Application of the quasi-random lattice model to rare-earth halide solutions for the computation of their osmotic and mean activity coefficients

This work dealt with the computation of the mean activity coefficients of rare-earth halide aqueous solutions at 25℃, by means of the Quasi Random Lattice（QRL） model. The osmotic coefficients were then calculated consistently, through the integration of the Gibbs-Duhem equation. Using of QRL was mainly motivated by its dependence on one parameter, given in the form of an electrolyte-dependent concentration, which was also the highest concentration at which the model could be applied. For all the electrolyte solutions here considered, this parameter was experimentally known and ranged from 1.5 to 2.2 mol/kg, at 25 ℃.Accordingly, rare- earth halide concentrations from strong dilution up to 2 mol/kg about could be considered without need for best-fit treatment in order to compute their osmotic and mean activity coefficients. The experimental knowledge about the parameter was an advantageous feature of QRL compared to existing literature models. Following a trend already observed with low charge electrolytes,a satisfactory agreement was obtained with the experimental values for all the investigated rare-earth chlorides and bromides. For the sake of compactness, in this work the considered rare-earth halides were all belonging to the P63/m space group in their crystalline（anhydrous） form.

Activity coefficient and solubility of yttrium in Fe-Y dilute solid solution

The density functional theory （DFT） and density functional perturbation theory （DFPT） within the quasi-harmonic ap-proximation were employed to investigate the activity coefficient of Y in dilute Fe-Y solid solution. The ground states of Fe-Y com-pounds and the thermodynamic properties of bcc Fe were calculated, and the stable and metastable structures of Fe-Y compounds were predicted as well. With the temperature increasing, the Y activity coefficient in bcc Fe matrix increased rapidly, and the interac-tion between Y and Fe became more favorable. Based on the calculated thermodynamic properties, the solubility of Y in bcc Fe ma-trix as a function of temperature was predicted, and compared with the experimental data.

Effect of Rare Earth Elements on Kinetics of Salt Bath Vanadizing

Adding rare earth into permeating agent has an obvious catalytic effect on vanadizing on steel surface, and the vanadizing rate can increase about 30%～40%. The case depth ( x ) of the samples which have undergone different periods of vanadizing time at 950 ℃ was measured. These depth values ( x ) and its corresponded time ( t ) were substituded into the experimental formula, i.e., x n=Kt (ln x=(1/n) ln K+(1/n) ln t ), and were processed by mono linear regression. It is found that x and t have the relationship of x 2=Kt . Addition of rare earth can promote reaction of the permeating agent, and increase vanadium potential of the agent. Rare earth, as a strong reductant, makes the oxide on the steel surface reduced, and thus activates the steel surface. Permeating of rare earth into steel and the VC layer intensifies the crystal fault density, and, together with its excellent chemical activation, makes carbon atoms diffuse easily. These functions of rare earth can decrease the diffusion activation energy of the carbon atoms, and therefore has catalytic effect on permeation.

Effect of roasting activation of rare earth molten salt slag on extraction of rare earth,lithium and fluorine

A new process was proposed to extract rare earth elements(REEs),Li and F from electrolytic slag of rare earth molten salt by synergistic roasting and acid leaching.Firstly,the thermodynamic analysis of roasting reaction was carried out,then the effects of roasting factors on leaching REEs,Li and F in slag were investigated.In additions,the mineral phase and morphology of molten salt slag,roasting slag and acid leaching slag were characterized,and the migration mechanism of REES,Li and F minerals in roasting and leaching process was analyzed.The results show that the synergistic roasting and activation of molten salt slag by CaO and Al_(2)(SO_(4))_(3)are thermodynamically feasible.The optimum roasting conditions are as follows:molten salt slag of 20 g,Al_(2)(SO_(4))_(3)of 31.25 g and CaO of 6.25 g,roasting temperature of 1173.15 K and reaction time of 2 h,under this condition,the leaching rates of Nd,Pr,Gd,Li and F are 92.47%,91.56%,91.08%,96.69%and 96.8%,respectively.X-ray powder diffraction(XRD)and scanning electron microscopy-energy dispersive X-ray spectroscopy(SEM-EDS)analysis show that the rare earth fluoride(REF3)in molten salt slag transforms into soluble rare earth oxide(REO)after roasting and activation.After leaching,the leaching residue is mainly strip CaSO4,indicating that REES,Li and F can be fully extracted from molten salt slag.

