Effect of electrolysis voltage on electrochemical reduction of titanium oxide to titanium in molten calcium chloride

The electrochemical reduction of solid TiO2 directly to solid metal is a promising alternative to the current Kroll process. The present work is aimed at studying the effect of electrolysis voltage on the rate of electrochemical reduction. The products of electrochemical reduction of TiO2 and Ti2O were examined using the scanning electron microscopy （SEM） and X-ray diffraction （XRD） techniques. The results show that Ti2O was reduced to low valent titanium oxide at 1.5 -1.7 V, which was the result of ionization of oxygen. TiO2 and Ti20 were reduced to titanium metal at 2.1-3.1 V, which was the co-action of ionization of oxygen and calciothermic reduction. The oxygen content decreased rapidly with voltage increasing from 2.1 to 2.6 V, while it changed little from 2.6 to 3.1 V. The optimized cell voltage was 2.6-3.1 V.

Effect of fluoride ions on coordination structure of titanium in molten NaCl–KCl

The effects of fluoride ions(F^(-)) on the electrochemical behavior and coordination properties of titanium ions(Ti^(n+)) were studied in this work,by combining electrochemical and mathematical analysis as well as spectral techniques.The α was taken as a factor to indicate the molar concentration ratio of F^(-) and Ti^(n+).Cyclic voltammetry(CV),square wave voltammetry(SWV),and open circuit potential method(OCP)were used to study the electrochemical behavior of titanium ions under conditions of various α,and in-situ sampler was used to prepare molten salt samples when α equal to 0.0,1.0,2.0,3.0,4.0,5.0,6.0,and 8.0.And then,samples were analyzed by X-ray photoelectron spectroscopy(XPS) and Raman spectroscopy.The results showed that F^(-) in molten salt can reduce the reduction steps of titanium ions and greatly affects the proportion of valence titanium ions which making the high-valence titanium content increased and more stable.Ti^(2+) cannot be detected in the molten salt when α is higher than 3.0 and finally transferred to titanium ions with higher valence state.Investigation revealed that the mechanism behind those phenomenon is the coordination compounds(TiCl_(j) F_(i)^(m-)) forming.

Electrochemical reduction mechanism of Zn^(2+)in molten NaCl-KCl eutectic

A process comprising selective chlorination and molten salt electrolysis was proposed to develop an efficient and environmental-friendly technology for zinc recovery from metallurgical dusts.The theoretical feasibility of this technology was firstly estimated based on thermodynamic fundamentals.Subsequently,the electrochemical behavior of Zn^(2+)on tungsten electrode was investigated in molten NaCl-KCl eutectic at 973 K by many electrochemical transient methods.The results showed that the reduction of Zn^(2+)on tungsten electrode was found to be a one-step process exchanging two electrons with the initial reduction potential of-0.74 V(vs Ag/AgCl),and the electrode process was considered as quasi-reversible and controlled by diffusion.The diffusion coefficient of Zn^(2+)ions in the melts was determined in the order of 10^(-5)cm^(2)/s.Finally,the electrolytic preparation of zinc was carried out by potentiostatic electrolysis in molten NaCl-KCl-ZnCl_(2)eutectic at-1.6 V(vs Ag/AgCl).Spheroidic granular metal with silver-white luster was attained after electrolysis for 9.5 h,and identified as pure Zn.The present study confirms that it is practically feasible to extract pure zinc metal by direct electrolysis of ZnCl_(2)in molten NaCl-KCl eutectic,and provides a valuable theoretical reference for the efficient recovery of zinc from metallurgical dusts.

Electrochemical Reduction of Niobium lons in Molten NaF-CaF_2

The mechanism of the electrochemical reduction of niobium ions in molten NaF-CaF_2 (2 : 1 mol) wasinvestigated by means of cyclic voltammetry and chronoamperometry. It is found that the reduction ofNb ( V ) proceedsintwosteps : Nb ( V)→ Nb (Ⅳ)→Nb ( 0 ) . Theelectrochmical reaction Nb ( Ⅳ) + 4e →Nb( 0 ) is a reversible and diffusion-controlled process.

Electrochemical Reduction of Yttrium Ions

The cathodic electrode process of Y^(3+) ions on the Mo electrode in the LiCl-KCl molten salt with YCl_3(3wt%) in the temperature range of 450～530℃ has been investigated using cyclic voltammetry and chronopotentiometry.The convolution technique has been applied to the treatment of cyclic voltammogram.The results show that the reduction mechanism of Y^(3+) ion is Y^(3+)+3e=Y,a simple one-step process.The cathodic process is very close to a reversible process under lower scanning rates,and is diffusion-controlled.The cathodic product is an insoluble product.

