NaCl-KCl-IrCl3熔盐体系中电沉积Ir层的机理（英文）

在NaCl-KCl-IrCl3熔盐体系中利用循环伏安法和计时电位法研究Ir的沉积机理并通过恒电位法在Pt基体上制备出Ir层。利用扫描电子、显微镜(SEM)能谱仪(EDS)和X射线衍射仪(XRD)对Ir层的表面形貌和成分进行分析。结果表明:在NaCl-KCl-IrCl3熔盐体系中Ir的电沉积过程为Ir3+获得3个电子一步沉积为Ir,并且Ir(Ⅲ)→Ir(0)的电极反应过程为可逆扩散控制过程;在1063、1113、1143和1183K下Ir(Ⅲ)离子的扩散系数分别为0.60×10-4、1.23×10-4、2.77×10-4和4.40×10-4cm2-s,Ir(Ⅲ)在NaCl-KC-IrCl3熔盐体系中电极反应的活化能Ea=162.61kJ/mol;沉积电位对所获得的Ir层的形貌有较大影响,其中在峰值电位下所获得的Ir层较厚;熔盐温度对电沉积Ir层的形貌也有较大影响,在较低熔盐温度下获得的Ir层较薄,较高熔盐温度获得的Ir层的孔隙较多。     

LiCl-KCl-MgCl2-Gd2O3熔盐共电沉积制备Mg-Li-Gd合金（英文）

在823K和973K的条件下,采用恒电流密度共电沉积法在LiCl-KCl-MgCl2-Gd2O3熔盐体系中制备Mg-Li-Gd合金,并运用XRD、SEM、EDS和OM对所制备合金进行微观组织分析。结果表明:在开始的30min内,主要是Mg和Gd的沉积,所得合金含96.53%Mg,3.20%Gd和0.27%Li(质量分数),然后Li迅速沉积。可以通过控制电解时间或改变Gd2O3的浓度调节Mg-Li-Gd合金的组成。XRD分析可知,在Mg-Li-Gd合金中存在Mg3Gd相和Mg2Gd相。从Gd元素的面扫描分析可知,Gd元素主要分布在Mg-Li-Gd合金的晶界处。Gd的添加增强了合金的抗腐蚀能力。     

LiF—NaF—K2TiF6熔盐中Ti（Ⅳ）的电化学还原

用循环伏安法和卷积技术研究了ＬｉＦ－ＮａＦ低共熔体中，以Ｋ２ＴｉＦ６形式加入的Ｔｉ（Ⅳ）在铂电极上钥极还原机理，计算了各还原步骤所传递的电子数。结果表明：Ｔｉ（Ⅳ）的电化学还原机理为耦联均相歧化反应的三步骤电荷传递反应。     

氧化钪在nNaF.AlF3-ScF3熔盐体系中的溶解

通过三因子三水平正交实验设计，研究了Sc     

NaCl-KCl共熔盐中Zn2+的电化学还原机理(英文)

为了开发高效、环境友好型冶金粉尘中锌回收技术,提出一种将选择性氯化和熔盐电解相结合的工艺。首先,通过热力学论证上述处理工艺的理论可行性。然后,采用多种暂态电化学测试方法研究973K时NaCl-KCl共熔盐中Zn²⁺在钨电极上的电化学行为。结果表明,Zn²⁺的还原过程是一步转移2个电子的反应,起始还原电位为-0.74 V(vs Ag/AgCl);且为受扩散控制的准可逆过程,计算得到Zn²⁺的扩散系数为10^-5cm²/s数量级。最后,在NaCl-KCl-ZnCl₂熔盐中于-1.6 V (vs Ag/AgCl)进行恒电位电解,电解9.5 h、后获得银白色类球状金属颗粒,经分析证实为金属Zn。本研究表明,在NaCl-KCl共熔盐中直接电解ZnCl₂提取金属锌是可行的,为冶金粉尘中锌的高效回收提供了有益的理论参考。     

Pb(Ⅱ)在LiCl-KCl-MgCl_2-PbCl_2熔盐体系中的电化学行为(英文)

在LiCl-KCl-PbCl2-MgCl2熔盐体系中借助循环伏安和计时电位技术对Pb(Ⅱ)的电化学行为以及Pb、Mg、Li的共沉积过程进行探讨,用不同的方法测算得到铅离子在熔盐中的扩散系数。循环伏安和计时电位的研究结果均表明,Li在先析出的Pb上发生欠电位沉积,生成液态的Li-Pb合金,而在熔盐中加入MgCl2后,会有相应的Mg-Li-Pb合金生成。用恒电流密度(6.21A/cm2)电解2h制备Mg-Li-Pb合金,并运用XRD对所得合金进行分析测试。结果表明,在Mg-Li-Pb合金中存在β-Li、PbLi3、Mg2Pb等合金相,并可以通过控制熔盐中PbCl2和MgCl2的浓度来改变合金相的组成。     