活化方式对稀土尾矿中硅铝活化的影响

稀土尾矿含有数量可观的可用于分子筛合成的硅铝物种,而目前天然矿物绿色合成分子筛的难点在于矿物活化。本文以稀土尾矿为原料,分别采用热活化、碱熔活化和亚熔盐活化三种方式对稀土尾矿进行活化,将稀土尾矿中处于高聚态的硅铝物种解聚为具有反应活性的单聚态硅铝物种,为稀土尾矿合成分子筛奠定基础,以实现稀土尾矿的二次利用。采用XRF、XRD、SEM-EDS等表征手段对活化稀土尾矿的化学成分、物相组成和表面微观形貌进行分析,研究不同方式对稀土尾矿活化的影响。结果表明,热活化稀土尾矿中SiO2晶型仍较稳定,活化效果不明显;碱熔活化和亚熔盐活化能较完全地活化稀土尾矿,且碱熔活化更能实现稀土尾矿的高效活化,同时升高碱熔活化温度能促进稀土尾矿的活化。当NaOH与稀土尾矿质量比为3,碱熔活化温度为450℃时,稀土尾矿中活性硅铝物种的溶出率为84.2%和63%。本研究结果可为天然矿物绿色合成分子筛及稀土尾矿资源二次利用提供一定的理论基础。

稀土对盐浴渗钒动力学的影响

在盐浴渗钒中添加稀土对钢表面渗钒有明显的催渗作用 ,渗钒速度约提高 30 %～ 40 %。对 95 0℃经不同时间渗钒的试样测定渗层深度(x)。将x及所对应时间 (t)代入经验公式xn=Kt(lnx =lnK/n +lnt/n) ,经一元线性回归处理可知 ,x与t之间满足x2 =Kt抛物线关系。添加稀土可以加快渗剂反应而增大渗剂钒势。稀土的强还原性使钢件表面的氧化物还原而活化其表面。稀土渗入钢基体和VC渗层 ,会增大晶体缺陷密度 ,使碳原子扩散易于进行。稀土的添加可降低碳原子的扩散激活能 ,起到催渗的效果。

稀土电解槽内电解质导热系数的计算

根据混合熔盐导热系数计算原则,通过计算稀土电解槽内电解质单组分熔盐导热系数,从而预测稀土电解槽内三元系电解质熔盐导热系数,为稀土电解槽内温度场的研究提供了一个重要物性参数。

电导法测定298K时NdCl_3在DMF和H_2O中的活度系数

应用电导法在298K时测定了稀土氯化盐NdCl3 在混合溶剂(DMF H2O)中的电导率;利用公式计算了NdCl3 的摩尔电导率;应用Kohlraush经验规则,使用Origin软件进行线性拟合,外推得到298K时NdCl3 在混合溶剂(DMF H2O)中的无限稀释摩尔电导率λ0 = 300.01 (S·cm2 ·mol-1);应用Debye Hücker 和OsagerFalkenhangen公式计算了NdCl3 在混合溶剂(DMF H2O) 中的活度系数,并讨论了在298K 时浓度对稀土盐NdCl3 溶液活度系数的影响,随稀土氯化盐溶液浓度的增加,稀土盐溶液的活度系数降低.

