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.     

Copper-nickel superalloys as inert alloy anodes for aluminum electrolysis

The superalloys Cu-Ni-Al, Cu-Ni-Fe, and Cu-Ni-Cr were studied as anodes for aluminum electrolysis. The alloys were tested for corrosion in acidic electrolyte molten salt and for oxidation in both air and oxygen. The results showed that the Cu-Ni-Al anodes possess excellent resistance to oxidation and corrosion, and the oxidation rates of Cu-Ni-Fe and Cu-Ni-Al anodes were slower than those of pure copper or nickel. During electrolysis, the cell voltage of the Cu-Ni-Al anode was affected most by the concentration of alumina in cryolite molten salt. The Cu-Ni-Fe anode exhibited corrosion resistance in electrolyte molten salt. Comparatively, the Cu-Ni-Cr anode showed poor resistance to oxidation and corrosion. The testing found that further study is warranted on the use of Cu-Ni-Al and Cu-Ni-Fe as inert alloy anodes. For more information, contact Zhongning Shi, Northeastern University, School of Materials and Metallurgy, WenhuiRoad No. 3, Shenynag, Liaoning 110004 China; e-mail znshi@163.com     

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…     

小型金属陶瓷惰性阳极的低温铝电解实验

本实验采用自行研制的小型镍铁尖晶石基惰性阳极 (直径 43mm)与冰晶石 -氧化铝系低温电解质 ,在 85 0℃下进行电解实验 ,保持阳极电流密度lA/cm2 ,实验共进行 11小时 ,得到了少量的金属铝。实验结果表明 ,在此电解温度下 ,构成惰性阳极的金属陶瓷材料抗电解质腐蚀的能力较强 ;阳极在实验后出现的裂纹说明材料的抗热震性有待进一步提高 ,而且本实验中惰性阳极与金属导杆的连接方式也需更深入研究。     

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。     

大型铝电解惰性阳极的研制

本文报导了新近研制开发的大型铝电解惰性阳极板(160×100×10mm)的制作过程,并对使用的原料准备、压制成型、烧结过程进行讨论。该阳极板可拼接为160×300~500×10mm大型阳极并组装为3000~6000A铝电解试验槽的惰性阳极。     

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 …     

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。     

铝电解惰性阳极的材料设计

综合评述了国内外迄今为主,在惰性阳极领域所做的部分代表性工作,分析了不同材质惰性阳极在实验室和工业化过程所遇到的困难。研究相关领域最近几年的新进展,如合金、陶瓷、腐蚀与防护等,将这些领域取得一些成果引入到铝电解惰性阳极材料的解决方案中,如对铝液无污染的复合电极材料以及将合金高温抗氧化涂层的概念,为铝电解惰性阳极的研究工作提供一些新思想。     

Results from 100 h electrolysis testing of NiFe2O4 based cermet as inert anode in aluminum reduction

1 Introduction Since the Hall-Héroult process was applied in aluminum production, an inert anode was always the target that the aluminum industry was seeking for in the new technology field[1]. Some selection criteria have been defined in order to ident…     

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。     

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％。     

Kinetics of Fe-30% Ni-12.5% Co invar alloy during high temperature oxidation

The oxidation behavior of Fe-30% Ni-12.5%Co Invar alloy possessing low thermal expansion-high strength has been studied by exposing it in temperature ranges of 1000–1200 in an air atmosphere. The formed oxide scale consisted of two layers, an outer layer and an inner layer, and the oxidation mechanism showed uniform growth for all oxidation conditions. The growth rate of the scale had a parabolic relationship with oxidation time, and the estimated activation energy for the growth of the whole oxide layer was approximately 19.84 kcal/mol. The outer scale consisted of five oxide layers, whose outermost scale consisted of major phase CoFe₂O₄ containing a particulate Fe₂O₃ phase. The oxide scale of Fe-30 Ni-12.5% Co had different compositions and phases from the Fe-30%Ni alloy investigated in previous studies. Especaally, when the alloy was exposed for a longer oxidation time and at a higher temperature, the volume fraction ratio of CoFe₂O₄ to Fe₂O₃ was found to increase     

Industrial testing of property-modified prebaked carbon anode for aluminum electrolysis

1　INTRODUCTIONInaluminumelectrolysis process ,thequantitygradeofcarbonanoderestrictsnotonlytheimprove mentofproductiontechniques ,butalsotheadvance mentofproductiontargets.Formany years ,largenumberofresearchesweredonetoimprovethephysi cal,chemicalandelectrochemicalperformanceoftheanodeinordertoenhancecurrentefficiency ,reduceenergyconsumption ,decrease productioncostandcleancircumstanceofaluminum plantanditssur roundingarea .Recently ,manylaboratoryresearchresultsweresuccessfullyappliedf…     

