Effect of metallic content on mechanical property of Ni/(10NiO-NiFe_2O_4) cermets

Ni/ （10NiO-NiFe2O4） cermets were fabricated by using cold pressing-sintering method. The phase composition and effect of metallic content on the mechanical properties such as bending strength, Vickers’ hardness, fracture toughness and thermal shock resistance were studied. The results show that the cermets consist of Ni, NiO and NiFe2O4. Within the range of metallic content from 0 to 17%（mass fraction）, the relative density decreases with the increase of metallic content and the decrease of sintering temperature, Vickers’ hardness decreases from 7097MPa to 4814MPa and the bending strength increases from 110MPa to 157MPa, and the fracture toughness reaches the optimal value of 5.11MPa·m 1/2 at the metallic content of about 10%. The residual strength after thermal shock testing falls sharply as the thermal shock temperature difference is above 200℃.The cermets samples, whose metallic content is 10% and 15%, respectively, exhibit promising property of thermal shock resistance at 960℃ with six cycles of heating and quenching testing.

Effect of BaO addition on relative density and electric conductivity of xNi/10NiO-NiFe_2O_4 cermets

xNi/10NiO-NiFe2O4 （x=5, 10, 17） cermets and those doped with 1% BaO （mass fraction） were prepared by cold isostatic pressing at 200 MPa and sintering in nitrogen atmosphere at 1 473 K. The effects of BaO addition on relative density, microstructure and electric conductivity of cermets were investigated. The results show that relative densities ofxNi/10NiO-NiFe2O4 cermets （x=5, 10, 17） doped with 1% BaO at 1 473 K in nitrogen atmosphere are increased by 0.49%, 1.45% and 2.99% compared with those of the undoped BaO cermets, respectively. Moreover, the electric conductivities （21.98, 28.37 and 50.10 S/cm） of xNi/10NiO-NiFe2O4 cermets （x=5, 10, 17） doped with 1% BaO at 1 233 K are improved compared with those （18.70, 22.79 and 39.58 S/cm） of xNi/lONiO-NiFe2O4 cermets （x=5, 10, 17）, respectively. This indicates that perhaps the addition of BaO or formation of BaFe204 and Ba2Fe2O5 has an active effect on electric conductivities ofxNi/10NiO-NiFe2O4 （x=5, 10, 17） cermets.

Effect of NiO content on corrosion behaviour of Ni-xNiO-NiFe_2O_4 cermets in Na_3AlF_6-Al_2O_3 melts

Ni-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 （un-）（favorable） to the densification 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.

Effect of sintering atmosphere on corrosion resistance of Ni/(NiFe_2O_4-10NiO) cermet inert anode for aluminum electrolysis

A comparative study on the corrosion resistance of 17Ni/（NiFe2O4-10NiO） cermet inert anode prepared in differentsintering atmospheres was conducted in Na3AlF6-Al2O3 melt. The results indicate that the corrosion rates of NiFe2O4-based cermetanodes prepared in the vacuum and the atmosphere with oxygen content of 2×10^-3 （volume fraction） are 6.46 and 2.71 cm/a,respectively. Though there is a transition layer with lots of holes or pores, a densified layer is formed on the surface of anode due tosome reactions producing aluminates. For the anode prepared in the atmosphere with oxygen content of 2×10^-3, the thickness of thedensification layer （about 50 μm） is thicker than that （about 30 μm） formed on the surface of anode prepared in the vacuum. Thecontents of NiO and Fe（II） in NiFe2xO4-y-z increase with the decrease of oxygen content in sintering atmosphere, which reduces thecorrosion resistance of the material.