Effect of fluoride addition on electrochemical behaviors of V(Ⅲ) in molten LiCl-KCl

X-ray photoelectron spectroscopy(XPS)and Raman spectroscopy were used to analyze the complexes in LiCl−KCl eutectic salt containing VCl_(3) and KF.The additional fluoride ions would replace chloride ions and combine with V(Ⅲ)to form VF_(6)^(3-).The electrochemical behavior of V(Ⅲ)was evaluated under condition of the molar concentration ratio of F−to Vn+(α)equal to 0:1,1:1,2:1,5:1,20:1 and 50:1,respectively.The results showed that a new reduction step appeared:VF_(6)^(3-)→V^(2+),and the reduction mechanism of vanadium ions became more complicated.The metallic vanadium was deposited on the tungsten electrode at−2.90 V in the LiCl−KCl melts for 6 h,and the products were characterized by SEM−EDS.It was indicated that the particle size of the product decreased with adding fluoride ions for the forming of the coordination compound VF_(6)^(3-).

Pure metal extraction from molten oxide slag by short-circuit galvanic cell

The oxygen-ion-permeable membrane galvanic short-circuit method has been developed, in which pure metal was directly extracted from the molten oxide slag, and no external voltage is applied. The galvanic cell employed in the experiment was as follows: graphite rod|[O]Fe+C saturation|ZrO2(MgO)|(FeO)(slag)|Fe rod. The reduction current in the galvanic cell consisted of an external short-circuit current and an interior short-circuit current in the oxygen-ion-permeable membrane. The real-time variation of external circuit reduction ratio of the molten slag could be obtained from the curve of the external circuit current to the time.

Pure metal extraction from molten oxide slag by short-circuit galvanic cell

The oxygen-ion-permeable membrane galvanic short-circuit method has been developed, in which pure metal was directly extracted from the molten oxide slag, and no external voltage is applied. The galvanic cell employed in the experiment was as follows: graphite rod|[O]_(Fe+C saturation)[ZrO_2(MgO)|(FeO)_(slag))|Fe rod. The reduction current in the galvanic cell consisted of an external short-circuit current and an interior short-circuit current in the oxygen-ion-permeable membrane. The real-time variation of external circuit reduction ratio of the molten slag could be obtained from the curve of the external circuit current to the time.

Study on Mechanism of Electrodeposition of Y(Ⅲ) in Molten LiF-YF_3-Y_2O_3 by Cyclic Voltammetry

The mechanism of the cathodic process of Y(Ⅲ) on platinum and molybdenum electrode in molten LiF YF 3 Y 2O 3 was investigated by means of cyclic voltammetry. The number of electron transferred was calculated. The results show that the electrochemical reduction of Y(Ⅲ) is a reversible one step three electrons reaction and the cathodic process is diffusion controlled. The reductive product easily forms the intermetallic compounds with the platinum electrode, but it is pure yttrium on the molybdenum electrode.

Cathodic Process of Ti(Ⅳ) in Molten LiF-NaF

The mechanism of the cathode reduction of Ti(Ⅳ) at platinum electrode in molten LiF-NaF containingvarious concentrations of K_2TiF_6 has been investigated by means of cyclic voltamrnetry and convolutiontechnique. The transfered electron number of each reduction step has been determined. It is found that thereduction of Ti(Ⅳ) proceeds in three steps: Ti(Ⅳ)→Ti(Ⅲ)→Ti(Ⅱ)→Ti(0). The first step is accompanied bythe chemical disproportionation reaction: ZTi(Ⅲ)→Ti(Ⅳ)+Ti(Ⅱ). The cathodic product is soluble and prob-ably forrns alloy with the platinurn electrode.

