Preliminary testing of NiFe_2O_4-NiO as ceramic matrix of cermet inert anode in aluminum electrolysis

1　INTRODUCTIONTheideaofusinginertanodes(alsocallednon consumableoroxygen evolvinganodes)inaluminumproductionisasoldastheHall H啨ｒｏｕｌｔｐｒｏｃｅｓｓ ,dat ingbacktothediscoveryofoneoftheinventors ,Hall[1] .Inertanodesareintendedtoreplacethecon sumablecarbonanodethatiscurrentlyused .Withacarbonanode ,thecellreactionisAl2 O3+ 3/ 2C =2Al+ 3/ 2CO2 (1)where　acryolite basedmelt(Na3AlF6 AlF3 CaF2 )atnear 96 0℃servesassolventforthealumina .Withaninertanode ,thecellreactionwillbeAl2 …     

Preparation and preliminary testing of cermet inert anode for aluminum electrolysis

1　INTRODUCTIONAluminumhasthelargest productivityamongthenonferrousmetals ,2 4Mtperyearintheworld .Whilegreatprogresshavebeenmadeintheprimaryaluminum production ,theindustrycontinuestopur sueresearchtosolvesomeformidablechallenges ,suchas quitealargeenergyintensity(14 0 0 0 15 0 0 0kW·hpertonaluminum) ,highcon sumptionofcarbonanode(5 0 0 6 0 0kgpertonalu minum) ,significantemissionsofgreenhousegas(1.71tpertonaluminum )andotherdetrimentalgases ,highcapitalinvestmentandcost[1] .Inertelectr…     

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。     

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…     

Electrical resistivity of NiFe_2O_4 ceramic and NiFe_2O_4 based cermets

NiFe2O4 ceramic and NiFe2O4 based cermets, expected to be used as the inert anodes in aluminum electrolysis, were prepared and their electrical resistivities were measured at different temperatures. The effects of temperature and composition on their electrical resistivities were investigated. The results indicate that the electrical resistivities of NiFe2O4 based cermets mainly depend on temperature, resistivity of ceramic matrix, composition and dispersion of the metal phase among ceramic matrix. The electrical resistivity of NiFe2O4 ceramic decreases from 10. 094 Ω · cm to 0. 475 Ω · em with increasing temperature from 573 K to 1 233 K. The electrical resistivities of NiFe2O4 based cermets are greatly lowered, but decrease with increasing the temperature with similar trend compared to that of NiFe2O4 ceramic. The resistivities of NiFe2O4 based cermets containing 5 % Ni, 5 % Cu and 5 % CuNi alloy are 0. 046 8, 0.066 8 and 0. 0532 Ω · cm at 1 233 K, respectively, which are all acceptable as inert anode materials compared to that of the current carbon anode used for aluminum electrolysis.     

铝电解用NiFe2O4-Cu金属陶瓷惰性阳极的制备

以高温固相合成法合成的NiFe2O4陶瓷粉体和金属Cu粉为原料, 采用冷压-烧结法制备了Cu含量在5%～20%之间的NiFe2O4-Cu金属陶瓷惰性阳极, 研究了烧结气氛和烧结温度对其物相组成、微观形貌和基本物理性能的影响. 结果表明 通过控制烧结气氛中氧分压在NiO和Cu2O的离解反应平衡氧分压之间, 可以制备出具有目标物相组成的NiFe2O4-Cu金属陶瓷; 烧结温度和保温时间对所得NiFe2O4-Cu金属陶瓷的相对密度有较大影响; NiFe2O4和Cu之间的不润湿性限制了NiFe2O4-Cu金属陶瓷烧结温度的提高和保温时间的延长, 在保证金属相分布均匀且不溢出的前提下, 所制备的NiFe2O4-Cu金属陶瓷的相对密度较小; 金属相Cu含量越高, NiFe2O4-Cu金属陶瓷最高烧结温度越低、最长保温时间越短, 从而相对密度越低、孔隙率越高; 除了尽量降低金属相含量外, 还可向NiFe2O4-Cu金属陶瓷中添加其他金属如Ni和Co等, 以改善陶瓷相与金属相之间的润湿性, 以提高烧结温度, 进而提高其相对密度和耐腐蚀性能.     