Corrosion of NiFe_2O_4-10NiO-based cermet inert anodes for aluminium electrolysis

NiFe2O4-10NiO-based cermet inert anodes for aluminium electrolysis were prepared and their properties were investigated in a lab-scale electrolysis cell. The results show that the inert anodes exhibit good performance during electrolysis in molten salt cryolite at 960 °C, but according to the analyses of phase compositions and microstructures through XRD, SEM/EDX and metallographic analysis, the metal in the anodes is preferentially corroded and many pores are produced on the anode surface after electrolysis. The preferential dissolution of Fe in the NiFe2O4 phase may lead to the non-uniform corrosion of NiFe2O4 grains. Moreover, a dense protective layer of NiFe2O4-NiAl2O4-FeAl2O4 is formed on the anode surface, which originates from the reaction of Al2O3 dissolved in the electrolyte with NiO or FeO, the annexation of NiFe2O4-NiAl2O4-FeAl2O4 to NiO and volume expansion. Thus, the dense NiFe2O4-NiAl2O4-FeAl2O4 layer inhibits the metal loss and ceramic-phase corrosion on the surface of the cermet inert anodes.

NiFe_2O_4/NiFeCuAlSn金属陶瓷的导电性能

对用粉末冶金法制备的几种NiFe2O4／NiFeCuAlSn金属陶瓷电阻率进行了测试与分析，结果表明：随着合金含量的增加，样品的导电性由半导体陶瓷导电性向金属导电性转变；在600-800℃温度范围内，由于样品中金属相的氧化加剧，导致导电性能下降，当金属含量为80％时，在1000℃下金属陶瓷中金属相氧化严重，并存在NiFe2O4陶瓷相被还原的现象，电阻率大幅上升；金属陶瓷导电性能的提高取决于金属相在陶瓷中的分布形貌，网状分布的金属相能有效地提高金属陶瓷的导电性能。

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·cm 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% Cu-Ni 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.

EFFECT OF Cu-Ni CONTENT ON THE CORROSION RESISTANCE OF(Cu-Ni)/(10NiO-90NiFe_2O_4)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 metallic phase content on mechanical properties of (85Cu-15Ni)/(10NiO-NiFe_2O_4) 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 (△t) 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 △t is above 200 ℃, the residual strength sharply decreases for sample CN0 and falls slowly for samples CN5-CN20.

Effect of metallic phase species on the corrosion resistance of 17M/(10NiO-NiFe_2O_4) cermet inert anode of aluminum electrolysis

NiFe2O4-based cermet inert anodes with metallic phase compositions of Cu, Ni and 85Cu15Ni were prepared by cold pressing-sintering. Their corrosion resistance was also investigated in Na3 AIF6-Al2O3 melts. The resuits show that the metallic phase species in cermets have no effect on the concentration of impurities in bath during electrolysis, the total steady-state concentration of impurities is almost the same, i.e. between 4.12 × 10^-4- 4.80 × 10^-4. There exists metal preferential corrosion for the cermet inert anode with metal Ni as metallic phase. For NiFe2 O4-based cermets, the cermet with metal Cu as metallic phase exhibits better corrosion resistance than the others.

Results from 100 h electrolysis testing of NiFe_2O_4 based cermet as inert anode in aluminum reduction

A 100 mm diameter cup-shaped inert anode for aluminum electrolysis consisting of cermet 17Ni/83(10NiO-90NiFe2O4) was prepared and the operating performance was evaluated in a laboratory cell with the electrolyte CR2.3 and Al2O3 concentration 7.43% (mass fraction). The results indicate that no major operational difficulties are encountered during the testing which lasts for 101.5 h and the inert anode exhibits good general performances. The steady-state average concentration of impurity Ni in the bath is close to the solubility, however, the Fe concentration is lower than its solubility. The contents of the main contaminants for aluminum produced are Ni 0.128 8%, Fe 1.007 4%. The corrosion rate of inert anode under electrolysis conditions based on the content of impurity Ni in metal aluminum is approximately 8.51 mm/a.

Preliminary testing of NiFe_2O_4-NiO-Ni cermet as inert anode in Na_3AlF_6-AlF_3 melts

The electrical conductivity of cermet 83(90NiFe2O4-10NiO)-17Ni at different temperatures was measured in air, the operating performance of inert anode was evaluated in a laboratory electrolysis cell with various electrolyte compositions. The results indicate that the electrical resistivity of cermet studied has negative temperature coefficient, which is the characteristic of semi-conducting material. The proper addition of AlF3 in the bath can improve the corrosion resistance of cermet inert anode, but excess adding amount will cause the catastrophic corrosion. Post-examination of anodes shows that metal Ni leaches preferentially on the anode surface. Chemical dissolution, electrolyte penetration as well as electrochemical dissolution serve as major corrosion mechanisms.