Ce与Ag-Cu-Zn系钎料合金中Pb或Bi反应的热力学分析

采用热力学研究方法 ,计算分析了稀土元素Ce与Ag -Cu -Zn系钎料合金中杂质元素Pb、Bi的活度系数与Ce、Pb、Bi浓度的关系。热力学计算表明 ,在以Ce、Pb或Bi为溶质 ,Ag、Cu或Zn为溶剂的金属熔体中 ,溶质元素的活度系数在Ce的某一浓度范围内出现“等活度系数”现象 ,此时溶质元素的活度系数与溶质元素的浓度无关 ,这一新的发现表明 ,热力学研究结果与金属学研究结果完全吻合。

电导法测定298K时YCl_3在混合溶剂(DMF-H_2O)中的活度系数

应用电导法测定了298K时稀土氯化盐YCl3在混合溶剂(DMF-H2O)中的活度系数,并分析了浓度对稀土盐溶液活度系数的影响.

293K时稀土氯化盐LaCl_(3)水溶液热力学性质的研究

在293K时测定了稀土氯化盐LaCl3在水溶剂中的电导率,利用公式计算了LaCl3的摩尔电导率,应用Kohlraush经验规则,外推得到293K时LaCl3水溶液的无限稀释摩尔电导率,应用电导法测定和计算了293K时LaCl3水溶液的平均活度系数,讨论了在指定温度时浓度对LaCl3水溶液的电导率、摩尔电导率和活度系数的影响.

A_3BGa_3Si_2O_(14)类晶体的旋光特性研究

报道了La3Ga5SiO14(LGS)同构物掺杂性改进后,用提拉法生长出A3BGa3Si2O14(A=Ca2+,Sr2+;B=Nb5+,Ta5+)系列的4种晶体。此类稀土晶体均为单轴晶,属三方晶系,32点群。采用改造过的分光光度计研究了这类晶体的透过率、旋光角、旋光率色散,并与LGS进行了比较。透射率光谱显示,ABGS类晶体在大于294 nm的可见光谱区和红外区是透明的,透过率均大于LGS。偏振光透过率曲线显示这类晶体自然旋光率较大,结果表明,这4种晶体的旋光率均大于LGS,其中SNGS旋光为最大,在波长0.30μm处,ρ=240.75(°).mm-1;在0.633μm处,ρ=34.73(°).mm-1。根据实验结果计算了这类晶体的波尔兹曼系数,与文献结果吻合很好。

电导法测定293K时稀土铒盐在DMF中的活度因子

应用电导法测定了293K时稀土铒盐在DMF中的活度因子,首先在293K时测定了稀土铒盐在DMF中的电导率,利用公式λ=(κ液-κ剂)×10-3/c计算了稀土铒盐的摩尔电导率,应用Kohlrausch经验规则λ=λ0(1-βc),使用Origin软件进行线性拟合,作图外推求得稀土铒盐在DMF中的无限稀释摩尔电导率λ0值,利用Debye-Hücker和Osager-Falkenhangen公式计算了稀土铒盐在DMF中的活度因子,并讨论了293K时浓度对稀土铒盐在DMF中活度因子的影响.结果显示,随着稀土铒盐溶液浓度的增加,稀土铒盐溶液的活度因子降低.

电导法测定298K时稀土氯化盐在水中的活度系数

应用电导法测定了298 K时4种稀土氯化盐 ErCl3、DyCl3、NdCl3 和 YCl3 在极性水溶剂中的电导率,计算了稀土氯化盐的摩尔电导率,利用Debye Hücker和Osager Falkenhangen公式计算了稀土氯化盐在水中的活度系数.实验了298 K时稀土盐水溶液浓度对活度系数的影响,结果表明,随稀土氯化盐水溶液浓度的增加,其活度系数降低.

