Phase evolution of 17(Cu-10Ni)-(NiFe_2O_4-10NiO) cermet inert anode during aluminum electrolysis

17（Cu-10Ni）-（NiFe2O4-10NiO） cermets were prepared by cold pressing and sintering in nitrogen atmosphere, and tested as inert anode for aluminum electrolysis at 960 °C for 10 and 40 h, respectively. Microstructures and phase compositions of the as-sintered and post-electrolyzed samples were investigated. The impurity contents in the electrolyte and the cathode metal were detected in order to investigate the corrosion characteristic of the elements of Fe, Ni and Cu in the anode. A dense NiFe2O4 layer was observed on the surface of anode and thickened with prolonging the electrolysis time. In the newly formed dense ceramic layer, NiO phase disappeared as a result of being swallowed by NiFe2O4 phase, and the metal phase was oxidized during the electrolysis in which Cu element showed a higher dissolution rate than Fe and Ni elements. The formation process of the dense ceramic layer during the electrolysis was presented and explained by using the corrosion mode of the metal phase and the transformation mechanism from NiO phase to NiFe2O4 phase.

Effect of additive BaO on corrosion resistance of xCu/(10NiO-NiFe_2O_4) cermet inert anodes for aluminum electrolysis

xCu/（10NiO-NiFe2O4） cermet and 1BaO-xCu/（10NiO-NiFe2O4） cermet（x=5,10,17） inert anodes were prepared as potential inert anodes for aluminum electrolysis and their corrosion resistance to traditional electrolyte was studied with anodic current density of 1.0 A/cm2 in laboratory electrolysis.The substantial corrosion of metal Cu was observed,many pores appeared on the surface of anode and electrolytes infiltrated inside anodes during the electrolysis.The wear rates of 5Cu/（10NiO-NiFe2O4）,10Cu/（10NiO-NiFe2O4）,17Cu/（10NiO-NiFe2O4）,1BaO-5Cu/（10NiO-NiFe2O4）,1BaO-10Cu/（10NiO-NiFe2O4） and 1BaO-17Cu/（10NiO-NiFe2O4） are 2.15,6.50,8.30,4.88,4.70 and 4.48 cm/a,respectively.The addition of BaO to 10Cu/（10NiO-NiFe2O4） cermet and 17Cu/（10NiO-NiFe2O4） cermet is advantageous because BaO can effectively promote densification and thus improve corrosion resistance.But the addition of BaO to 5Cu/（10NiO-NiFe2O4） cermet is unfavorable to corrosion resistance because additive BaO at the grain boundary of anode accelerates possibly the corrosion of cermet.

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.

Effects of polyaniline on electrochemical properties of composite inert anodes used in zinc electrowinning

In order to search for a suitable anode material used in zinc electrowinning in place of Pb-Ag alloy,Al/Pb-PANI（polyaniline）-WC（tungsten carbide） composite inert anodes were prepared on aluminum alloy substrate by double pulse electrodeposition（DPE） of PANI and WC particles with Pb2＋ from an original plating bath.Thereafter,anodic polarization curves,cyclic voltammetry curves and Tafel polarization curves for the composite inert anodes obtained under different PANI concentrations in the original plating bath were measured,and the microstructural features were also investigated by scanning electron microscopy（SEM）.The results show that Al/Pb-PANI-WC composite inert anode obtained under PANI concentration of 20 g/L in the original plating bath possesses uniform microstructures and composition distributions,higher electrocatalytic activity,better reversibility of electrode reaction and corrosion resistance in a synthetic zinc electrowinning electrolyte of 50 g/L Zn2＋,150 g/L H2SO4 at 35 °C.Compared with Pb-1%Ag alloy,the overpotential of oxygen evolutions for the composite inert anode are decreased by 185 mV and 166 mV,respectively,under 500 A/m2 and 1000 A/m2.

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.

THERMAL STRESSES RELAXATION DESIGN OF Ni/NiFe_(2)O_(4) SYSTEM FUNCTIONALLY GRADED CERMET INERT ANODE

The thermal stresses relaxation of Ni/NiFe2O4 system functionally graded cermet inert anode for aluminum electrolysis was optimally designed. The transient thermal stresses of the inert anode under complex boundary condition during high-temp （955℃） electrolysis were calculated using the finite-element software ANSYS, the influence of different parameters on the distribution of the thermal stresses were analyzed. The results showed that, during the process of thermal shock, the thermal hoop tensile stress on the surface of the anode is very large, which is possibly the major cause of anode crack; when the radius of the anode is between 0.05-0.15m, a range that can be realized by recent manufacturing technology, the optimum composition distribution exponent p is 0.25; The hoop tensile stresses reduce with the decrease of anode scale and also decrease with the decrease of the convection coefficient between the electrolyte and the anode.