Sintering of the NiFe_2O_4-10NiO/xNi Cermet

The sintering behavior of NiFe2 O4-10NiO/xNi cermet which was used as the most prospective inert anode materials for aluminum electrolysis was studied by examining the effects of raw powder particle size, sintering temperature, and the contents of Ni. The results show that fine particle size enables the powder to have high driving force for sintering. High temperature is beneficial to densification, but the ultra-high temperature does harm to the improvement of the density. The samples of NiFe2O4-10NiO/SNi has the highest relative density of 97.28 % when it is sintered at 1 350 ℃, but it decreases to 95.23 % when sintered at 1 400 ℃. Low addition of Ni has a great help to the sintering of NiFe2 O4-10NiO matrix. When the samples are sintered at 1 350 ℃ and the mass fraction of Ni is 5%, the highest relative density is gained, but the density decreases with the further increase of Ni contents. The low density of the sintered samples of NiFe2 O4-10NiO/17Ni is attributed to the high volume fraction of pores.

Electrical conductivity of Cu/(10NiO-NiFe_2O_4) cermet inert anode for aluminum electrolysis

Cu/(10NiO-NiFe2O4) cermets containing mass fractions of Cu of 5%, 10%, 15% and 20% were prepared, and their electrical conductivities were measured at different temperatures. The effects of temperature and content of metal Cu on the electrical conductivity were investigated especially. The results indicate that the metallic phase Cu distributes evenly in 10NiO-NiFe2O4 ceramic matrix. The mechanism of electrical conductivity of Cu/(10NiO-NiFe2O4) cermets obeys the rule of electrical mechanism of semiconductor, the electrical conductivity for cermet containing 5% Cu increases from 2.70 to 20.41 S/cm with temperature increasing from 200 to 900 ℃. The change trend of electrical conductivity with temperature is similar with each other and it increases with increasing temperature and content of metal Cu. At 960 ℃, the electrical conductivity of cermet increases from 2.88 to 82.65 S/cm with the content of metal Cu increasing from 0 to 20%.

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

Sintered samples of nickel ferrite nickel oxide ceramic, usually used as the ceramic phase of cermet inert anode in aluminum electrolysis, were prepared and characterized. The solubilities of NiFe 2O 4 NiO ceramics were measured using an equilibration technique in the Na 3AlF 6 10%AlF 3 5%CaF 2 5 %Al 2O 3 melts at 960 ℃. Electrical resistivity was also measured for NiFe 2O 4 NiO ceramic samples prepared using the usual ceramic technique as function of temperature and content of NiO with an improved pyroconductivity test device, consisting of a specially constructed closed furnace and a Potentiostat/Galvanostat, based on the conventional direct current four probe technique. Results show that, under the experimental conditions, the solubility of Fe from NiFe 2O 4 is 0.06% and Ni from NiFe 2O 4 is 0.008%. The solubility of Fe and Ni from NiFe 2O 4 NiO ceramic is inversely related to each other. The solubility of Ni increases but overall solubility of NiFe 2O 4 NiO ceramics decreases with increasing NiO content. The studied ceramic samples have a semiconductor behavior where electrical resistivity ρ decreases with increasing temperature and the resistivity ρ increases with increasing porosity. The resistivity ρ of NiFe 2O 4 NiO ceramic shows a minimum with increasing the content of NiO at various temperatures.

Effect of CaO doping on corrosion resistance of Cu/(NiFe_2O_4-10NiO) cermet inert anode for aluminum electrolysis

The CaO-doped Cu/（NiFe2O4-10NiO） cermet inert anodes were prepared by the cold isostatie pressing-sintering process, and their corrosion resistance to Na3AlF6-K3AlF6-Al203 melt was studied. The results show that the relative density of 5Cu/（NiFe2O4-10NiO） cermet sintered at 1 200 ℃ increases from 82.83% to 97.63% when 2% CaO （mass fraction） is added. During the electrolysis, the relative density of cermet inert anode descends owing to the chemical dissolution of additive CaO at ceramic grain boundary, which accelerates the penetration of electrolyte. Thus, the corrosion resistance to melts of Cu/（NiFe2O4-10NiO） cermet inert anode is reduced. To improve the corrosion resistance of the cermet inert anode, the content of CaO doped should be decreased and the technology of cleaning the ceramic grain boundary should be applied.

