Developing and studying the properties of Pb–TiO2 alloy coated lead composite anodes for zinc electrowinning

Abstract

A new anodic material for zinc electrowinning from sulphate electrolytes has been developed. This is a lead–titanium alloy coated lead composite electrode containing titanium nanoparticles. The titanium is present in the lead matrix as n-type TiO₂. It has been established that the optimal content of the Ti in the composite coatings is about 0·5 wt-%. The behaviour of the lead–titanium anodes during the zinc electrowinning has been studied by means of galvanostatic polarisation investigations. The depolarising of the anodic reaction at lead–titanium composite electrodes is attributed to the increased anode area during continued polarisation. The processes occurring on the lead–titanium anodes during zinc electrowinning have been studied by cyclic voltammetry. The surface morphology of the composite lead–titanium electrodes was investigated by scanning electron microscopy.     

阳极氧化法制备TiO2膜在模拟深海热液区的耐腐蚀性能

以恒压阳极氧化方法在钛基体上制备TiO₂氧化膜,使用水热釜模拟深海热液区的条件研究其耐腐蚀性能。采用XRD、SEM、接触角测定仪对氧化膜以及腐蚀试样产物进行晶型、表面结构、化学成分和亲疏水性能测定,使用动电位扫描方法对其进行极化曲线测试。结果表明,钛试样和阳极氧化钛试样在模拟深海环境条件下,经过腐蚀反应在表面都生成了一层非致密的TiO₂ 膜,对基体并不能起到保护作用,而阳极氧化生成的致密TiO₂ 膜对基体能够起到很好的保护作用。经腐蚀后钛试样表面有TiH₂相的形成,腐蚀电位负移0.45 V。而阳极氧化钛试样表面没有TiH₂相的形成,且腐蚀电位负移较小,表现出良好的耐腐蚀性能。     

Anodic Behavior of a Titanium–Aluminum Hybrid Electrode: Formation of Hydroxide-Oxide Compounds

The electrochemical behavior of a titanium–aluminum hybrid electrode in aqueous solutions of electrolytes containing halide ions (F^– and Cl^–) was studied. The effects of current density, solution composition, and ratio of the working surface area of titanium and aluminum on the anodic dissolution rate of a Ti?Al hybrid electrode and its electrochemical characteristics were revealed. The joint anodic dissolution of aluminum and titanium in the aqueous media under study made it possible to obtain precursors of the highly disperse oxide system Al₂O₃–TiO₂. Data of X-ray and electron-microscopic analysis confirmed the results obtained.     

Electrochemical stability of anodic titanium oxide films grown at potentials higher than 3 V in a simulated physiological solution

The cathodic behaviour of oxides formed on titanium electrodes in physiological solutions at potentials between 3 and 5 V (vs. SCE) was studied by cyclic voltammetry. In case of anodic polarization at potentials higher than 3 V (vs. SCE), a cathodic peak at ∼0.4 V (vs. SCE) appears in the cathodic scan, which could be due to the reduction of unstable peroxides. The results show that this peak depends on the anodic potential and the oxidation time. This behaviour supposedly is due to the formation of unstable titanium peroxides like TiO₃ during anodization. Based on repetitive oxidation-reduction processes can be concluded that the created amount of TiO₃ inside of the TiO₂ surface layer seems to be constant.     

Preparation of titanium dioxide nanotube arrays on titanium mesh by anodization in (NH4)2SO4/NH4F electrolyte

The self‐organized titanium dioxide (TiO₂) nanotube arrays on titanium mesh were prepared by electrochemical anodization with the neutral electrolyte containing ammonium sulfate and ammonium fluoride in a two‐electrode electrochemical cell. The effects of the fluoride ion concentration, the anodic potential, and the oxidation time on the formation of the titanium dioxide nanostructures on titanium mesh with complex geometry were investigated. The anodized titanium mesh was characterized by field emission scanning electron microscope and in situ high temperature X‐ray diffraction. The results show that the titanium dioxide nanotube arrays are grown in a radially outward direction around the titanium wire. The optimized anodization condition for preparing titanium dioxide nanotube arrays with superior architecture on the titanium mesh is 0.5 wt% of ammonium fluoride, 20 V of applied potential, and 20 min of oxidation time. The amorphous titanium dioxide nanotubes on titanium mesh turn to anatase phase at 400 °C and further to rutile phase at 650 °C.     