氟化物熔体中电解共沉积硼化钛的阴极过程

采用循环伏安法首次研究了ＬｉＦ－ＮａＦ－Ｋ２ＴｉＦ６－ＫＢＦ４熔盐体系中钛离子和硼离子在铂、钼电极上电化学还原及电合成硼化钛的阴极过程机理。对恒电位电解的沉积物进行了Ｘ射线衍射分析。结果表明，当体系中硼钛摩尔比Ｂ／Ｔｉ大于２时，钛与硼可在同一电位下实现电解共沉积并反应生成硼化钛。

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）在铂电极上阴极还原机理，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。

氧化物熔渣的电化学还原

提出了一种从氧化物熔渣中直接提取金属的电化学方法,即采用氧离子渗透膜原电池短路法,用碳作还原剂,在CaO SiO2 Al2O3 FeO熔渣中,利用阴极合金化原理,获得无碳铁合金。结果表明:在本实验条件下,熔渣中FeO浓度越高,外电路短路电流越大。发现熔渣的还原电流包括外电路短路电流和氧离子膜的内部短路电流,可利用外电路短路电流来监测熔渣的外电路还原率。

LiF-NaF-KF-K_2TiF_6熔盐中Ti(IV)的电化学还原及电结晶过程(英文)

采用循环伏安法和计时电流法研究了700℃时LiF-NaF-KF-K2TiF6熔盐中Ti(IV)在铂电极上阴极电化学还原机理以及电结晶过程。结果表明:Ti(IV)的电化学还原机理为三步骤电荷传递反应:Ti(IV)+e→Ti(III);Ti(III)+2e→Ti(I);Ti(I)+e→Ti(0),且阴极过程可逆;电结晶过程为瞬时形核。

熔盐体系中电沉积制备TiB_2镀层的研究现状

介绍了熔盐体系中电沉积制备TiB2镀层技术中熔盐的选择、电镀工艺和参数的选择,概述了不同熔盐体系中B离子、Ti离子在阴极沉积的电化学机理以及TiB2的合成机理,论述了TiB2惰性阴极在铝电解工业中的研究现状,最后分析了熔盐体系中石墨电极上制备TiB2镀层的可行性。

LiF-NaF-KF-K_2TiF_6-KBF_4熔体中电沉积TiB_2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。

Ti(Ⅳ)在氯化物熔体中的电化学还原

研究了ＫＣｌＬｉＣｌ熔体中Ｔｉ（Ⅳ）的电化学还原机理和钛沉积及沉积动力学，计算了各还原步骤传递的电子数。结果表明，Ｔｉ（Ⅳ）的电化学还原为三步电荷传递反应，即：Ｔｉ４＋→Ｔｉ３＋→Ｔｉ２＋→Ｔｉ。Ｔｉ（Ⅳ）的电化学还原速度由离子扩散速度来控制。在一定熔体组成及温度下，沉积物的性质依赖于电解时间及电解电位。在ＫＣｌＬｉＣｌ熔体中阴极电位为５００ｍＶ（相对钼电极），电解时间为４ｈ时，可获得粘附性能好的钛沉积物，并观察到沉积物为细小结晶堆积起来的多孔体。钛的纯度可达９９．９％。

氟离子对2种牙科用钛合金耐腐蚀性的影响

目的在模拟口腔环境下,探讨氟离子对Ti-12Zr合金和Ti-6Al-4V合金耐腐蚀性的影响。方法 2种钛合金在含有不同浓度NaF(0%、0.05%、0.1%、0.2%)的酸性人工唾液(pH=4.0)电解池中测得极化曲线;然后将试件浸泡于恒温的实验溶液中,扫描电镜(SEM)下观察各组试件的表面形貌。结果 2种钛合金在酸性人工唾液中的自腐蚀电位、极化电阻随着NaF浓度的升高而减小,自腐蚀电流密度随着NaF浓度的升高而增大;且当NaF浓度高于0.1%时2种钛合金的自腐蚀电位、极化电阻以及自腐蚀电流密度的变化明显(P<0.05);同时,扫描电镜结果显示当NaF浓度高于0.1%时2种钛合金表面开始发生严重的腐蚀;Ti-12Zr合金在NaF浓度为0.2%酸性人工唾液中的极化电阻明显高于Ti-6Al-4V合金(P<0.05)。结论氟离子可降低Ti-12Zr合金及Ti-6Al-4V合金的耐腐蚀性,且在NaF浓度高于0.1%时更为明显。

Ti35合金在含氟离子硝酸中电化学腐蚀行为（英文）

采用电化学测试系统测试了Ti35合金在含有不同氟离子浓度的6mol/L硝酸溶液中的开路电位(OCP)、极化曲线、电化学阻抗谱(EIS),探讨了氟离子对Ti35合金耐蚀性能的影响。结果表明:随着氟离子浓度的增加,合金耐蚀性下降,但总体而言合金仍具有良好的耐蚀性。影响合金耐蚀性转变的氟离子浓度临界值约为1.25 mmol/L,进一步应用混合电位理论,解释合金耐蚀性转变的原因。