Electrical conductivity of Cu/（10NiO-NiFe2O4） 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 metallic content on mechanical property of Ni/（10NiO-NiFe2O4 ） cermets

1 INTRODUCTIONThe use of inert or non-consumable anodes forreplacement of consumable carbon anodes in Hall-H啨roult electrolysis cells for the production of alu-minum has been a technical and commercial goalfor many decades .In the present process ,consumable carbon an-odes are used,andthe anode product is CO2. Withaninert anode ,the cell reaction will be :Al2O3=2Al +23O2(1)The basic requirements for aninert anode are :1) to exhibit a lowcorrosion rate in the high tem-perature melts an…     

Densification and sintering dynamics of 10NiO-NiFe2O4 composites doped with CaO

The effects of CaO content in the range from 0 to 4.0%, and sintering temperature on the phase composition, relative density and electrical conductivity of 10NiO-NiFe2O4 composites doped with CaO were studied. The results show that there is no change of structure for NiO or NiFe2O4; there is apparent oxygen absorbing and releasing behavior during the heating process in air for 10NiO-NiFe2O4 composites. Introduction of CaO can accelerate the densification of 10NiO-NiFe2O4 composites. The maximum value of relative density is 98.75% for composite doped with 2.0% CaO and sintered at 1 200 ℃, which is beyond about 20% for the undoped composites. The sintering activated energy of sample containing 2% CaO decreases by 15.87 kJ/mol, compared with that of the undoped sample.     

Sintering of the NiFe2O4-10NiO/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.     

Preparation and properties of 4.25Cu-0.75Ni／NiFe2O4 cermet

4.25Cu-0.75Ni/NiFe₂O₄ cermets were prepared by doping NiFe₂O₄ ceramic matrix with the mixed powders of Cu and Ni or Cu-Ni alloy powder as the electrical conducting metallic elements. The effects of technological parameters, such as the adding modes of metallic elements, the ball milling time, the sintering time and the sintering temperature, on the relative density and resistivity of the cermets were studied. The results show that the resistivity of 4.25Cu-0.75Ni/NiFe₂O₄ cermets decreases with increasing temperature, and has a turning point at 590 °C, which is similar to that of NiFe₂O₄ ceramic. The sintering temperature and adding modes of metallic elements have a great influence on the properties of 4.25Cu-0.75Ni/NiFe₂O₄ cermets. When the sintering temperature increases from 1200 °C to 1300 °C, the relative density increases from 89.86% to 95.33%, and the resistivity at 960 °C decreases from 0.11 Ω · cm to 0.03 Ω · cm, respectively. When the metallic elements are added with the mixed powders of Cu and Ni, the cermets of finely and uniformly dispersed metallic phase, high density and electric conductivity are obtained. The relative density and resistivity at 960 °C are 90.23% and 0.04 Ω · cm respectively for the cermet samples sintered at 1200 °C for 2 h, which are both better than those of the cermets prepared under the same technique conditions but with the metallic elements added as 85Cu-15Ni alloy powders. Foundation item: Project (G1999064903) supported by the National Key Fundamental Research and Development Program of China; project(2001AA335013) supported by the National High Technology Research and Development Program of China; project (50204014) supported by the National Natural Science Foundation of China     

Influence on performance and structure of spinel LiMn2O4 for lithium-ion batteries by doping rare-earth Sm

The spinel LiMn₂O₄ used as cathode materials for lithium-ion batteries was synthesized by mechano-chemistry fluid activation process, and modified by doping rare-earth Sm. Thesting of X-ray diffraction, cyclic voltammograms, charge-discharge and SEM was carried out for LiMn₂O₄ cathode materials and the modified materials. The results show that the cathode materials doped rare earth Li _x Mn_2−y Sm _z O₄ (0.95⩽x⩽1.2, 0⩽y⩽0.3, 0⩽z⩽0.2) exhibit standard spinel structure, high reversibility of electrochemistry and excellent properties of charge-discharge. In EC: DMC(1 : 1)+1 mol/L LiPF₆ electrolyte with discharge capacity more than 130 mA · h/g, and its capacity is deteriorated less than 15% after 300 cycles at room temperature and less than 20% after 200 cycles at 55°C. At the same time, Crystal Field Theory was applied to explain the function and mechanism of doped rare earth element. Foundation item: Project (02JJY2081) supported by the Natural Science Foundation of Hunan Province     

