LiF—CaF2,NaF—CaF2和KF—CaF2系熔体热力学参量及相图的计算

本文将ＤＣＡ模型应用于ＬｉＦ－ＣａＦ２，ＮａＦ－ＣａＦ２和ＫＦ－ＣａＦ２熔体，并假设在这些熔体中存在络合离子ＣａＦ３，利用已有的上述混合熔体量热和熔盐相图的实验数据估计了熔体模型中的参数，并计算了熔体的混合热力学参量及相图，计算结果与实验结果吻合较好。     

KF－LiCl－CaCl_2系相图研究

用目测变温法、差热分析法及Ｘ射线粉末法测定了ＫＦ─ＬｉＣ─ＣａＣｌ_２系熔盐相图，发现ＫＦ在ＬｉＣｌ－ＣａＣｌ_２熔盐溶液中呈负偏差，并对ＫＦ－ＬｉＣｌ－ＣａＣｌ_２系相图和已经研究的ＫＦ－ＬｉＣｌ－ＢａＣｌ_２及ＫＰ－ＬｉＣｌ－ＳｒＣｌ_２系相图进行了讨论，发现碱土金属氟化物的初晶面积和溶解能参数之间存在一定的关系．     

电渣重熔用CaF_2＋Al_2O_3和CaF_2＋Al_2O_3＋CaO系熔渣传氧的研究

利用ＺｒＯ_２固体电解质氧浓差电池测定了电渣重熔用ＣａＦ_２＋Ａｌ_２Ｏ_３和ＣａＦ_２＋Ａｌ_２Ｏ_３＋ＣａＯ系熔渣的氧渗透率，考察了熔渣成分及温度对熔渣传氧性能的影响．在１６７３—１８７３Ｋ和０．１ＭＰａ的氧气氛下，侧得这两个渣系熔渣的氧渗透率分别为１×１０－（２０）—６×１０－（１９）和１×１０￣（２１）—５×１０￣（１８）ｍｏｌＯ_２·ｃｍ￣（－１）·ｓ￣（－１）；随ＭｎＯ_２，Ｆｅ_２Ｏ_３，Ｃｒ_２Ｏ_３，ＴｉＯ_２，ＣａＦ_２含量和碱度（ＣａＯ／ＳｉＯ_２）的增高，熔渣的氧渗透率增大，ＭｎＯ_２和Ｆｅ_２Ｏ_３的影响尤为显著；随温度的升高，熔渣的氧渗透率增大，且可按速率过程来处理ＣａＦ２基多元复杂熔渣的传氧过程。     

CO还原CaO－SiO_2－Al_2O_3－Fe_tO渣系研究

研究了在１７２３Ｋ下ＣＯ还原ＣａＯ－ＳｉＯ_２－Ａ１_２Ｏ_３－Ｆｅ_ｔＯ渣系。根据ＣＯ_２红外分析仪测定的出口气体中ＣＯ_２浓度变化，计算了炉渣的表现还原速度常数Ｋ_ａ和还原速度常数Ｋ。结果表明，加入Ａｌ_２Ｏ_３，提高了ＣａＯ－ＳｉＯ_２－Ｆｅ_ｔＯ的Ｋ_ａ和Ｋ值；炉渣碱度不变时，随着Ｆｅ_ｔＯ含量的增加，Ｋ_ａ呈增加趋势，但Ｋ则呈抛物线趋势变化；当ＦｅＯ的光学碱度∧_ＦｅＯ为１．０或０．８７时，Ｋ_ａ随该四元渣系光学碱度的增加而线性增加，而Ｋ则呈递减趋势。用炉渣规则溶液模型计算了ＣａＯ－ＳｉＯ_２－Ａｌ_２Ｏ_３－Ｆｅ_ｔＯ四元渣系的Ｆｅ_ｔＯ活度ａ_Ｆｅ_ｔＯ。     

KF—LiCl—CaCl2系相图研究

用目测变温法，差热分析法及Ｘ射线粉末法测定了ＫＦ－ＬｉＣｌ－ＣａＣｌ２系熔盐相图，发现ＫＦ在ＬｉＣｌ－ＣａＣｌ２熔盐溶液中呈负偏差，并对ＫＦ－ＬｉＣｌ－ＣａＣｌ２系相图和已经研究的ＫＦ－ＬｉＣｌ－ＢａＣｌ２及ＫＦ－ＬｉＣｌ－ＣｒＣｌ２系相图进行了讨论，发现碱土金属氟化物的初晶面积和溶解能参数之间存在一定的关系。     

