1500℃

In recent years, more and more high Al2O3 iron ores were used in East Asia, especially in China, which increased the Al2O3 content in blast furnace (BF) slag and resulted in poor metallurgical properties of slag. Adding MgO-bearing flux is one of the methods to improve the metallurgical properties of slag with high Al2O3. However, there is lack of theoretical basis for the proper MgO/Al2O3 ratio. Therefore, the properties of slag in SiO2-CaO-MgO-Al2O3 system were investigated based on viscosity experiments and phase diagram analyses at 1500℃, and the proper MgO/Al2O3 ratio was explored according to the Al2O3 content in slag. The experimental results show that: (1) in the case of Al2O3 content less than 14mass%, there is no limitation of the MgO/Al2O3 ratio, and the amount of MgO in slag can be determined according to the hearth tempera-ture and desulfurization;(2) in the case of Al2O3 content between 15 and 17mass%, the proper MgO/Al2O3 ratio should be 0.40-0.50;(3) in the case of Al2O3 content between 18 and 20mass%, the proper MgO/Al2O3 ratio should be 0.45-0.55. Consequently, the three-segment control theory of MgO/Al2O3 for BF slag was built, and the actual BF performances proved the validity and applicability of this theory. The research contents and results can give theoretical guidelines for stable BF operation in a wide range of Al2O3 content of 12-20mass%.

Study on the Phase Diagram of CsCl-CeCl_3-HCl(11%)-H_2O System and the Properties of the Compounds

The equilibrium solubility of CsCl CeCl 3 HCl(11%) H 2O quaternary system at 25 ℃ has been determined by the physic chemical analysis method, and the phase diagram was plotted. Two new double salts 3CsCl·CeCl 3·3H 2O and CsCl·CeCl 3·4H 2O obtained from the complicated system were identified and characterized by XRD, TG DTA, DSC, UV and fluorescence spectroscopy. Studies on the fluorescence excitation and emission show that 3CsCl·CeCl 3·3H 2O and CsCl·CeCl 3·4H 2O have upconversion luminescence of infrared visible range, and the upconversion emission intensity increases with the increase of ratio of CeCl 3 in CsCl.

柴达木盆地南翼山背斜构造区卤水自然蒸发实验

柴达木盆地南翼山背斜构造区卤水属高钙、低镁的氯化钙型卤水,微量元素硼、锂、锶、碘等含量相对较高,具有较高的综合利用价值。选取南翼山背斜构造区约3 000 m处深层卤水在自然状态下蒸发结晶,分析各种离子在固、液相中的分布规律、盐类结晶规律、结晶形态及微量离子的富集规律。结果表明:在室外自然状态下蒸发时,析出的盐中发现了不常见的异性结构的石盐、钾石盐和疑似K(NH_(4))Mg_(2)Cl_(6)·12H_(2)O的类光卤石;石盐阶段和钾石盐阶段析盐规律符合Na^(+),K^(+),Mg^(2+)∥Cl^(-)—H_(2)O相图,钾石盐、光卤石、南极石阶段符合K^(+),Na^(+),Ca^(2+),Mg^(2+)∥Cl^(-)—H_(2)O体系25℃简干图;微量离子中,Li^(+)、Br^(-)、I^(-)一直富集,其他离子在蒸发后期有不同程度的析出,三氧化二硼可以富集至18.77 g/L,Li^(+)最高可以富集至6.520 g/L。蒸发所得的钾混盐是提钾优质原料,实验结果可以为后期综合利用提供参考。

柴达木盆地深层卤水自然蒸发试验

近几年柴达木盆地勘查出了大储量深层卤水,为低钾、高钙、高钠、不饱和、高钙镁比(8.21∶1)的氯化钙型卤水,且硼、锂、锶含量相对较高,具有较高的综合利用价值。因此选取盆地西部某矿区2800 m深处卤水,在自然状态下蒸发结晶,研究盐类结晶规律及微量元素离子的富集规律,结果表明:在室外自然状态下蒸发时,主离子结晶路线符合K^(+),Ca^(2+),Mg^(2+)//Cl^(-)—H_(2)O体系25℃相图的基本规律;析盐过程主要为石盐→光卤石+石盐→铵钾光卤石+南极石+石盐→南极石+石盐;光卤石阶段有铵钾光卤石[(NH_(4))K_(2)Mg_(3)Cl_(9)·18H_(2)O]析出,液相中微量的Li^(+)、B_(2)O_(3)始终处于富集状态;在钾盐析出区间,钾的析出率为53.84%、产率为1.14%。

Study on BaB_2O_4-Na_2B_2O_4-K_2B_2O_4 Ternary System

The phase diagram of BaB_2O_4-Na_2B_2O_4-K_2B_2O_4 ternary system has been studied by combination of experimental measurement with theoretical calculation.On the basis of selfconsistent thermodynamic analysis of three sub-binary phase diagrams,the optimized the- rmodynamic data of these sub-binary systems are extrapolated to ternary system by asymmet- rical Toop approach,and the BaB_2O_4-Na_2B_2O_4-K_2B_2O_4 ternary phase diagram is calculated. In comparison with a measured typical vertical section,the calculated ternary phase diagram is quite satisfactory.