Plasma-electrolytic oxidation of titanium in Zr(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>-containing electrolyte

It is shown that anodic oxide coatings with a thickness of several to 300 νm can be obtained on titanium by varying the charge spent on (Q). The prevailing phase in the coatings is ZrO₂ in monoclinic and tetragonal modifications. The content of zirconium in the layers is up to 20 at %. Distributions of titanium, zirconium, and oxygen in the cross sections of the coatings are obtained, and the effect of Q on the formation and elementary and phase compositions of the coatings is studied. Tentative experiments clarifying the effects of bipolar anodic-cathodic polarization and electrolyte aging on the composition of coatings are carried out. The coatings are shown to be stable at temperature variations in the range of 20–700°C and to decrease the contact corrosion current at the (titanium + coating)—St3 steel interface by a digit of 10–15 in 3% NaCl.     

Anodic Spark Coatings on Titanium and АМцМ Alloy from Baths Containing Aluminum Polyphosphate Complexes

The effect of the concentration of aluminum oxalate in an aqueous electrolyte containing sodium hexametaphosphate on the elemental and phase composition of the resulting coatings was studied with the use of ²⁷Al NMR spectroscopy, x-ray diffraction, and x-ray spectral analysis. With an increase in the concentration of Al₂C₆O₁₂ · nH₂O, the content of aluminum in surface films grows on titanium and descends on the aluminum alloy. The coatings become enriched with the crystalline AlPO₄ phase. The results obtained confirm that the components of an electrolyte penetrate into anodic layers via high-temperature thermolysis of hydrated aluminum polyphosphates in the near-channel zone of electrical breakdowns.     

Corrosion Resistance of Titanium Palladized by Electro-Sparking with Subsequent Anodic Plasma-Heating in Aqueous Electrolyte

The effect of anodic heating in electrolytic plasma (AHEP) on the corrosion and electrochemical behavior of titanium with electro-spark palladium coatings in 10–40% H₂SO₄ solutions at 100°C is studied. It is shown that the treatment by the AHEP method enhances the corrosion resistance of palladized titanium by more than one exponent. This is due to the formation of palladium-containing oxide–carbide layers.     

Characterisation of anodic oxide films formed on titanium and two ternary titanium alloys in hydrochloric acid solutions

The purpose of this paper is to characterise the anodic oxide films formed on titanium and two ternary titanium alloys, Ti‐15Mo‐5Al and Ti‐10Mo‐10Al in 1%, 10% and 20% hydrochloric acid solutions at 25, 50, and 75°C. The anodic film on titanium in hydrochloric acid is stable between + 0.6 V (SCE) and + 2.0 V (SCE). For our new ternary titanium alloys, the passive film is formed at about + 0.6 V (SCE) and is stable to + 2.0 V (SCE). The anodic polarization curves for alloys differ from the base metal curve, presenting two peaks for the critical passivation current density in the active‐passive potential range. At the first current peak (the first critical passivation potential E_cr1) a porous titanium pentaoxide (Ti₃O₅) is formed. When the potential reaches the second current peak (the second critical passivation potential E_cr2) the compact and protective titanium dioxide (TiO₂) is formed. The impedance spectra exhibit the typical behaviour for a passive film i.e. a near capacitive response illustrated by a phase angle close to − 90 ° over a wide frequency range. The oxide film on titanium and its alloys in hydrochloric acid solutions exhibits a high resistance and a low capacitance (with the increase of the potential) attributed to the surface roughness decrease as the oxide layer thickens.     

