Densification, microstructure and mechanical properties of SiO2-cBN composites by spark plasma sintering

SiO₂-cBN composites were consolidated by spark plasma sintering at 1473-1973 K. The effects of cBN content and sintering temperature on the relative density, phase transformation, microstructure and mechanical properties of the SiO₂-cBN composites were investigated. The relative density of the SiO₂-cBN composites increased with increasing SiO₂ content. The phase transformation of cBN to hBN in SiO₂-cBN composites was identified at 1973 K, showing the highest transformation temperature in cBN-containing composites. The SiO₂-20 vol% cBN composites sintered at 1673 K showed the highest hardness and fracture toughness of 12.5 GPa and 1.5 MPa m^1/2, respectively.     

Melt differentiation and crystallization of clinker minerals in a CaO-SiO2-Al2O3-Fe2O3 pseudoquaternary system

In the CaO-SiO₂-Al₂O₃-Fe₂O₃ pseudoquaternary system, the solid solutions of Ca₃SiO₅ [C₃S(ss)], Ca₂SiO₄ [C₂S(ss)], Ca₂(Al_xFe_1 − x)₂O₅ with 0.40 ≤ x ≤ 0.57 (ferrite) and Ca₃Al₂O₆ [C₃A(ss)] were crystallized out of a complete melt with 52.9 mass% CaO and Al₂O₃/Fe₂O₃ = 0.70. When the melt was cooled from 1673 K at 80 K/h, the crystals of ferrite with x = 0.40, C₃S(ss) and C₂S(ss) would start to nucleate from the melt at 1630 K. During further cooling, the x value of the precipitating ferrite would progressively increase and eventually approach 0.57 at 1613 K. The resulting ferrite crystals showed a zonal structure, the x value of which successively increased from the cores toward the rims. Actually, the x values of 0.43 and 0.52 were confirmed for, respectively, the cores and rims by EPMA. As the simultaneous crystallization of zoned ferrite, C₃S(ss) and C₂S(ss) proceeded, the coexisting melt would become progressively enriched in the Al₂O₃ component. After the termination of the ferrite crystallization, the C₃A(ss), C₃S(ss) and C₂S(ss) crystallized out of the differentiated melt. The end result was the four phase mixture of ferrite, C₃A(ss), C₃S(ss) and C₂S(ss), being free from the nucleation of Ca₁₂Al₁₄O₃₃ solid solution.     

Effects of cubic BN addition and phase transformation on hardness of Al2O3-cubic BN composites

The Vickers hardness of dense Al₂O₃-cubic BN (cBN) composites prepared by spark plasma sintering under a moderate pressure of 100 MPa at 1200-1600 °C was investigated at indentation loads of 0.098-19.6 N. The BN grains in the Al₂O₃-BN composite prepared at 1300 °C showed no transformation from the cBN to hBN phase, and the hardness was 59 GPa at 0.098 N. The hardness of the Al₂O₃ matrix in the Al₂O₃-BN composites containing 10-30 vol% cBN prepared at 1300-1400 °C was around 25 GPa at 0.098 N, which was higher than monolithic Al₂O₃ bodies prepared at the same temperatures. The hardness of the Al₂O₃ matrix in the Al₂O₃-BN composites decreased with increasing sintering temperature. The increase in the hardness of the Al₂O₃ matrix may be due to the decrease in the size of Al₂O₃ grains in the Al₂O₃-BN composites owing to the addition of cBN particles and the decrease in sintering temperature. The Meyer exponents of the monolithic Al₂O₃ bodies and Al₂O₃-BN composites were 1.90-1.94 independent of cBN content.     

Effect of CeO2 addition on densification and microstructure of Al2O3-YSZ composites

Alumina (Al₂O₃) and alumina-yttria stabilized zirconia (YSZ) composites containing 3 and 5 mass% ceria (CeO₂) were prepared by spark plasma sintering (SPS) at temperatures of 1350-1400 °C for 300 s under a pressure of 40 MPa. Densification, microstructure and mechanical properties of the Al₂O₃ based composites were investigated. Fully dense composites with a relative density of approximately 99% were obtained. The grain growth of alumina was inhibited significantly by the addition of 10 vol% zirconia, and formation of elongated CeAl₁₁O₁₈ grains was observed in the ceria containing composites sintered at 1400 °C. Al₂O₃-YSZ composites without CeO₂ had higher hardness than monolithic Al₂O₃ sintered body and the hardness of Al₂O₃-YSZ composites decreased from 20.3 GPa to 18.5 GPa when the content of ZrO₂ increased from 10 to 30 vol%. The fracture toughness of Al₂O₃ increased from 2.8 MPa m^1/2 to 5.6 MPa m^1/2 with the addition of 10 vol% YSZ, and further addition resulted in higher fracture toughness values. The highest value of fracture toughness, 6.2 MPa m^1/2, was achieved with the addition of 30 vol% YSZ.     