稀土盐浴渗钒的研究

研究了稀土对盐浴渗钒工艺及渗层某些(?)能的影响。结果表明,渗钒剂中添加稀土元素具有明显的催渗作用,渗钒速度约提高28%;稀土渗钒渗层的耐磨性、耐蚀性和抗氧化性均有所提高。稀土通过增大渗剂钒势、活化钢的表面、降低碳原子扩散激活能来提高渗钒速度。

稀土微肥对盐胁迫下菘蓝种子萌发及幼苗抗氧化系统的影响

【目的】研究外源稀土微肥对盐胁迫下菘蓝种子萌发、幼苗生长及幼苗抗氧化系统的影响,探究稀土微肥对菘蓝盐胁迫伤害的缓解效应,为稀土微肥在药用植物栽培中的应用提供理论依据。【方法】以蒸馏水为对照(CK),施加0.05%~0.50%的外源稀土微肥对100 mmol/L NaCl胁迫下的菘蓝种子及幼苗进行缓解处理,测定种子的发芽率、发芽势、发芽指数和活力指数,幼苗的株高、根长和鲜重以及幼苗中超氧阴离子自由基(O-2·)产生速率、过氧化氢(H2O2)含量、抗氧化酶活性等指标。【结果】100 mmol/L NaCl胁迫下,菘蓝种子的发芽率、发芽势、发芽指数和活力指数分别较CK下降66.67%、65.58%、58.30%和72.79%;幼苗的株高、根长、鲜重和干重分别下降41.06%、44.83%、40.76%和42.06%;幼苗中的O-2·产生速率和H2O2含量分别升高163.21%和121.13%,超氧化物歧化酶(SOD)、过氧化物酶(POD)和抗坏血酸过氧化物酶(APX)活性分别升高77.78%、24.78%和51.47%,过氧化氢酶(CAT)活性下降57.47%;在施加0.05%~0.50%的外源稀土微肥后,菘蓝种子的各项发芽指标、幼苗生长及抗氧化生理指标优于100 mmol/L NaCl处理,尤以0.30%稀土微肥处理的种子发芽指标和幼苗生长指标最高,幼苗中的O-2·产生速率和H2O2含量最低,抗氧化酶(SOD、CAT、POD、APX)活性最高。盐胁迫下,稀土微肥与幼苗中的O-2·产生速率和H2O2含量呈负相关,与抗氧化酶活性呈正相关;O-2·产生速率与H2O2含量呈极显著正相关(P<0.01,下同),O-2·产生速率和H2O2含量均与SOD、POD和CAT活性间呈极显著负相关。【结论】施加适当浓度的稀土微肥可提高盐胁迫下菘蓝种子的萌发能力,促进幼苗生长,增强幼苗中抗氧化酶活性,降低活性氧积累,缓解盐胁迫伤害,尤以0.30%的稀土微肥处理缓解效果较佳。

Study on Optical Activities of A3BGa3Si2O14 Crystals

Four crystals with the general formula of A3BGa3Si2O14 （A = Ca^2＋, Sr^2＋; B=Nb^5＋ , Ta^5＋） grown by using the Czoehralsky technique were reported. They are all uniaxial and belong to 32 point group. Their transmission, rotatory angle and specific rotation dispersion were investigated by speetrophotometer and compared with LGS. The transmission spectra show that they are transparent in the visible wavelength region beyond 294 nm and infrared region, and their transmission are all larger than that of LGS.The transmission spectra between parallel polasizers show that they have large optical activities which are larger than that of LGS. Of the four crystals, Sr3NbGa3Si2O14 has the largest optical activity ： 240.75 （°）·mm^-1 at 0.30 μm wavelength, 34.73 （°） ·mm^-1 at 0. 633 μm wavelength. The Bohzmann＇s coefficients of these crystals were calculated, which were in good agreement with earlier measurement in other reference.