Effect of metallic phase content on mechanical properties of （85Cu- 15Ni）/（10NiO-NiFe2O4） cermet inert anode for aluminum electrolysis

（85Cu-15Ni）/（10NiO-NiFe2O4） cermets were prepared with Cu-Ni mixed powders as toughening metallic phase and 10NiO-NiFe2O4 as ceramic matrix. The phase composition, microstructure of composite and the effect of metallic phase content on bending strength, hardness, fracture toughness and thermal shock resistance were studied. X-ray diffraction analysis indicates the coexistence of （Cu-Ni）, NiO and NiFe2O4 phases in the cermets. Within the content range of metallic phase from 0% to 20% （mass fraction）, the maximal bending strength （176.4 MPa） and the minimal porosity （3.9%） of composite appear at the metallic phase content of 5%. The fracture toughness increases and Vickers＇ hardness decreases with increasing metal content. When the thermal shock temperature difference （At） is below 200 ℃, the loss rate of residual strength for 10NiO-NiFe2O4 ceramic is only 8%, but about 40% for （85Cu-15Ni）/（10NiO-NiFe2O4）cermets. As At is above 200 ℃, the residual strength sharply decreases for sample CN0 and falls slowly for samples CN5-CN20.     

新型炼铝电极材料

研制了一种新型铝电解金属陶瓷惰性阳极,阳极基体由Fe-Ni-Co-Al-O构成.在电解温度960℃,氧化铝质量浓度为6.0%,阳极电流密度为1.0 A/cm2,分子比为2.6的电解质中对其进行了10 h的电解.电解过程平稳,电解铝产品纯度达到96%～99%,阳极气体中氧气的含量为98%,反电动势为2.45 V,高于理论值0.25～0.35 V.此阳极具备较好的导电性、抗氧化和耐腐蚀性.采用X射线衍射和电子探针微分析仪(EPMA)对电解后的阳极进行分析,发现阳极表面存在铁酸镍、铝酸铁等尖晶石型化合物,阳极表面下层为铝酸铁、钴酸镍等陶瓷相以及金属相;金属相和陶瓷相相互弥散分布构成结构致密的金属陶瓷层.     

NiFe2O4基金属陶瓷惰性阳极的腐蚀研究进展

综述了近年来国内外铝电解用NiFe2O4基金属陶瓷惰性阳极在阳极组元的溶解与分布、腐蚀率的预测与测定以及氧化物和金属相对阳极腐蚀的影响三个方面所做的研究工作。     

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.     

大尺寸NiFe2O4-10NiO/17Ni型金属陶瓷惰性阳极的制备

研究以PVA为主要成分的粘结剂体系的热分解特性对大尺寸粉末压坯脱脂行为的影响,发现PVA的不均匀热分解是造成大尺寸粉末压坯脱脂失效的原因之一,开发一种具有稳定热分解反应特性的新型粘结剂体系,实现大尺寸粉末压坯的无缺陷热脱脂;研究烧结气氛、金属相的添加对NiFe2O4-10NiO致密化行为的影响。结果表明：N2气氛烧结及加入Ni可有效提高NiFe2O4-10NiO陶瓷基体的烧结致密度,1350℃时于N2气氛中烧结的NiFe204．10NiO／5Ni型金属陶瓷材料的相对密度达到97．28％。采用优化工艺实现d120mmX140mm深杯状NiFe2O4-10NiO／17Ni金属陶瓷惰性阳极脱脂预烧坯的烧结,所得烧结坯平均相对密度为95．21％。     

铝电解金属陶瓷惰性阳极的机械加工及大型化研究

本文用普通钻头和设计的专用走具,采用传统机械加工方法对金属陶瓷铝电解惰性阳极钻孔,同时也研究了金属陶瓷惰性阳极的磨削、抛光等加工方法。用这些方法成功地解决了金属陶瓷铝电解惰性阳极的机械加工和大型化问题。     

Densification of Ni-NiFe_2O_4 cermets for aluminum electrolysis

1INTRODUCTION Aluminumelectrolysisconsumesenormous energyandresources,andtheconsumptionwillbeconsiderablydecreasedbyintroductionofinert anodeandwettablecathode.However,underthe toughworkingconditionofaluminumelectrolysis,i.e.highlycorrosiveNa3AlF6Al2O3moltensalts athightemperature(940960℃),theinert anodesnecessaryforthesuccessfulproductionofaluminummighthavethefollowingproperties:be insolubleinafluoridemelt,beresistanttowards anodeoxygen,havegoodelectricalconductivity,possessadequatestr…     