EFFECT OF STRUCTURAL PARAMETERS ON THE THERMAL STRESS OF A NiFe_(2)O_(4)-BASED CERMET INERT ANODE IN ALUMINUM ELECTROLYSIS

Inert anode has been a hot issue in the aluminum industry for many decades. With the help of FEA （finite element analysis） software ANSYS, a model was developed to simulate the thermal stress distribution working condition of an inert anode. To reduce its thermal stress, the effect of some parameters on the thermal stress distribution was investigated, including the anode height, the anode radius, the hole depth, the hole radius, and the radius of inner chamfer and outer chamfer. The results showed that in the actual working condition of an inert anode, there existed a large axial tensile stress near the tangent interface between the anode and bath, which was the major cause of anode breaking. Increasing the anode height and reducing the hole depth properly seemed to be beneficial for the stress distribution. With the increase of anode radius, the stress distribution became better first and then deteriorated, the reasonable value was between 0.045 to 0.06m. The hole radius had a significant effect on the stress and a smaller radius would reduce the thermal stress. The effect of the radius of the inner chamfer and the outer chamfer was less than other parameters.

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.

Effect of electrolysis superheat degree on anticorrosion performance of 5Cu/(10NiO-NiFe_2O_4) cermet inert anode

5Cu/(10NiO-NiFe2O4) cermet inert anodes were prepared by cold-pressing and sintering process, and the effect of superheat degree of melting K3AlF6-Na3AlF6-AlF3 on their anticorrosion performance was studied under electrolysis conditions. The results show that, the fluctuation of cell becomes small with increasing of superheat degree, which is helpful to inhibit the formation of cathodic encrustation; the concentration of impurities from inert anode in bath goes up to certain degree, but it is far smaller than those in traditional high-temperature bath. Increasing the superheat degree of melting K3AlF6-Na3AlF6-AlF3 has unconspicuous effect on the contents of impurities in cathodic aluminum. The total mass fractions of Fe, Ni and Cu in aluminum are 15.38% and 15.09% respectively under superheat degree of 95 and 195 ℃. From micro-topography of anode used view, increasing the superheat degree can aggravate corrosion of metal Cu in inert anode, and has negative influence on electrical conductivity of electrode to some extent.

Electrical Conductivity and Corrosion Resistanceof ZnFe _(2)O _(4) Based Materials Used as Inert Anodefor Aluminum Electrolysis

ZnFe 2O 4 and ZnFe 2O 4 based materials were tested to obtain the electrical conductivity and corrosion resistance in melting bath for aluminum electrolysis. The results proved that adequate additives, such as Ni 2O 3 CuO, Cu, ZnO and CeO 2 would increase the electrical conductivity, and the ZnFe 2O 4 based anodes with these additives were of good corrosion resistance. The current density on anode, the mole ratio of NaF/AlF 3 (MR) and the content of alumina in the bath effect the anode corrosion rate in different way.

Current Efficiency, Corrosion and Structural Changes in SnO2-Sb2O3-CuO Inert Anodes for Aluminium Electrolysis

A systematic study was conducted on current efficiency （CE）, corrosion and structural changes in SnO2-based inert anodes （made of 96wt%SnO2＋2wt%Sb2O3＋2wt%CuO） on a laboratory Hall-Heroult aluminium cell. The influence of operating parameters and electrolyte composition on the CE and corrosion process were evaluated. The CE was found to be more than 90% and catastrophic corrosion took place at low percent of Al2O3, high percent of LiF, low cryolite ratio and high current densities. From all the structural changes that took place in the SnO2-based inert anodes, we assumed that the most important contribution was due to the migration of CuO towards the outer limits of the constituent grains of SnO2 based ceramic. The complex process occurred during the formation of various phases and their sintering ability both directly depended on Cu/Sb molar ratio.