Molten salt synthesis of neodynium oxyfluoride in various fluoride media with different fluoride ion activities

Neodymium oxyfluoride has received much attention in the fields of anionic solid electrolytes.luminescent,catalytic and magnetic materials because of its structure combined advantages of rareearth cations with F^(-)and O_(2)^(-)anions.In this work,neodynium oxyfluoride was synthesized by the reaction between neodymium oxide and four fluoride media with different fluoride ion activities.The synthesis processes in molten LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),NaF-CaF_(2)-NdF_(3)and NaF-KF-NdF_(3)are observed in situ by a confocal scanning laser microscope.The expansion of neodymium oxide particle is observed in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts,and the growth of needle crystals on neodymium oxide particle is clearly observed in molten NaF-CaF_(2)-NdF_(3).Based on scanning electron microscopy(SEM)-energy dispersive X-ray spectroscopy(EDS)and X-ray diffraction(XRD)analyses of products,neodynium oxyfluoride was successfully synthesized in the four fluoride media.The neodynium oxyfluoride generated in the LiF-CaF_(2)-NdF_(3),LiF-NdF_(3),and NaF-KF-NdF_(3)melts is a tetragonal structure.However,in molten NaF-CaF_(2)-NdF_(3),neodynium oxyfluoride with a rhombohedral structure is formed.It is suggested that the substitution of Na(Ⅰ)and Ca(Ⅱ)for Nd(Ⅲ)can transform NdOF from tetragonal structure to rhombohedral structure.The growth rate of needle crystals generated in molten NaF-CaF_(2)-NdF_(3)was calculated based on the result of a confocal scanning laser microscope,and it is found that the reaction kinetics of crystal formation is zero-order reaction.The effect of fluoride media on the structure and morphology of formed NdOF were evaluated by XRD,X-ray photoelectron spectroscopy(XPS)and SEM.The neodymium oxyfluoride prepared in the fluoride media with high fluoride ion activity has low binding energy of F 1 s.The ratio of adsorbed oxygen to lattice oxygen for neodymium oxyfluoride prepared in molten LiF-NdF_(3)is larger than those in the other three fluoride media,so it can have better catalytic performance.

稀土(钇)对钨钼原子扩散系数的影响

利用双辉等离子表面冶金技术在Q235钢表面渗稀土(钇)钨钼形成共渗合金层。通过对渗层合金元素的分布进行分析,计算出钨钼原子的扩散系数和扩散激活能来分析稀土(钇)的加入对钨钼原子扩散产生的影响。结果表明:稀土(钇)的加入使钼原子在渗层中的扩散系数平均增大1.89倍。钨原子的扩散系数平均降低了0.89倍。稀土(钇)的加入使钼原子在渗层中离表面12～15,24～25,35～36μm处钼原子扩散激活能分别降低了5737.72,6511.72,7853.38J/mol。钨原子扩散激活能提高了998.5,106.37,2904.56J/mol,稀土(钇)对钼原子具有催渗作用,对钨原子没有明显催渗作用。

等离子钨、钼和钇共渗时钇原子对渗层的交互作用

利用双层辉光等离子渗金属技术，在20号钢表面进行钨．钼一钇和钨．钼共渗，并获得合金渗层。利用扫描电镜（SEM）和能谱仪（EDS）进行微观组织分析和成分分布检测，用x射线衍射仪（XRD）进行结构分析，用Fick第二扩散定律分别计算上述二元共渗和三元共渗渗层的钨、钼扩散系数以及扩散激活能。研究表明：钨-钼-钇和钨-钼共渗渗层组织均为柱状晶，渗层与基体之间有一条分界线。稀土钇的加入细化了渗层的组织；钨．钼．钇共渗层物相主要为：Fe（W，Mo，Y），Fe3Mo，Fe17Y2，W，Y等；钨一钼共渗渗层物相主要为：Fe（w，Mo）；钇的加入使渗层中钼在距表面12～15，24～25，35～36μm处的扩散系数分别提高了1．72，1．85，2．10倍，平均增大1．89倍。而钨原子的扩散系数在加入稀土元素后减小了0．92，0．99，0．76，平均降低了0．89倍；稀土钇的加入降低了钼原子的扩散激活能，说明了稀土钇对钼具有催渗作用，但对钨没有催渗作用。