Effect of NiO content on corrosion behaviour of Ni-xNiO-NiFe2O4 cermets in Na3AlF6-Al2O3 melts

5Ni-xNiO-NiFe2O4 cermets with different NiO contents were prepared and the corrosion behaviour in Na3AlF6-Al2O3 melts was investigated in laboratory electrolysis tests. The results indicate that adding NiO is unfavorable to the densifieation of NiFe2O4-xNiO ceramics, while small Ni doping can greatly improve the sintering property. The electrolysis tests show that excess NiO is beneficial to the reduction of Fe while has little effects on that of Ni in the bath; the steady-state concentrations of Ni, Fe are below the corresponding solubilities of NiFe2O4-xNiO, implying that corrosion mechanism changes while electrifying. Post-electrolysis examination of anodes shows that Ni metal leaches at the anode surface, yet the substrate ceramic prevents the penetration of bath and the further loss of metal phase.     

铁酸镍基金属陶瓷惰性阳极材料的研究进展

惰性阳极铝电解技术的发展主要基于经济和环境的考虑,对铝电解工业的长远发展具有重要意义,已成为铝电解工业进步的关键技术。合金惰性阳极具有易加工成形、良好的抗热震性和导电性,金属陶瓷惰性阳极兼顾陶瓷的高温热稳定性及金属的高导电性和高韧性,二者已成为惰性阳极的主要候选材料体系,并进行了工程化铝电解试验研究。近年来,惰性阳极的研究集中在合金阳极表面保护膜形成与溶解的动态平衡控制、金属陶瓷组成与结构优化、惰性阳极的电解腐蚀机制及抑制技术等方面。综述了铝电解用合金阳极和金属陶瓷惰性阳极的近期研究进展,从材料学的角度介绍铁酸镍基金属陶瓷的组成优化、烧结、电解腐蚀特性等方面的最新研究成果。     

基于GA-BP的NiFe2O4基金属陶瓷阳极优化设计

采用BP神经网络对铝电解NiFe2O4基金属陶瓷惰性阳极的电解腐蚀过程进行了系统辨识。建立了以Al2O3质量浓度、电解温度、分子比、面积比和电流密度为输入,腐蚀率为输出的网络模型。在材料的设计中,采用了GA-BP优化方法,BP网络参与GA迭代计算时对个体的评价。应用结果表明,NiFe2O4基金属陶瓷惰性阳极的电解腐蚀率预测结果与实测值吻合;优化设计的结果与实验值很接近。     

17（Cu-10Ni）-（NiFe2O4-10NiO）基金属陶瓷在铝电解过程中的相演变（英文）

采用冷压气氛烧结制备17(Cu-10Ni)-(NiFe2O4-10NiO)金属陶瓷,并作为阳极在960°C下分别进行10和40h的铝电解试验。对电解前后金属陶瓷的显微结构、物相成分进行分析检测。对电解质及阴极金属中的杂质含量进行分析,研究阳极组成中Fe、Ni和Cu元素的腐蚀行为。研究发现:在电解过程中,在材料表面形成NiFe2O4相致密层,该致密层随电解时间的延长而增厚。在NiFe2O4相致密层形成与增厚过程中,出现NiFe2O4相吞噬NiO相和金属相氧化的现象,金属陶瓷中Cu元素优先腐蚀溶解。并着重讨论NiFe2O4相致密层形成与增厚过程中金属相的腐蚀形式及NiO相向NiFe2O4相的转变机制。     

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.     

惰性阳极基体材料NiFe2O4尖晶石的研制

本文用Ni2O3和Fe2O3为原料制备了铝电解用惰性阳极基体材料NiFe2O4尖晶石,详细介绍了整个制备过程。通过对NiFe2O4尖晶石的含量、真密度以及开口孔隙率等重要指标进行研究比较,最终得出了制备NiFe2O4尖晶石最佳工艺条件,并用最佳工艺条件重新制取试样进行热腐蚀实验。     

铝电解惰性阳极研究

进行了镍基惰性阳极在熔融质中通电情况下的腐蚀实验,介绍了镍基惰性阳极的抗冲击力,抗腐蚀等性能。