CaO－SiO_2－Al_2O_3－FeO熔渣起泡行为的研究

在１５００℃下，用Ｘ射线透视装置研究了ＣａＯ－ＳｉＯ_２－Ａｌ_２Ｏ_３－ＦｅＯ熔渣被石墨还原过程中渣的起泡行为，测定了熔渣的起泡指数和起泡率等参数．结果表明，随熔渣碱度上升，其起泡率增大而起泡指数却下降．同时考察了ＭｇＯ，ＣａＦ_２，Ｎａ_２Ｏ等添加物对熔渣起泡行为的影响．通过对熔渣起泡指数的因次分析得到，熔渣起泡指数与熔渣粘度，密度，表面张力及重力加速度ｇ有如下关系：     

含挥发组分B_2O_3渣系活度的测定方法

本文以Ｓｎ作熔剂，以石墨作坩埚，在一个半密闭的石墨容器内，用“熔渣－金属”化学平衡法测定了含挥发性组分Ｂ２Ｏ３的ＣａＯ－Ｂ２Ｏ３二元系中ＣａＯ的活度；用α函数积分法计算了Ｂ２Ｏ３的活度．实验结果与文献报道的利用相图和生成自由能计算得到的数据相符．     

晶格形变情况下Ga－In－As体系热力学研究

由已有热力学和相图实验数据，用Ｃａｌｐｈａｄ技术优化出一组描述Ｇａ－Ｉｎ－Ａｓ三元体系热力学性质的数学模型，定量估算了在用外延法制作ＩＩＩ－Ｖ族化合物时，由于外延层和衬底晶格不匹配，外延分子晶格弹性形变的形变能对固液平衡相图的影响，计算相图和实验结果基本一致．     

含挥发组分B_2O_3渣系活度的测定方法SCIEI

本文以Ｓｎ作熔剂，以石墨作坩埚，在一个半密闭的石墨容器内，用“熔渣－金属”化学平衡法测定了含挥发性组分Ｂ２Ｏ３的ＣａＯ－Ｂ２Ｏ３二元系中ＣａＯ的活度；用α函数积分法计算了Ｂ２Ｏ３的活度．实验结果与文献报道的利用相图和生成自由能计算得到的数据相符．     

Ca-Dy2O3-Fe体系反应的动力学研究

分析了Ｃａ－Ｄｙ２Ｏ３－Ｆｅ体系高温还原－扩散制备ＤｙＦｅ２热力学可能性,应用收缩核模型确定扩散是该体系反应的控制步骤,并进行了ＸＲＤ,ＥＤＸ与ＳＥＭ分析,得知在高温下可用Ｃａ还原Ｄｙ２Ｏ３生成Ｄｙ,Ｄｙ向Ｆｅ中扩散生成ＤｙＦｅ２,同时求得ＤｙＦｅ２的表观活化能为２１０ｋＪ／ｍｏｌ。     

KF-LiCl-BaCl_2及LiF-LiCl-BaCl_2相图的测定SCIEI

本文测定了KF-LiCl-BaCl_2及LiF-LiCl-BaCl_2的伪三元相图。并就改变一价氟化物阳离子半径的变化和相图中初晶区面积的关系进行了讨论。     

THERMODYNAMIC CALCULATION MODELS FOR TiO_2-BASED SLAG MELTS

1.IntroductionTheincreasingdemandsf0rlownitrogensteelproductsgiveriset0greatenthusiaJsmtouseTiO2-basedfluxfordenitrogeniZationofsteel[1-3].ManyexperimentscondrmedthatTi0z-basedslagshavehighernitridecaPacitiesandaPpeartobeonekind0fthemosteffectivefiuxesf0rdeIiltrogenization.Butasfarastherm0dynamicstudiesareconcerned,littleworkhasbeenreported0nthethermodynamiccalculationm0delsforTiO2-base'slags[4],especiallyf0rmulticomponentslagswithtitania-Inadditi0n,aJsaresultofusingvanadium-bearingtitani…     

PHASE DIAGRAMS OF KF-LiCI-BaCl_2 AND LiF-LiCI-BaCl_2 SYSTEMS

The phase diagrams of molten salt systems KF-LiCI-BaCl_2 and LiCI-LiF-BaCl_2 havebeen determined by visual polythermal method.The relationship between the change of cationradius of monovalent fluoride and the areas of primary crystal region in the phase diagrams isdiscussed.     

Application of annexation principle to the study of thermodynamic properties of ternary molten salts CaCl_2-MgC_2-NaCl

Based on the practical basis of measured activities and phase diagrams as well as in the light of the mass action law, the model of inseparable cations and anions of molten salts and mattes, and the annexation principle of two kinds of solutions in binary melts, the calculating model of mass action concentrations of molten salts CaCl_2-MgCl_2-NaCl was formulated. The results of calculation not only agree with experimental values, but also obey the mass action law, testifying that the model formulated can embody the structural characteristics of these ternary salts, and that the model of inseparable cations and anions as well as the annexation principle of two kinds of solutions in binary melts are also appficable to these ternary salts.     

