Cu-Ni-Al金属阳极抗氧化耐腐蚀性能研究

本文对铝电解阳极材料Cu—Ni—Al合金进行抗氧化耐腐蚀性能测试，结果说明Cu—Ni—Al阳极在空气和氧气中具有良好的抗氧化性，其中温度和气氛对该合金材料抗氧化影响很大；在不同条件下，电解质组成为NaCl-CaF2-Al2O3的熔盐中溶解损失比较小。在熔盐中腐蚀速率随着温度升高、电解质分子比降低而增大。     

Electrochemical dissolution of cemented carbide scrap and electrochemical preparation of tungsten and cobalt metals

In this study, WC and WC-6 wt% Co scraps were utilized in molten salt state as two consumable anodes to circulate tungsten and cobalt during electrolysis. Because of poor dissolution of cemented carbide scrap in NaCl-KCl salt, tungsten trioxide was added to NaCl-KCl salt as active substance to improve the dissolution of the anode. Therefore, dissolutions of WC and WC-6 wt% Co anodes were studied at different tungsten trioxide contents. It was shown that addition of tungsten trioxide significantly increased dissolution of the anode. The addition of tungsten trioxide drastically reduced charge transfer impedance and accelerated the dissolution. The electrolyte resistance also reduced slightly. The electrolysis of WC anode was investigated at optimal tungsten trioxide content. Tungsten with single phase was obtained at current density of 0.1 A·cm⁻² for 8 h. The electrolysis of WC-6 wt% Co anode was also explored using same tungsten trioxide content. The data suggested that electrolysis time and current density greatly influenced the composition of cathode product. The preliminary conditions were determined for separation of tungsten and cobalt. Overall, the electrochemical preparations of cobalt and tungsten metal were achieved by two-step electrolysis processes.     

铝电解用NiFe2O4-10NiO基金属陶瓷惰性阳极的耐腐蚀性能

制备铝电解用NiFe2O4-10NiO基金属陶瓷惰性阳极,并在实验室电解槽中考察其电解腐蚀性能。结果表明,电解过程中虽然惰性阳极在960°C熔盐电解质中表现出优异的耐腐蚀性能,但采用XRD、SEM/EDX和金相分析其物相组成和微观结构后发现,电解后阳极中的金属相发生了优先腐蚀,在阳极表面产生大量孔洞。NiFe2O4相中的 Fe 元素的优先溶解可能导致 NiFe2O4晶粒的不均匀腐蚀。溶解在电解液中的 Al2O3与阳极中的 NiO 或FeO 发生反应生成的 NiFe2O4-NiAl2O4-FeAl2O4相对 NiO 相的吞并以及体积膨胀,阳极表面形成致密的NiFe2O4-NiAl2O4-FeAl2O4保护层。因此,致密的NiFe2O4-NiAl2O4-FeAl2O4保护层可以阻挡阳极表面金属相的损失和陶瓷相的腐蚀。     

添加剂BaO对铝电解用xCu/（10NiO-NiFe_2O_4）金属陶瓷惰性阳极腐蚀性能的影响

制备铝电解用xCu/（10NiO-NiFe2O4）和1BaO-xCu/（10NiO-NiFe2O4）（x=5,10,17）金属陶瓷惰性阳极,在传统电解质中以电流密度1.0A/cm2进行实验室电解腐蚀实验。结果表明：金属Cu被腐蚀,在阳极表面留下了许多孔洞从而导致在电解过程中电解质向阳极内部渗透;金属陶瓷5Cu/（10NiO-NiFe2O4）,10Cu/（10NiO-NiFe2O4）,17Cu/（10NiO-NiFe2O4）,1BaO-5Cu/（10NiO-NiFe2O4）,1BaO-10Cu/（10NiO-NiFe2O4）和1BaO-17Cu/（10NiO-NiFe2O4）的腐蚀速率分别为2.15,6.50,8.30,4.88,4.70和4.48cm/a;添加剂BaO对10Cu/（10NiO-NiFe2O4）和17Cu/（10NiO-NiFe2O4）金属陶瓷的抗腐蚀性能是有利的,因为添加剂BaO能有效提高其致密度从而提高其抗腐蚀性能;但BaO对5Cu/（10NiO-NiFe2O4）金属陶瓷的抗腐蚀性能是不利的,可能是因为聚集在晶界的添加剂BaO加速了金属陶瓷的腐蚀。     