Effect of metallic phase species on the corrosion resistance of 17M/（10NiO-NiFe2O4） cermet inert anode of aluminum electrolysis

1 INTRODUCTIONThere are many disadvantages in the presentaluminumelectrolysis with carbon anode ,such assevere energy consumption,carbon wasting,envi-ronmental pollution and so on.Inert electrode sys-tem can overcome these disadvantages[1 3]. Re-cently ,the researches of the inert anode materialshave mainly been concentrated on alloys[4]and cer-met materials[5 ,6]. NiFe2O4based cermets , whichpossess not only high electrical conductivity ofmetal but also good corrosion resistance of cera…     

The Effect of Bi2O3 on the Structure and Microwave Dielectric Properties of Ba6-3xNd8＋2xTi18O54 System（x=2/3）

The structures and dielectric properties of Ba6-3xNd8＋2xTi18O54 system（x=2/3） doped with different contents of Bi2O3, whose final molecular formula is Ba6-3x（Nd1-yBiy）8＋2xTi18O54 were investigated. It is indicated that the dielectric constant increases greatly whereas Q value（f0=4 GHz） decreases with the increase of Bi2O3 content. However, the temperature coefficient could be controlled below 0±30×10^-6/℃ in the experiment. These phenomena are related to the appearance of a new phase, Bi4Ti3O12, which has high dielectric constant. Also, that Bi^3＋（0.13 nm） substitutes for Nd^3＋（0.099 5 nm） will increase the unit cell volume, which will lead to the enlargement of the octahedron B site occupied by Ti^4＋. So the spontaneous polarization of Ti^4＋ ions will be strengthened. Besides, Bi^3＋ will fill up some vacancies which Ba^2＋ or Nd^3＋ ions leave in two A1 sites and four A2 sites. More positive ions polarize, which also contributes to higher dielectric constant. The samples got with the optimium properties are sintered at 1 200 ℃ for 4 h, when y=0.25, ε≈110, Q≈5 400（f0=4 GHz）, TCC=-4.7×10^-6/℃; When y=0.3, ε≈120, Q≈5 000（f0=4 GHz）, TCC=-24×10^-6/℃.     

Forming regularity and relation between composition and property of B2O3-BaO-ZnO glass

B2O3-BaO-ZnO glass was prepared by using conventional melt quenching technology. The forming regularity and the relationship between the composition and the property of B2O3-BaO-ZnO glass were investigated. The results show that the composition range for forming B2O3-BaO-ZnO glass is very wide, but the content of B2O3 has a limit within mole fraction of 25%-75%. When the content of B2O3 is over the limit, the melt will be divided into two phases with different compositions and structures, whereas too low content of B2O3 will result in the crystallization of the melt during the cooling process. The thermal expansion coefficient, the transition temperature and the resistivity of the glass at room temperature are (5-10)×10-6 ℃-1, 480-620 ℃ and (1.5-3.0)×1010 Ω·m, respectively.     

Effect of electrolysis superheat degree on anticorrosion performance of 5 Cu/（10NiO-NiFe2O4） 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.     

Structures and magnetic properties of nanocomposite CoFe2O4-BaTiO3 fibers by organic gel-thermal decomposition process