熔融CaCl2-MgCl2体系的粘度

用旋转柱体法系统测量了CaCl2-MgCl2熔融盐体系的粘度,考察了熔融CaCl2-MgCl2体系粘度随温度和组成的变化关系.比较了实验测得的数据与文献报道值,根据熔融盐体系粘度变化规律对熔融体系结构进行了推断.实验测得熔融物体系粘度随温度升高而明显降低,由于所用试剂含有少量杂质,与文献报道的纯CaCl2和MgCl2的粘度值相比,实验测得值出现偏差.熔融CaCl2-MgCl2混和体系的粘度明显要比纯物质的粘度大,这说明在熔融条件下,CaCl2-MgCl2体系生成了体积较大的配合物粒子,增加了熔体粘度.在不同的温度条件下,由于有不同组成的配合物生成,体系粘度最大值对应了不同熔体组分.     

Application of annexation principle to the study of thermodynamic properties of ternary molten salts CaCl2-MgCl2-NaCl

Based on the practical basis of measured activities and phase diagrams as well as in the light of the mass action law, the model of inseparable cations and anions of molten salts and mattes, and the annexation principle of two kinds of solutions in binary melts, the calculating model of mass action concentrations of molten salts CaC12-MgCl2-NaCl was formulated. The results of calculation not only agree with experimental values, but also obey the mass action law, testifying that the model formulated can embody the sauctural characteristics of these temary salts, and that the model of inseparable cations and anions as well as the annexation principle of two kinds of solutions in binary melts are also applicable to these ternary salts.     

Phase diagrams of Li2MoO4-Na2MoO4 and Na2MoO4-K2MoO4 systems

The phase diagrams of the Li2MoO4-Na2MoO4 and Na2MoO4-K2MoO4 systems have been reassessed using differential thermal analysis together with high-temperature and room-temperature X-ray diffraction analysis. The results showed that the compound Li2MoO4.6Na2MoO4 did not exist; however, it confirmed the existence of the compound Li2MoO4.3Na2MoO4 in the Li2MoO4-Na2MoO4 systen＇ls. With regard to the system of Na2MoO4-K2MoO4, we could not confirm the results reported by Bukhanova who claimed that the system was eutectic type with 1：1 and 1：2 intermediate compounds, refuting the statement of Amadori who thought there was an apparent phase boundary at high temperature in α-solid solution region of the Na2MoO4-K2MoO4 binary system. The revised phase diagrams of these systems are illustrated in this article. These experimental results are in agreement with the computerized prediction using the support vector machine-atomic parameter method for the assessment of phase diagrams.     

含B2O3渣系的热力学计算模型

根据炉渣结构的共存理论和相图，推导了ＣａＯＢ２Ｏ３和ＦｅＯＦｅ２Ｏ３Ｂ２Ｏ３渣系的热力学计算模型。结果表明：（１）理论计算的ＣａＯＢ２Ｏ３渣系的作用浓度ＮＣａＯ及ＮＢ２Ｏ３与实测的活度ａＣａＯ及ａＢ２Ｏ３一致；（２）理论计算的ＦｅＯＦｅ２Ｏ３Ｂ２Ｏ３渣系的氧化能力ＮＦｅｔＯ与实测的炉渣ＦｅｔＯ的活度值相符合。这说明本文提出的热力学计算模型是合理的。     

Al-Si-Fe三元系热力学计算与评估

利用Calphad技术和应用Pandat相图计算软件,重新评估了Al-Si-Fe体系液相投影图,550、727、800℃等温截面,以及不同成分合金在1 477℃时的液相混合焓。结果表明,计算所得相图及液相混合焓与实验数据相符,该工作建立的热力学模型及参数可作为外推建立Al-Zn-Si-Fe等高元体系数据库的基础,并对相关体系的材料设计工作具有重要的指导意义。     

PREDICTION OF THERMODYNAMIC PROPERTIES OF THE FeO-CaO-SiO_2 MELTS FROM WILSON EQUATION

1.IntroductionIn0rdert0c0mpensateforash0rtc0ming0fclassicaltherm0dynamics,manyempiricalorsemiempiricalmodelsbased0nthethe0ryofregularsolutionshavebeendevel0pedforpredictingthethermodynamicpr0pertiesofternaryandevenmulticomponentmoltenslags[l'2].Ac0mmoncharacteristic0fthemist0usem0reempiricalappr0aches.Ifonlybinarydataareusedtopredictthetherm0dynamicpr0pertiesofaternarysystem,thedeviationsofpredictedvalueswillbelarger;ifthevauesneedtomatchtherequiredaccuracytaporti0n0fexperimentaldataofaternary…