TiB2涂层熔盐电沉积制备与表征

炭阴极在铝电解槽中受熔盐和铝液腐蚀而影响寿命,而TiB₂涂层是铝电解槽理想的阴极材料。本文以石墨为基体,在KF-KCl-K₂TiF₆-KBF₄熔盐中以0.4-0.7A.cm_-2^{电流密度、}700-800℃温度电沉积TiB₂涂层,通过XRD衍射仪、SEM-EDS、表面粗糙度测量仪及附着力测试仪对不同电流密度和温度下制备的涂层进行表征。结果表明：在石墨基体上可以得到均匀连贯的TiB₂涂层;增大电流密度、降低电解温度可以细化涂层晶粒,提高涂层致密性;在0.6 A.cm_-²、750℃最优电沉积条件下制得的TiB₂涂层的厚度为229 μm,择优取向为<110>,表面粗糙度为14.85 μm,涂层与石墨基体的结合力为6.39 MPa。     

铝在NaCl－AlCl_3熔盐体系中的电化学沉积

采用循环伏安法研究了铝在融熔氯化钠—氯化铝体系中的阴极电化学沉积过程。在碱性熔体中阴极还原质点为ＡｌＣｌ４在酸性熔体中还原质点为Ａｌ２Ｃｌ７，而ＡｌＣｌ４通过溶剂平衡反应来影响铝的沉积过程。Ａｌ２Ｃｌ７的还原反应是准可逆的，反应机理复杂，可能是前置化学步骤或自催化反应。     

CeO2在CeF3–LiF–BaF2熔盐中的溶解过程及电化学行为研究

本文研究了CeO₂在CeF₃–LiF–BaF₂熔盐中的溶解机理,并采用钼金属电极研究了生成的Ce(III)在CeF₃–LiF–BaF₂熔盐中的电化学行为。通过循环伏安曲线、计时电流法、恒电位电解法研究了Ce(III)的电解还原机理,并采用XRD、SEM、EDS对溶解反应产物和电解产物进行了物相、成分和微观组织分析。结果表明：CeO₂通过可与CeF₃反应生成CeOF进而溶解于CeF₃–LiF–BaF₂熔盐中,CeOF可被直接电解还原生成金属Ce,Ce(III)在Mo电极上的电化学反应是一个单步的三电子可逆过程,反应受扩散控制。     

Electrochemical co-deposition of magnesium based alloy from molten salts

Magnesium based alloys with aluminum and zinc were obtained through electrochemical co-deposition from LiCl-NaCl-MgCl2 melt. The possibility of electrochemical co-deposition was discussed in detail by electro-analytical methods including cyclic voltametry, square wave voltametry, and chronopotentiometry. The co-deposition happens when the concentration of aluminum and zinc ions is kept at low value and the current density is high enough. The components of alloy elements can be controlled by fixing the components of the feeding salts. A laboratory experiment of the preparation by step-current co-deposition was also performed and certain compositions of the Mg-Al, and Mg-Zn were obtained. The alloys obtained from the co-deposition show a typical as-cast microstructure. The best conditions of electrolysis such as temperature, amount of addition and mode of feeding were discussed in detail.     

Electrochemical production of Sn-filled carbon nanotubes in molten salts

Sn-filled carbon nanotubes(CNTs) were prepared in situ by electrolysis of graphite in molten LiCl/SnCl2 mixtures. Transmission electron microscopy(TEM) investigation shows that the as-made products contain abun-dance of carbon nanotubes and most of them are filled with metal nanoparticles or nanorods. Some nanotubes are e-ven inserted with long continuous nanowires more than several micrometers in length. Selected area electron diffrac-tion(SAED) patterns and energy dispersive X-ray spectroscopy(EDS) of the filled nanotubes confirm the presence of Sn inside the nanotubes. The encapsulated Sn was further identified as β-Sn with tetragonal structure. Based on the experimental results, a possible growth mechanism of the Sn-filled nanotubes was also discussed.     