The nanocomposite xCoFe₂O₄-(1−x)BaTiO₃ (x=0.2, 0.3, 0.4, 0.5, molar fraction) fibers with fine diameters and high aspect ratios (length to diameter ratios) were prepared by the organic gel-thermal decomposition process from citric acid and metal salts. The structures and morphologies of gel precursors and fibers derived from thermal decomposition of the gel precursors were characterized by Fourier transform infrared spectroscopy, X-ray diffractometry and scanning electron microscopy. The magnetic properties of the nanocomposite fibers were measured by vibrating sample magnetometer. The nanocomposite fibers consisting of ferrite (CoFe₂O₄) and perovskite (BaTiO₃) are formed at the calcination temperature of 900 °C for 2 h. The average grain sizes of CoFe₂O₄ and BaTiO₃ in the nanocomposite fibers increase from 25 to 65 nm with the calcination temperature from 900 to 1 180 °C. The single fiber constructed from these nanograins of CoFe₂O₄ and BaTiO₃ has a necklace-like morphology. The saturation magnetization of the nanocomposite 0.4CoFe₂O₄-0.6BaTiO₃ fibers increases with the increase of CoFe₂O₄ grain size, while the coercivity reaches a maximum value when the average grain size of CoFe₂O₄ is around the critical single-domain size of 45 nm obtained at 1 000 °C. The saturation magnetization and remanence of the nanocomposite xCoFe₂O₄-(1−x)BaTiO₃ (x=0.2, 0.3, 0.4, 0.5) fibers almost exhibit a linear relationship with the molar fraction of CoFe₂O₄ in the nanocomposites.     

Bonding mechanism of X10CrNi18-8 with Ni/Al_2O_3 composite ceramic by pressureless infiltration

An alloy steel/alumina composite was successfully fabricated by pressureless infiltration of X10CrNi18-8 steel melt on 30%(mass fraction) Ni-containing alumina based composite ceramic(Ni/Al2O3) at 1 600 ℃.The infiltration quality and interfacial bonding behavior were investigated by SEM,EDS,XRD and tensile tests.The results show that there is an obvious interfacial reaction layer between the alloying steel and the Ni/Al2O3 composite ceramic.The interfacial reactive products are(FexAly)3O4 intermetallic phas...     

Thermoelectric properties of Ca3Co4O9 ceramics

Ca₃Co₄O₉ ceramics were prepared using the sol-gel process with ordinary pressing sintering and their thermoelectric properties were measured from room temperature to 673 K. The experimental results show that single phase Ca₃Co₄O₉ can be fabricated at 750–900 °C in different citrate acid molar proportions for 0.2–1.0. For all the oxides, both the Seebeck coefficients S and the electrical conductivities κ increase with the increasing temperature. The Seebeck coefficients S are all positive. The thermal conductivities k increase with the increasing temperature also and the lattice thermal conductivity κ _l plays an important role to the thermal conductivity κ. The citrate acid molar proportions have a large influence on the particle sizes, which influences the thermoelectric properties of the ceramics. The figure of merit increases with the increasing temperature and reaches 4.5×10⁻⁵ K⁻¹ at 573 K for the sample in the citrate acid molar proportion of 0.46.     

Electrical conductivity of （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts

The effects of contents of AlF3 and Al2O3, and temperature on electrical conductivity of （Na3AlF6-40%K3AlF6）- AlF3-Al2O3 were studied by continuously varying cell censtant （CVCC） technique. The results show that the conductivities of melts increase with the increase of temperature, but by different extents. Every increasing 10 ℃ results in an increase of 1.85 × 10^-2, 1.86× 10^-2, 1.89 × 10^-2 and 2.20 × 10^-2 S/cm in conductivity for the （Na3AlF6-40%K3AlF6）-AlF3 melts containing 0%, 20%, 24%, and 30% AlF3, respectively. An increase of every 10 ℃ in temperature results an increase about 1.89× 10^-2, 1.94 × 10^-2, 1.95 × 10^-2, 1.99× 10^-2 and 2.10× 10^-2 S/cm for （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts containing 0%, 1%, 2%, 3% and 4% Al2O3, respectively. The activation energy of conductance was calculated based on Arrhenius equation. Every increasing 1% of AlF3 results in a decrease of 0.019 and 0.020 S/cm in conductivity for （Na3AlF6-40%K3AlF6）-AlF3 melts at 900 and 1 000 ℃, respectively. Every increase of 1% Al2O3 results in a decrease of 0.07 S/cm in conductivity for （Na3AlF6-40%K3AlF6）-AlF3-Al2O3 melts. The activation energy of conductance increases with the increase in content of AlF3 and Al2O3.     