铝电解NiFe2O4基惰性阳极材料纤维增强体的选择

以NiO和Fe2O3为原料采用固相烧结法合成NiFe2O4尖晶石,通过向其中添加短纤维制备纤维/NiFe2O4惰性阳极材料。为选择适合于NiFe2O4基惰性阳极材料的纤维增强体,对几种纤维在NiFe2O4基体中的高温稳定性进行考察。结果表明,高温下碳纤维、玻璃纤维、氧化铝纤维和碳化硅纤维与NiFe2O4基体是热力学不相容的;1 200℃时镀镍碳纤维和镍纤维不能在基体中稳定存在;1 400℃时ZrO2(f)与NiFe2O4基体具有良好的物理和化学相容性,添加3%ZrO2(f)(质量分数)阳极试样的力学性能得到明显改善。因此,ZrO2(f)可作为NiFe2O4基惰性阳极的纤维增强体。     

Fe-29Ni-17Co合金的热变形行为

在实验温度为900-1200℃,应变率为0.001-1 s-1的条件下,对Fe-29Ni-17Co合金进行热压缩试验。热压缩过程中的动态再结晶导致材料的流变软化。用双曲正弦方程分析材料的流变行为,并确定了相应的材料常数A, n 和α,其中得到的表观活化能为423 kJ/mol。材料的应力峰值与稳态应力对Zener-Hollomon参数显示出简单的指数依赖关系。用Avrami方程分析了动态再结晶动力学,得到相应的指数为2.7,高于文献报道的2,这与连续动态再结晶机制有关。采用Cingara方程搭建峰值流变曲线,得到应变指数c约为0.85,比有关报道的不锈钢的c值0.2高,这点更加强了关于进行Fe-29Ni-17Co合金动态回复或连续动态再结晶研究的想法。     

惰性阳极铝电解的理论能耗和理论能耗电压

本文提出了惰性阳极铝电解中以氧化铝中α-Al2O3含量，电解温度和室温为变量的理论能耗计算公式和以氧化铝中α-Al2O3含量，电解温度，室温和电流效率为变量的理论能耗电压计算公式。     

The effect of hot-dipped aluminum coatings on Fe-8Al-30Mn-0.8C alloy

The morphology and microstructure of an intermetallic layer formed on the surface of Fe-8Al-30Mn-0.8C alloy by hot-dip aluminization treatment have been examined in detail. The phases present in the coating are unambiguously identified by means of transmission electron microscopy. After aluminization, a two layer coating was formed consisting of an external Al layer and a (Fe, Mn)₂Al₅ intermetallic on top of the substrate. The (Fe,Mn)₂Al₅ compound has an orthorhombic structure with lattice parameters a = 0.752 nm, b = 0.667 nm and c = 0.417 nm. The activation energy (E_FeMnAl) for the growth of such an intermetallic layer is calculated to be 52.7 kJ/mol. These results are different from those observed in aluminized low-carbon steel (E_Fe). The difference between E_FeMnAl and E_Fe is attributed to the alloying elements (Mn) in the present alloy. Environmental salt fog corrosion and high temperature oxidation tests were carried out to examine the corrosion and oxidation resistance. The results indicated that both the corrosion and oxidation resistance of the Fe-8Al-30Mn-0.8C alloy treated by hot-dip aluminization can be significantly increased.     

Pilot study of mechanism of property-modified anode in aluminum electrolysis

1　INTRODUCTIONAluminummetallurgyadoptsthemethodofhightemperaturemeltsaltelectrolysisdevelopedonehun dredyearsago .Intheprocessofresearchanddevel opmentinthisfield ,physicalchemistry ,electro chemistry ,materialscience ,roboticizedtechnologyandsoonwerecombinedwithaluminummetallurgytechniques,makingthebasicprincipleoftheHall Heroultprocessbeingmoredeeplyrealizedbypeople .Furthermore ,thistechnologywasdevelopedcon stantlyandbecamemoreandmoreperfectinordertofurthersaveenergy ,reducerawmateri…     

Selective oxidation of Fe-30Ni alloy in a low-temperature range (433–473 K)

Fe-30Ni alloy specimens were oxidized for 10–240 min at 433–473 K in pure oxygen at a pressure of 1.33×10⁴ Pa. The thickness of oxide films was measured by a multiple-angle-of-incidence ellipsometer. The kinetics of film growth were found to obey a parabolic rate law. The depth-profiling of oxidized surfaces, performed with simultaneous use of Auger electron spectroscopy (AES) and argon-ion sputter-etching technique, reveals that iron component is selectively oxidized and an iron-depeletion zone is formed in the underlying alloy. The thickness of the iron depletion zone increases with increasing oxidation time or oxidation temperature. During surface oxidation of the alloy, the transport rate of iron component in the film is almost equal to the interdiffusion rate in the underlying alloy, indicating the establishment of a steady state. The values of the interdiffusion coefficient, , of the underlying alloy estimated from the depth-composition profiles are more than 10 orders of magnitude as large as the values extrapolated from the lattice diffusion data of the corresponding alloy obtained at high temperature. The enormously large values of may be explained in terms of the vacancy (monovacancy or divacancy)-enhanced lattice diffusion mechanism.