Anodic plasma electrolytic nitrocarburising of VT22 titanium alloy in carbamide and ammonium chloride electrolyte

The structure of alpha- and beta-titanium alloy VT22, its microhardness, surface roughness, wear and corrosion resistance after anodic plasma electrolytic nitrocarburising in an electrolyte containing carbamide and ammonium chloride were investigated. An X-ray diffractometer and a scanning electron microscope were used to characterize the phase composition and structure of the modified surface. Tribological properties of the treated titanium alloy were evaluated using a ball-on-disc tribometer under lubricated testing conditions. The effect of processing temperature on corrosion resistance of the plasma electrolytic nitrocarburising samples was examined by means of potentiodynamic polarization in Ringer’s solution. It was shown that the anodic nitrocarburising provides saturation of the titanium alloy with oxygen, nitrogen and carbon and the formation of TiO₂ with a rutile structure and a nitrogen/carbon solid solution in titanium. The anodic plasma electrolytic nitrocarburising at all treatment temperatures diminishes the wear rate of the titanium alloy samples and the surface roughness. Friction coefficient of treated samples can be reduced by 4.7 times. The anodic nitrocarburising results in an enhanced corrosion resistance since the corrosion potential increases by an order of magnitude.     

Inhibition of the acid corrosion of iron with triphenyl tetrazolium chloride

The efficiency of 2, 3, 5-triphenyl tetrazolium chloride (TTC) as an inhibitor for acid corrosion of hot-rolled low carbon steel was studied. The effect of TTC on the corrosion rate was measured in 5 N H₂SO₄ at various temperatures and concentrations. It was found that TTC has a significant inhibiting effect on the corrosion of the metal; protection efficiencies approaching 97% were measured. The inhibitor shifts the free corrosion potential in the anodic direction and polarizes both the cathodic and the anodic half-reactions. The effect is more pronounced for the anodic half-reaction near the corrosion potential. It changes the apparent activation energy of corrosion to a value characteristic of diffusion processes.     

Electrochemical behaviour of zinc in chloride and acetate solutions

The corrosion behaviour of zinc in chloride medium was investigated in the absence as well as the presence, of acetate ions. The temperature effect was also investigated by varying the temperature in a range of 298 to 328 K, while the pH was kept constant at 8.5. Polarization resistance (R _p ) and activation energy (E _a ) values were determined, by means of potentiodynamic and EIS measurements. Thermodynamic properties were evaluated with the current-potential measurements. The temperature, ionic species and the parts of oxide film on anodic and cathodic processes are discussed. It was shown that zinc acetate [Zn(CH₃COO)₂] formation could provide important protection with other zinc corrosion products, against the attack of corrosive environment. The text was submitted by the authors in English.     

Anodic passivity of some titanium base alloys in aggressive environments

The passivity of titanium, binary Ti‐15Mo and ternary Ti‐15Mo‐5Al alloys in hydrochloric acid solutions was studied by potentiostatic, potentiodynamic, linear polarization and electrochemical impedance spectroscopy (EIS) techniques. The anodic passivity of binary Ti‐15Mo and ternary Ti‐15Mo‐5Al titanium alloys differs from that of the base metal in hydrochloric acid solutions. The corrosion potentials of both alloys are nobler than of the titanium because the beneficial effect of molybdenum. The critical passivation current density for binary Ti‐15Mo alloy is higher than of titanium; this fact can be explained by the instability of the constituent phases in hydrochloric acid solutions. Ternary Ti‐15Mo‐5Al alloy exhibits two critical passivation current densities (i_cr1 and i_cr2) with higher values than of the base metal and two critical passivation potentials (E_cr1 and E_cr2); at the first critical passivation potential (E_cr1) the porous titanium trioxide (Ti₃O₅) is formed and at the second critical passivation potential (E_cr2) this oxide is converted to a still higher valence oxide, the compact and protective titanium dioxide (TiO₂). The dissolution current densities in the passive range of alloys are higher than of the base metal due the dissolution of the alloying elements in this potential range. The alloys are more resistant than titanium presenting lower corrosion rates. A three time constants equivalent circuit was fitted: one time constant is for the double layer capacity (C_dl) and for the passive film (R_p); another time constant is for the charge transfer reactions visualised by a constant phase element (CPE) and a resistance (R₁); the third time constant is for diffusion processes through the passive film represented by a resistance (R₂) and a Warburg element (W).     