氧化钪在nNaF·AlF_3ScF_3熔盐体系中的溶解

通过三因子三水平正交实验设计, 研究了Ｓｃ２Ｏ３ 在ｎＮａＦ·ＡｌＦ３ＳｃＦ３ 熔盐体系中的溶解度与熔盐成分及温度的关系。结果表明, 冰晶石的分子比与ＳｃＦ３ 的含量是影响溶解度的主要因素,ＳｃＦ３ 含量的增加与分子比的降低有利于Ｓｃ２Ｏ３ 的溶解。随温度的升高,Ｓｃ２Ｏ３ 的溶解度增大, 但温度影响显著性相对较小。在冰晶石分子比为２ ．１ 、ＳｃＦ３ 含量９ ％ 时,Ｓｃ２Ｏ３ 的溶解度可达５ ％ 以上。     

Na2WO4-WO3-ZnO体系熔盐镀钨

对Ｎａ２ＷＯ４－ＷＯ３－ＺｎＯ体系熔盐镀钨工艺进行了详细研究,得到了获得金属钨镀层的工艺条件。结果表明：在空气气氛中,当氧化钨的浓度为１５％～３０％时,于８５０～９５０℃能得到金属钨镀层且镀层表面平整;当其它条件都相同时,在铜基体上获得钨镀层比钼基体上所需的温度略高一些;扫描电镜照片显示钨镀层与钼基体之间有明显分界面,元素线扫描结果证实镀层与钼基体间扩展层厚度仅为２．５μｍ,基本不形成扩散层;不同     

Preparation of TiB2 coatings by electroplating in molten salt

Titanium diboride （TIB2） coatings were prepared by electroplating in fluoride-chloride electrolytes （KF-KC1） containing K2T1F6 and KBF4 as the electrochemically-active components. An attempt was made to correlate the thermodynamic prediction and experimental observations. Thick, adherent, and uniform TtB2 coatings were obtained and the coating microhardness reaches the value of 33 GPa. The effects of the current density on the mechanical properties, structures, and morphologies of the coatings were studied. XRD analysis indicates that the preferred orientation of the coatings is （001）, which is in accordance with the prediction of the two-dimensional crystal nuclei theory. Thermodynamic prediction and experimental results show that some phases such as TixCy and BaCb are absent at the interface, which indicates the substrate and coatings bind mechanically or physically. Some cracks exist at the interface, which is attributed to the difference between the coefficients of thermal expansion of TiB2 and graphite.     

Correlation between molten vanadium salts and the structural degradation of HK-type steel superheater tubes

HK steels are among the most used heat-resistant cast stainless steels, being corrosion-resistant and showing good mechanical properties at high service temperatures. These steels are widely used in reformer furnaces and as superheater tubes. During service, combustion gases leaving the burners come in contact with these tubes, resulting in corrosive attack and a large weight loss occurs due to the presence of vanadium, which forms low melting point salts, removing the protective oxide layer. In this work the external surface of a tube with dramatic wall thickness reduction was analyzed using light microscopy, scanning electron microscopy, and transmission electron microscopy. The identification of the phases was achieved by energy dispersive spectroscopy (EDS) analyses. The results showed oxides arising from the external surface. In this oxidized region vanadium compounds inside chromium carbide particles were also observed, due to inward vanadium diffusion during corrosion attack. A chemical reaction was proposed to explain the presence of vanadium in the metal microstructure.     

镁合金表面新颖多层的耐腐蚀Mg-Al金属间化合物涂层(英文)

通过AlCl3-NaCl熔盐扩散表面改性,在镁合金表面制备多层的Mg-Al金属间化合物层。熔盐扩散的处理温度为400 °C,此温度低于纯铝粉扩散的处理温度。熔盐扩散处理后,在镁合金表面形成 Al12Mg17、Al0.58Mg0.42和Al3Mg2多相层的金属间化合物涂层。通过电化学阻抗实验将表面改性和未经表面改性的镁合金的耐蚀性进行比较,发现镁合金表面经过熔盐扩散处理的极化电阻远大于未经表面改性镁合金的。这是因为在镁合金表面形成均匀的多相金属间化合物层。     

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.     

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.     

LiF-NaF-KF-K2 TiF6-KBF4熔体中电沉积TiB2的阴极过程

采用循环伏安法研究了700℃时46.5LiF-11.5NaF-42KF(摩尔分数,%)熔盐中Ti(Ⅳ)(c(K2TiF6)=0.2 mol/L)和B(Ⅲ)(c(KBF4)=0.4 mol/L)在铂电极上的电化学还原机理,计算了各还原步骤传递的电子数。研究了LiF-NaF-KF-K2TiF6-KBF4(c(K2TiF4)=0.3 mol/L,c(KBF4)=0.3,0.6,0.9 mol/L)熔盐中电化学合成TiB2的阴极过程机理。结果表明:Ti(Ⅳ)的电化学还原为三步电荷传递反应,且阴极过程近似可逆;B(Ⅲ)在铂电极上的电化学反应机理为简单的三电子一步反应,阴极过程近似可逆;Ti(Ⅳ)和B(Ⅲ)可在同一电位下发生共沉积并反应生成TiB2。