ZnFe2O4基材料在NaF-AlF3-Al2O3熔盐中的腐蚀

采用锌铁尖晶石材料作为铝电解惰性阳极,考察了这种阳极在 熔盐中的腐蚀 行为,阳极电流密度为0～2.5A/cm2．实验结果表明,锌铁尖晶石材料在阳极极化条件下的NaF-AlF3-Al2O3熔盐中具有很好的耐腐蚀性能．在低电流密度下,阳极材料的腐蚀速度随电流密度的增大而增大,最高的腐蚀速度出现于0.5～0.75A/cm2．此后,腐蚀速度随电流密度的增大而降低．实验证明,高阳极电流密度(＞1.5A/cm2)、熔盐电解质中保持高Al2O3含量和低NaF/AlF3摩尔比,对降低阳极材料的腐蚀速度有利,这也将是惰性阳极应用的重要条件．     

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。     

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。     

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。     

Effect of adding methods of metallic phase on microstructure and thermal shock resistance of Ni/（90NiFe2O4-10NiO） cermets

Ball mixing and electroless plating were respectively used as the adding methods of metallic phase to prepare Ni/（90NiFe2O4-10NiO） cermets for the inert anode in aluminum electrolysis. The microstructure and thermal shock resistance of cermet samples were studied. The results show that, for the samples prepared by ball mixing method, aggregation of metallic phase is found in either the green blocks or sintered samples and the extent of aggregation increases with the increase of metal content. For 6.5Ni/（90NiFe2O4-10NiO） cermets prepared with electroless plating method, the homogeneous and fine metallic particles are found in either the green compacts or sintered samples, but the relative density and thermal shock residual strength decrease by 3% and 28%-58% respectively, compared with samples prepared with ball mixing method.     

电流密度对铝电解NiFe_2O_4基金属陶瓷惰性阳极腐蚀的影响

在Na3AlF6-K3AlF6-AlF3-Al2O 3熔体中,研究电流密度对22(Ni+Cu)/(NiFe2O4-10NiO)金属陶瓷惰性阳极腐蚀速率的影响,并分析腐蚀后阳极的微观结构。结果表明,随着电流密度的升高,NiFe2O4基金属陶瓷惰性阳极腐蚀从以化学溶解腐蚀为主逐渐转变为以电化学腐蚀为主,腐蚀率先降低而后增大。当电流密度从1.0 A/cm2增大至1.6 A/cm2时,阳极年腐蚀率从1.22 cm/a降低至0.137 cm/a;进一步提高电流密度至4.0 A/cm2时,阳极年腐蚀率增大到4.96 cm/a。     

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％。     

Yb_2O_3掺杂对15(20Ni-Cu)/(NiFe_2O_4-10NiO)金属陶瓷性能的影响

采用冷压-烧结技术制备NiFe2O4-10NiO基金属陶瓷材料;通过对烧结体的显微结构和物相组成、电导率、电解试样的表层形貌、电解质和阴极铝的杂质增量等的分析检测,研究Yb2O3掺杂对15(20Ni-Cu)/NiFe2O4-10NiO金属陶瓷致密度、导电率和耐腐蚀性能的影响。结果表明:1 300℃烧结的0.5%Yb2O3-15(20Ni-Cu)/(NiFe2O4-10NiO)金属陶瓷具有较好的性能,相对密度为98.53%,960℃时的电导率为53.06 S/cm,电解腐蚀后金属腐蚀层厚度为20~30μm,总杂质增量为0.079 g。     

NiFe2O4基金属陶瓷惰性阳极腐蚀组元在电解质中的传质研究

通过计算铝电解用NiFe2 O4基金属陶瓷惰性阳极腐蚀组元Fe、Ni和Cu在铝电解质中的传质系数,讨论了不同过热度下不同阳极腐蚀组元在电解质中的传质行为.结果表明,过热度对不同腐蚀组元的影响不明显,Cu的抗腐蚀性能最好,Ni次之,而Fe最差.     

提高KF-AlF3-Al2O3熔体中Cu-Al基阳极的耐腐蚀性

采用恒电流和动电位极化技术研究经预氧化的和未经预氧化的Cu-Al基阳极(Cu-10Al和Cu-9.8Al-2Mn)在KF-AlF₃-Al₂O₃熔体中的阳极行为。将合金在700℃下进行短时间(8 h)氧化,然后在800℃下施以0.4 A/cm²的电流密度进行1 h恒电流极化。测定扫描速率为0.01 V/s的动电位曲线。对在阳极表面冻结的熔体样品进行XRD分析,并在实验后对阳极进行SEM分析,以研究合金表面形成的氧化皮的物相。所有阳极材料的稳态电位都在2.30~2.50 V(vs Al/AlF₃)范围内。根据动电位极化获得的数据计算阳极的腐蚀速率。结果表明,经预氧化的阳极比未经预氧化的阳极具有更低的腐蚀速率。     

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.     

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…     

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.     

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…     

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。     

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 …     

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.