铝电解用NiFe_2O_4基金属陶瓷的制备

以铝电解惰性阳极为应用目标 ,制备了不同金属相 (Cu Ni)含量的Ni Cu NiFe2 O4 金属陶瓷 ,研究了烧结气氛、温度和保温时间对其性能的影响 ,解决了烧结过程中氧化物陶瓷的离解和金属相被氧化的问题 ,比较了不同烧结条件下所得试样的基本物理参数 ,找到了较优的Ni Cu NiFe2 O4 金属陶瓷制备工艺。结果表明 :Cu NiFe2 O4 金属陶瓷的金属相中添加 15wt%Ni后 ,可以提高金属相的液相线温度 ,改善金属相对NiFe2 O4 陶瓷相的润湿性能 ,从而可在保证金属相不溢出且分布均匀的前提下 ,大大提高金属陶瓷的烧结温度和保温时间 ,显著提高金属陶瓷的致密度 ,进而改善金属陶瓷惰性阳极的耐腐蚀性能和导电性能。

气氛对NiFe_2O_4陶瓷烧结致密化的影响

采用不同的烧结工艺制备了NiFe2O4陶瓷材料,研究了真空、大气、N23种气氛对NiFe2O4陶瓷材料烧结致密度的影响,解决了烧结过程中NiFe2O4陶瓷的离解问题。结果表明:在制备NiFe2O4陶瓷过程中,烧结气氛严重影响着陶瓷的离解和致密化;真空烧结将导致NiFe2O4陶瓷的离解,N2气氛保护烧结所制备出的NiFe2O4陶瓷样品的密度较大气气氛烧结所制备出的样品的密度高出14.6%～32.6%。分析结果表明:因NiFe2O4陶瓷高温失氧所带来的表面能和晶体缺陷的差异是影响其致密化的关键;无论在何种气氛下烧结,提高烧结温度都有利于提高NiFe2O4样品的烧结密度。

NiFe_2O_4基金属陶瓷材料的制备及其耐腐蚀性能

采用传统粉末冶金技术制备了铝电解用Cu NiFe2O4和Ni NiFe2O4金属陶瓷惰性阳极,并对其在Na3AlF6 Al2O3熔体中的腐蚀行为进行了研究。研究结果表明:NiFe2O4基金属陶瓷阳极的腐蚀行为与热力学计算结果吻合;金属Cu与NiFe2O4陶瓷的润湿性能不好,Cu NiFe2O4金属陶瓷的致密化和导电性能难以提高;致密度过低时,会导致金属相高温氧化和电解质浸渗,电极肿胀、开裂;在电解过程中,5%Cu NiFe2O4存在金属相聚集和在陶瓷基体中Fe优先溶解的现象,但金属铜并未发生阳极溶解;5%Ni NiFe2O4金属陶瓷易实现致密化烧结,在电解过程中表现出良好的耐腐蚀性能,会发生金属Ni的阳极溶解,并存在陶瓷基体中铁优先溶解的现象。

金属含量对Cu-Ni-NiFe_2O_4金属陶瓷导电性能的影响

制备了添加不同含量的Cu和Ni金属粉末作为导电组元的NiFe2O4基金属陶瓷材料,研究了材料的物相组成、显微组织以及金属相含量对材料致密度和电导率的影响。研究结果表明,所制备的金属陶瓷材料由NiFe2O4和Cu Ni合金相组成,其中细小且形状不规则的(Cu Ni)相均匀地镶嵌在NiFe2O4陶瓷基体上;试样的致密度在金属含量为0～20%范围内存在极大值;Cu Ni NiFe2O4金属陶瓷遵循半导体导电机理,其电导率随着温度的升高和金属含量的增大而增大。