Depolarised gas anodes for aluminium electrowinning

Consumable carbon anodes are used in the electrowinning of aluminium by the Hall-Heroult process.Emissions of CO2 may be eliminated by introducing an inert oxygen evolving anode,which however will require a higher anode potential.An alternative approach is to use a natural gas or hydrogen gas anode to reduce the CO2 emissions and lower the anode potential.Preliminary laboratory experiments were carried out in an alternative molten salt electrolyte consisting of CaCl2-CaO-NaCl at 680 °C.Porous anodes of platinum and tin oxide were tested during electrolysis at constant current.The behaviour of inert anode candidate materials such as tin oxide and nickel ferrite were also studied.     

Corrosion behavior of Cu-Ni-Ag-Al alloy anodes in aluminium electrolysis

The behavior of Cu-Ni-Ag-Al alloy used as anode for aluminum electrolysis was directly visualized in a two-compartment see-through cell during electrolysis, and its performances were tested at 850℃ in acidic electrolyte molten salts consisting of 39.3%NaF-43.7%AlF3-8%NaCl-5?F2-4%Al2O3 for 40 h in a laboratory cell. The results show that nascent oxygen oxidizes the anodic surface to form oxide film at the beginning of electrolysis. X-ray diffraction analysis of alloy surface show that the oxide film on the anodic surface consists of CuO, NiO, Al2O3,CuAl2O4 and NiAl2O4. However, SEM image shows the oxide film is porous, loose and easy to fall into electrolyte and to contaminate aluminum. The corrosion mechanism of metal anodes was analyzed.     

Preliminary testing of NiFe2O4-NiO-Ni cermet as inert anode in Na3AlF6-AlF3 melts

1 Introduction It is well known that the current aluminum reduction cell with carbon consumable anode has many disadvantages. So the concept of inert anode was introduced, with which the disadvantages can be avoided completely. A lot of research work has…     

The Effect of Pre-oxidation Treatment on Corrosion Behavior of Ni–Cu–Fe–Al Anode in Molten CaCl<Subscript>2</Subscript> Salt

This article presents Ni–Cu–Fe–Al alloy as a novel inert anode used in FFC process (the Fray Farthing Chen) in molten calcium chloride salts for producing titanium. The alloy was prepared by vacuum induction melting; then utilized as anode material in molten CaCl₂ for 16 h at 900 °C. Morphology and the corrosion behavior of the samples were analyzed using scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The product on the cathode was analyzed using X-ray diffraction (XRD). After 16 h electrolysis of anodes, EDS and SEM analysis of the samples showed that the corrosion depth of the non-oxidized sample was shorter. Corrosion attacks more severe for the pre-oxidized sample than the non-oxidized sample, which indicated that the corrosion resistance of outer layer is higher on the non-oxidized sample. The XRD results show that the TiO₂ pellets were successfully reduced to the lower oxides using the Ni–Cu–Fe–Al inert anode.     

Fe-30Ni-5NiO alloy as inert anode for low-temperature aluminum electrolysis

Fe-30Ni-5NiO alloy anodes were prepared by a spark plasma sintering process for aluminum electrolysis. NiO nano-particles with the size of ∼20 nm were dispersed in the anodes. The oxidation behaviors of the anodes were investigated at 800°C and 850°C, respectively. The electrolysis corrosion behaviors were tested in a cryolite-alumina electrolyte at a low temperature of 800°C with anodic current densities of ∼0.5 A/cm². The results indicated that the oxidation kinetic of the anodes followed a parabolic law. A continuous Fe₂O₃ film selectively formed on the surface of the anode during the electrolysis process. A semi-continuous Al₂O₃ layer was observed at oxide film/alloy interface, probably caused by an in-situ chemical dissolution process.     