Effect of CaO doping on corrosion resistance of Cu/（NiFe2O4-10NiO） 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.     

First-principle investigation on stability of Co-doped spinel λ-Mn4-xCoxO8

The mechanism of stability of Co-doped spinel λ-MnO2 that is referred to as spinel LixMn2O4 （x=0） was studied by using the first-principle calculation method. The total energy and formation enthalpy can be decreased remarkably due to the Co substation, resulting in a more stable structure ofλ-MnxCr2-xO4. The bond order and DOS analysis were given in detail to explain the nature of stability improvement. The calculated results show that as the content of Co dopant increases, the bond order of Mn-O becomes larger and the peak of density of states around Fermi level shifts toward lower energy. The charge density distribution illustrates that the Mn-O bonding is ionic and partially covalent, and the covalent Mn-O bonding becomes stronger with the increase of Co dopant content. The results confirm that the Co-doping will enhance the stability of λ-MnO2 and hence improve the electrochemistry performance of LixMn2O4.     

Effects of nucleating additives on crystallization and properties of CaO-B2O3-SiO2 glass-ceramics

ZrO₂, TiO₂ and P₂O₅ were doped in CaO-B₂O₃-SiO₂ glass-ceramics as nucleating additives. Effects of different nucleating additives on the phase separation and crystalline behaviors were investigated by using gradient temperature furnace, DTA and XRD. Then, sintering process of the glass-ceramics was investigated by testing sintering shrinkage, dielectric constant and loss. The experimental results shows that the glass-ceramics doped with nucleating additives represents higher crystallization, with ZrO₂ as an exceptional effective dopant to promote the precipitation of wollastonite crystal. Finally, ZrO₂ containing glass-ceramics was chosen to study the influence of sintering temperature and soaking time with the help of X-ray diffraction analysis and density measurement. The glass-ceramics can be well consolidated at 850 °C for 10 min, with low dielectric constant (5.87) and loss (3.21 × 10⁻⁴), which is desirable for LTCC application.     

Structure and stability of Li-Mn-Ni composite oxides as lithium ion sieve precursors in acidic medium

A series of spinel Li-Mn-Ni composite oxides with theoretical chemical formula of LiNixMn2-xO4 (0≤x≤1.0) were synthesized by liquid phase method. Their structure and morphology were characterized by X-ray diffractometry (XRD) and scanning electron microscopy (SEM),respectively. The stability of these Ni-substituted spinel oxides prepared at different temperatures was investigated in acidic medium as well. The results show that Ni can be brought into the spinel framework completely to form well-crystallized ...     

Microstructure and microwave dielectric properties of CaO-B2O3-SiO2 glass ceramics with various B2O3 contents

The effects of B2O3 addition on both the sintering behavior and microwave dielectric properties of CaO-B2O3-SiO2 (CBS) glass ceramics were investigated by Fourier transform infrared spectroscopy (FTIR),X-ray diffractometry (XRD) and scanning electron microscopy (SEM).The results show that the increasing amount of B2O3 causes the increase of the contents of [BO3],[BO4] and [SiO4],which deduces the increase of CaB2O4 and α-SiO2 and the decrease of CaSiO3 correspondingly.No new phase is observed throughout the...     

Impedance spectroscopy study on Mn1＋xFe2-2xTixO4 （0≤x≤0.5） ferrites

The complex impedance spectroscopy and surface morphology of Mn_1+x Fe_2−2x Ti _x O₄ (0⩽x⩽0.5) system, prepared using a conventional solid state reaction technique, were investigated. The impedance spectroscopy measurements were carried out at room temperature in the frequency range of 42–5 MHz. The electrical processes in the samples were modeled in the form of an equivalent circuit made up of a combination of two parallel RC circuits attributed to grain and grain boundaries. The DC conductivity obtained by extrapolation of AC data using impedance spectroscopy and four-probe method increases at 10% doping of Ti ions. The energy-dispersive X-ray (EDX) pattern confirmed the homogeneous mixing of the Mn, Fe, Ti and O atoms in pure and doped ferrite samples.