The effects of spark anodizing treatment of pure titanium metals and titanium alloys on corrosion characteristics

This study evaluated the surface characteristics of oxide films on commercially pure titanium metals (CP-Ti; Grade 2 and Grade 3) and titanium alloy (Ti6Al4V and Ti6Al7Nb) samples formed by an anodic oxidation treatment, and investigated the effects of anodization on the corrosion characteristics. FE-SEM, XRD, and Raman spectroscopy were used to evaluate the micromorphology and crystalline structure of the oxide films. The corrosion resistance of the sample groups was evaluated using open-circuit potential and cyclic polarization tests. After anodic oxidation up to dielectric breakdown with the same electric current, 150-200 nm-sized pores were distributed homogeneously on pure titanium metal samples, partially occluded pores were observed on the Ti6Al4V alloy, and there was an inhomogeneous size and distribution of pores on the Ti6Al7Nb alloy. The titanium dioxide films formed through anodic oxidation contained a phase mixture of anatase and rutile. The cyclic polarization tests showed that all the tested sample groups were not susceptible to localized corrosion. The as-received and anodically oxidized CP-Ti grade 3 groups showed a higher corrosion resistance than the other groups. The mean E_corr values of the anodically oxidized sample groups, except for the anodized Ti6Al7Nb alloy, showed higher values than those of the respective as-received sample groups. In particular, the Ti6AL7Nb alloy showed a statistically higher E_corr value in the anodized group than in the as-received group (p < 0.05).     

Korrosionseigenschaften dünner Schichten im System Ti?B?N

Corrosion properties of thin coatings in the Ti? B? N system Thin titanium nitride TiN, boride TiB₂ and boronitride Ti(B, N) hard coatings were deposited on titanium substrates by the PVD-process Magnetron-Sputter-Ion-Plating (MSIP). They were characterized by X-ray diffractometry, SEM and WDX-analysis. With increasing B-content the Vickers hardness of the coatings increases. Photoelectron spectroscopic measurements show that all coatings are covered in atmosphere by thin oxid layer. Titanium nitride is electrochemically in 1 N sulphuric acid stable up to 1.3 V (SHE), above 1.3 V it becomes oxidized to titanium oxide TiO₂ and nitrogen N₂. The oxidation products were detected with XPS. Corrosion tests in nitric acid HNO₃ show that the corrosion resistance of titanium nitride is lower than the resistance of titanium. The corrosion of titanium boride and titanium boronitride in sulphuric acid is more intensive compared to titanium nitride. The borides cannot be passivated, but dissolve completely by anodic polarization.     

Computational modeling of cathodic limitations on localized corrosion of wetted SS 316L at room temperature

The ability of a SS 316L surface wetted with a thin electrolyte layer to serve as an effective cathode for an active localized corrosion site was studied computationally. The dependence of the total net cathodic current, I_net, supplied at the repassivation potential E_rp (of the anodic crevice) on relevant physical parameters including water layer thickness (WL), chloride concentration ([Cl⁻]) and length of cathode (Lc) were investigated using a three-level, full factorial design. The effects of kinetic parameters including the exchange current density (i_o,c) and Tafel slope (β_c) of oxygen reduction, the anodic passive current density (i_p) (on the cathodic surface), and E_rp were studied as well using three-level full factorial designs of [Cl⁻] and Lc with a fixed WL of 25 μm. The study found that all the three parameters WL, [Cl⁻] and Lc as well as the interactions of Lc × WL and Lc × [Cl⁻] had significant impact on I_net. A five-factor regression equation was obtained which fits the computation results reasonably well, but demonstrated that interactions are more complicated than can be explained with a simple linear model. Significant effects on I_net were found upon varying either i_o,c, β_c, or E_rp, whereas i_p in the studied range was found to have little impact. It was observed that I_net asymptotically approached maximum values (I_max) when Lc increased to critical minimum values. I_max can be used to determine the stability of coupled localized corrosion and the critical Lc provides important information for experimental design and corrosion protection.     