EFFECT OF MnO_(2) ADDITIVE ON PERFORMANCES OF NiFe_(2)O_(4) SPINEL BASED INERT ANODE

The NiFe2O4 inert anode is synthesized by high-temperature solid-state reaction method using NiO and Fe2O3 as main raw materials and adding MnO2 powder as additive. Archimedes method using water immersion technique is used to measure the sintering performances of sampies. The static thermal corrosion rates of samples are measured by weight loss. SEM is employed for the observation of material microstructure, and phase structure of the sample surface after corrosion is determined by XRD. The experimental results indicate that a suitable MnO2 additive content is 2%, while the sintering performance is the best, and the static thermal corrosion rate is the lowest. Because of MnO2 dopant enriching at crystal boundary, the corrosion reaction of molten salt to crystal grain creates Mn2AlO4 phase, which is denser than NiFe2O4 phase, and prevents the cryolite molten salt to penetrate into the inert anode, thus reducing the corrosion.

Bubble behavior in aluminum reduction cell with inert anode

The bubble behavior is one of the key factors for the design and the process of aluminum reduction cell using inert anode.A see-through cell is constructed to investigate the bubble flow behavior and the electrolyte flow pattern induced by bubbles.The test results show that the electrolyte is driven by the bubble to move around the cathode,and also some vortices occur in local areas.The bubble generated at the anode bottom undergoes the processes of formation,growth,sliding,detachment and coalescence.However,the bubble generated at the middle of anode detaches rapidly from the anode surface and moves upward and collides with other bubbles,which results in coalescence or break-up.Most bubbles are released into the atmosphere at the liquid surface,while some other bubbles taken by the electrolyte flush to the height higher than the mean horizontal level of the liquid and then drop down and move horizontally and they are released finally.Some bubbles are kept unbroken and are sliding on the electrolyte surface.The diameter of bubble generated at inert anode is smaller than that of bubble generated at graphite anode.Moreover,the bubbles on inert anode are spherical,which was different from those in tubular or disk form on graphite anode.

Corrosion of Zinc Ferrite Based Inert Anodes in AlF_3-NaF-Al_2O_3 Melts Under Conditions of Anodic Polarization

ZnFe2O4-based inert anodes were made to conduct the aluminum electrolysis tests. The corrosion behaviors of the inert anodes were examined and discussed. Experiment results prove that: (1) ZnFe2O4-based inert anodes are good corrosion resistant to AlF3-NaF-Al2O3 melts under the conditions of anodic polarization; (2) High anodic current density ( > 1.5 A·cm-2), high alumina concentration and low ratio of NaF/AlF3 in the molten salts will be the most important conditions for using inert anode.

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%.

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.

SYNTHESIS OF NANO-ZnO PARTICLES FOR ALUMINUM METALLURGY AS INERT ANODE MATERIAL

Nano-ZnO particle was produced by evaporating zinc powders in air at air flow-rate from 0.2 to 0.6m3/h. Nano-ZnO particles was formed by the oxidation of the evaporated zinc vapor. X-ray diffraction shows the powders to be ZnO with lattice parameters of a=0.3249nm and c=0.5205nm. The particle size is dependent upon the transit time from the source to the collection area. The size of particles was ranged between 81 to 103nm. The average density resulted was 4.865g/cm3. Normal ZnO and nano-ZnO were investigated to use them in aluminum metallurgy as an inert anode material. A certain amount of both oxides were molded subsequently inserted to the molten cryolite-aluminum oxide to investigate the corrosive behavior of both oxides. When the sintering temperature increased up to 1300℃, the weight loss ratio rose to 5.01%-7.33% and up to 7.67%-10.18% for nano-ZnO and normal ZnO, respectively. However, when the samples in the molten cryolite aluminum oxide were put for long time, the corrosive rate was found to be higher. It was found that the corrosive loss weight ratio of nano-ZnO anode was much lower than the normal one made from ordinary-ZnO providing that the nano-ZnO is more possible to be use inert anode material.

CORROSION MECHANISM OF SnO2-BASED INERT ANODES

According to the extent of their damage in cryolite melts,the corrosion of SnO_(2)-based inert anodes can be divided into three types,slight corrosion,m&rked corrosion and catastrophic corrosion.The conditions under which these three types take place and their mechanisms are different.Our work shows that depletion of oxygen containing ions in melts,high density,electrolyte penetration into the electrode and intergranular corrosion contribute greatly to marked corrosion and catastrophic corrosion and that the reduction reaction by aluminium only attacks the electrode slightly.

MODEL OF CONDUCTIVITY IN DOPED SnO_(2)-BASE INERT ANODES FOR Al-ELECTROWINNING

The variations of chemical bonding characteristics in doped SnO,-base inert anodes with various dopants are studied using CNDO/2 quantum chemical calculations.A new model of conductivity is derived.which is checked with literature data and our experimental results.Proper dopants can be selected with the model to reduce the resistivity of said electrode effectively.