固体电解质用于熔盐电解析氧过程的研究

将氧化物固体电解质制成析氧阳极,研究了在以析氧阳极和碳阴极构成的电解槽中氧化铝熔盐电解过程，测得分解电压约为1.67V，并定性地研究了固体电解质在冰晶石熔盐中的腐蚀问题，实验结果表明，电解条件下固体电解质管内外两表面间的电势差使固体电解质在冰晶石熔盐中存在溶解阻碍，有很好的耐腐蚀性能。     

铝电解中二氧化锡基（氢气）气体阳极

开发一种在低温电解质（850℃）铝电解中应用的新型二氧化锡基气体阳极以降低铝电解能耗和二氧化碳排放。在此种气体阳极中,氢气通入阳极后参与阳极反应,分别用石墨和铝作阴极和参比电极。采用循环伏安法研究此体系中铂和二氧化锡基电极上氧离子的电化学行为,并确定氧气的析出电势。然后,采用气体电极进行恒电流电解实验,相对于未通入气体和通入氩气,通入氢气后阳极出现明显的去极化现象（阳极电势约下降0.8 V）。实验结果表明,氢气已参与阳极三相界面（气体-电解质-电极）反应,为还原性气体阳极在铝电解上的应用提供了可行性。     

Laboratory-scale performance of a binary Cu-Al alloy as an anode for aluminium electrowinning

A binary Cu-Al alloy (9.4 wt.% Al) has been investigated as a potential inert anode for aluminium electrowinning. Anodes have been tested in a laboratory electrolysis cell both with and without preformed oxides. Electrolysis was conducted in cryolitic electrolytes with anode current densities of 0.5 A cm⁻². The anodes operated satisfactorily as measured by electrical parameters. However, substantial corrosion of the Cu-metal substrate was observed. The external oxide generated on pre-treated anodes was porous and allowed the electrolyte to penetrate through to the Cu-metal whereby corrosion was initiated. An untreated anode formed an in situ surface alumina film, but this did not prevent corrosion of the substrate.     

电解质对铝电解用阳极润湿性的研究

测试了熔融状态下三种不同组分的电解质对碳阳极和自制的镍铁尖晶石基金属陶瓷惰性阳极的润湿性.实验结果表明,电解质对惰性阳极的润湿性明显好于对碳阳极的润湿性,不同电解质成分对阳极的润湿角有一定影响.工业冰晶石中加入Al2O3能够改善电解质对阳极的润湿性,添加剂CaF2对提高电解质对惰性阳极的润湿性基本没有贡献.     

EFFECT OF Cu-Ni CONTENT ON THE CORROSION RESISTANCE OF （Cu-Ni）/（10NiO-90NiFe204） CERMET INERT ANODE FOR ALUMINUM ELECTROLYSIS

（Cu-Ni）/（10NiO-90NiFe204） cermet inert anodes containing metal Cu-Ni0, 5, 10, 15 and 20 wt pct were prepared and their corrosion resistance to Na3AlF6-Al2O3 melts was investigated. The results indicate that the content of metal Cu-Ni has little effect on the steady-state concentration of Ni in the electrolyte and the values could not be used to effectively differentiate their corrosion resistance. The steady-state concentration of Fe decreases from 304×10^-6 to 168×10^-6 and that of Cu increases from 21×10^-6 to 71×10^-6 with the content of metal Cu-Ni increasing from 0 to 20 wt pct. Post-examination shows that metallic phase Cu-Ni is corroded preferentially during electrolysis and many pores are left at the anode surface. Considering the corrosion resistance and electrical conductivity, the cermet containing metal Cu-Ni 5 wt pct should be selected and studied further.     

EFFECT OF Cu-Ni CONTENT ON THE CORROSION RESISTANCE OF (Cu-Ni)/(10NiO-90NiFe2O4) CERMET INERT ANODE FOR ALUMINUM ELECTROLYSIS

(Cu-Ni)/(10NiO-9ONiFe2O4 ) cermet inert anodes containing metal Cu-Ni 0,5, 10, 15 and 20 wt pet were prepared and their corrosion resistance to Na3AlF6-Al2O3 melts was investigated. The results indicate that the content of metal Cu-Ni has little effect on the steady-state concentration of Ni in the electrolyte and the values could not be used to effectively differentiate their corrosion resistance. The steady-state concentration of Fe decreases from 304×10-8 to 168×10-6 and that of Cu increases from 21×10-6 to 71×10-6 with the content of metal Cu-Ni increasing from 0 to 20 wt pct. Post-examination shows that metallic phase Cu-Ni is corroded preferentially during electrolysis and many pores are left at the anode surface. Considering the corrosion resistance and electrical conductivity, the cermet containing metal Cu-Ni 5 wt pct should be selected and studied further.     