Development of sintered Ti-30mass%Mo alloy and its corrosion properties

Ti-30mass%Mo alloy is characterized by far better corrosion resistance than pure titanium in non-oxidizing acid such as 35% HC1 solution. This alloy was newly developed in this work by a powder metallurgical process, because the conventional melting-casting process had difficulties in manufacturing the alloy owing to its heavy gravity segregation. The corrosion behavior of sintered Ti-30Mo alloy was studied by both immersion test and electro-chemical measurement. The corrosion rate of 1.3X10⁻²[mm/yearxxx] was obtained by immersion test in 35% HC1 solution, which was 10³ times superior to that of pure titanium. The potentio-dynamic polarization curve of this alloy in 35% HC1 solution showed more noble corrosion potential and lower anodic current density than those of pure titanium. The passive film formed on the alloy, in which Mo was enriched by preferential dissolution of titanium, thought to suppress the anodic reaction and improve its corrosion resistance.     

Spark anodizing behaviour of titanium and its alloys in alkaline aluminate electrolyte

Spark anodizing of titanium, Ti-6Al-4V and Ti-15V-3Al-3Cr-3Sn in alkaline aluminate electrolyte produces highly crystalline anodic films consisting mainly of Al₂TiO₅ with α- and γ-Al₂O₃ as minor oxide phases, irrespective of substrate composition. However, the apparent efficiency for film formation decreases in the following order: Ti-6Al-4V, titanium and Ti-15V-3Al-3Cr-3Sn. A large amount of aluminium species are incorporated from the electrolyte, probably by plasma-chemical reaction, and become distributed throughout the film thickness. This distribution indicates that the electrolyte penetrates near to the film/substrate interface through the discharge channels. Thus, the outwardly migrating aluminium ions under a high electric field can be present even in the inner part of the anodic films. Voids are developed at the film/substrate interface, particularly on the vanadium-containing alloys, reducing the adhesion of the anodic film to the substrate.     

电弧喷涂Al-Zn-Si-RE合金涂层在3.5%NaCl溶液中的电化学腐蚀行为(英文)

采用电弧喷涂方法在低碳钢表面获得高铝含量的Al-Zn-Si-RE涂层。通过测量Al-Zn-Si-RE涂层在3.5%NaCl溶液中的动电位极化曲线,腐蚀电位-时间曲线和电化学阻抗谱,系统地研究涂层的电化学腐蚀行为。通过将测量电化学阻抗谱拟合成等效电路图,研究涂层在3.5%NaCl溶液中浸泡不同时间的阻抗行为。结果表明:Al-Zn-Si-RE涂层与Zn-15Al涂层具有相似的极化行为,阳极极化曲线均无钝化特征,仅呈现出活性溶解,但其腐蚀性能优于Zn-15Al涂层。Al-Zn-Si-RE涂层可以给钢基体提供有效的牺牲阳极保护作用,且牺牲阳极保护作用在涂层腐蚀过程中占主导地位。此外,腐蚀电位-时间曲线和电化学阻抗谱结果表明:在浸泡过程中存在点蚀-溶解-再沉积、活化溶解、阴极保护、腐蚀产物引起的物理屏蔽和涂层失效五个腐蚀阶段。     

纳米颗粒增强TiO_2涂层的制备及其防污性能

为提高二氧化钛涂层的防污性能,采用KH-550硅烷改性锐钛矿型TiO_2颗粒,并充分分散于二氧化钛凝胶涂层中。通过降解亚甲基蓝溶液、细菌贴附试验、藻类贴附试验,分别评价了涂层的光催化性能、抗菌性能及抗藻类附着性能,并利用激光共聚焦显微镜及扫描电子显微镜对藻类在涂层表面的附着情况进行分析。结果表明,添加TiO_2纳米颗粒涂层的防污性能较未添加TiO_2纳米颗粒涂层有较大程度的提高。添加粒径为5~10 nm TiO_2颗粒的二氧化钛涂层对小球藻、三角褐指藻及小新月菱形藻的附着降低率分别达到了92.1%、71.5%和62.1%,相较于纯二氧化钛涂层对3种藻类的附着降低率分别提高了29.7%、68.4%和43.5%。TiO_2颗粒的加入可以有效地提高涂层的光催化性能,光催化使得涂层具有亲水、抗菌及自清洁的性能进而有利于提高涂层的防污性能。