电镀Al-Mn合金及后续阳极氧化对镁合金防护性能的影响

为提高镁合金的耐腐蚀性能,采用无机熔盐电镀技术在镁合金表面电镀铝锰合金,其后在草酸溶液中对铝锰合金镀层进行阳极氧化处理,以制备耐蚀性优良的阳极氧化膜。采用扫描电镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)等对阳极氧化膜的微结构进行表征,采用电化学测试方法对阳极氧化膜的耐腐蚀性能进行评价。结果表明,Al-Mn合金镀层在草酸溶液中形成的阳极氧化膜主要由稳态的α-Al2O3和亚稳态的γ-Al2O3所组成,并含有少量的MnO2及Al(MnO4)3,该阳极氧化膜具有很强的绝缘特性,其腐蚀电流密度较Al-Mn合金镀层下降了约3个数量级,较基体镁合金下降了约6个数量级,极大地提高了镁合金的耐腐蚀性。     

INTERFACIAL PHENOMENA AT BOUNDARIES OF MOLTEN ELECTROLYTE-CARBON ELECTRODE-LIQUID METAL IN ALUMINIUM ELECTROLYSIS CELL(PARTⅠ)

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Korrelation zwischen einigen beschleunigten Korrosionsprüfungen und Freibewitterungsprüfungen eines CuNiCr-Überzugs

Correlations between certain accelerated corrosion tests and outdoor weathering tests of a Cu-Ni-Cr coating The present paper deals with investigations into the corrosion resistance od a Cu-Ni-Cr coating designed for heavy duties. Thr tests were carried out under outdoor weathering conditions and in the laboratory. The correlations between the two types of tests are indicated. The corrosion tests were carried out in the sea climate of Znitmasch testing station at the coast of the Black sea. In the laboratory, two types of accelerated corrosion tests were carried out, one with salt spray mist; the other based on the ? Corrodkote”?method. The corrosion resistance of the tested Cu-Ni-cr coating was assessed by the system advised by Erdös and was expressed in the form of corrosion/time diagrams. With the aid of these diagrams, it is possible to find the correlation between the weathering tests and the accelerated laboratory tests.     

AZ31镁合金表面含纳米羟基磷灰石微弧氧化涂层的制备及性能研究

目的改善AZ31镁合金的耐腐蚀性能及生物活性。方法使用微弧氧化技术,分别在以六偏磷酸钠为主盐的电解液和以六偏磷酸钠为主盐、以纳米羟基磷灰石(HA)为添加剂的电解液中,在AZ31镁合金表面制备了微弧氧化涂层。通过扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)表征了涂层的微观形貌、元素特征和相组成。通过电化学方法和浸泡实验考察了涂层的耐蚀性。通过细胞实验评价了两种涂层的细胞相容性。结果电解液中的HA可以进入到微弧氧化涂层中,含HA的微弧氧化涂层较不含HA的更致密,且有封孔现象。电化学方法及浸泡实验结果表明,含HA的微弧氧化涂层的耐腐蚀性能更好。细胞表面粘附实验和细胞增殖实验也表明,经表面纳米HA微弧氧化处理后的AZ31镁合金生物相容性更好,且对MC3T3-E1细胞的增殖有促进作用。结论六偏磷酸钠电解液中添加纳米HA,可以在AZ31镁合金表面制备出含HA的微弧氧化涂层,且其耐腐蚀性能和生物活性均优于不含HA的微弧氧化膜。     

Effect of Ni content on corrosion behavior of Ni/（10NiO-90NiFe2O4） cermet inert anode

Ni/（10NiO-90NiFe2O4） cermet inert anodes with metal Ni content of 0, 5, 10, 15 and 20 （mass fraction, %） were prepared and their corrosion behavior in Na3AlF6-Al2O3 melts was investigated in laboratory electrolysis tests. The results indicate that the content of metal Ni in anodes has little effect on the steady-state concentration of impurities Ni and Fe in electrolyte and the values range in （114-173）×10^-6 and （287-385）×10^-6, but the content of impurities in the metal aluminum manifolds. There is preferential corrosion for metal Ni in NiO-NiFe2O4 based cermet anodes. Considering the corrosion resistance and electrical conductivity, the cermet containing 5%Ni （mass fraction） behaves best among NiO-NiFe2O4 based cermet anodes studied, and should be further studied.