Electrical conductivity relaxation in PVOH-LiClO4-Al2O3

We report on electrical conductivity relaxation measurements of solid polymer electrolytes (SPE) based on poly(vinyl alcohol) (PVOH) and LiClO₄ in which nanoporous Al₂O₃ particles with average pore diameter of 58 Å were dispersed. A power law frequency dependence of the real part of the electrical conductivity is observed as a function of temperature and composition. This behaviour is typical of systems in which correlated ionic motions in the SPE bulk material are responsible for ionic conductivity. This variation is well fitted to a Jonscher expression σ′(ω) = σ₀[1 + (ω/ω₀)^p] where σ₀ is the dc conductivity, ω₀ the characteristic angular frequency relaxation and p is the fractional exponent between 0 and 1. For a prototype membrane with composition 0.9PVOH − 0.1LiClO₄ + 7 wt.%Al₂O₃, it was found that the temperature dependence of σ₀ and ω₀, may be described by the VTF relationship, ? = ?₀ exp[−B/(T − T₀)], with approximately the same constant B and reference temperature T₀, indicating that ion mobility is coupled to the motions of the polymer chains. Moreover, p decreased with increasing temperature, from 0.68 at T = 319 K, to 0.4 at T = 437 K, indicating weaker correlation effects among mobile ions when the temperature is increased.     

Effects of CaSiO3 addition on sintering behavior and microwave dielectric properties of Al2O3 ceramics

The effects of CaSiO₃ addition on the sintering behavior and microwave dielectric properties of Al₂O₃ ceramics have been investigated. The addition of CaSiO₃ into Al₂O₃ ceramics resulted in the emergence of Ca₂Al₂SiO₇ and CaAl₂Si₂O₈, which acting as liquid sintering aids can effectively lower the sintering temperature of Al₂O₃ ceramic. The Q × f value of Al₂O₃-CaSiO₃ ceramics decreased with the CaSiO₃ addition increasing because of the lower Q × f value of Ca₂Al₂SiO₇ and CaAl₂Si₂O₈. Compared with the pure CaSiO₃ ceramic, the Al₂O₃-CaSiO₃ ceramic with 20 wt% CaSiO₃ addition possessed good dielectric properties of ?_r = 9.36 and Q × f = 13,678 GHz at the similar sintering temperature.     

Enhancement of pyrolysis gasoline hydrogenation over Pd-promoted Ni/SiO2-Al2O3 catalysts

Pyrolysis gasoline upgrading by hydrogenation and ring opening was investigated over highly loaded Ni catalysts supported on amorphous silica-alumina and incorporating promoters as Pd, seeking a higher aromatic reduction of this feedstock in order to meet stringent fuel regulations. The effect of Ni loading and Pd component on the activity of those systems was evaluated in a fixed bed reactor under the following operating conditions: T = 573 and 673 K, H₂:PyGas molar ratio = 10, P = 5.0 MPa, WHSV = 4 h⁻¹. The catalyst properties, measured by several characterization techniques (ICP-AES, XRD, N₂ adsorption-desorption isotherms, TPR, H₂-TPD, CO chemisorption, XPS, FTIR spectroscopy of adsorbed pyridine and NH₃-TPD), were related to their catalytic activity and selectivity. Interestingly, the increase in Ni loading from 24.4 to 33.2 Ni wt.% has a negative effect on both hydrogenation and ring opening activities, as it causes a drop in the BET surface area and a decrease in metal-support interaction, with a negative bearing on catalyst stability. On the other hand, the addition of Pd has a positive effect for hydrogenation, linked with the higher electronegativity of Pd⁰ species compared to those of Ni⁰, as well as with a greater stability of Pd-promoted catalysts during on-stream conditions. A linear correlation has been found between the total amount of desorbed H₂, as determined from H₂-TPD experiments on freshly reduced catalysts, and the initial turnover frequency.     

Spark plasma sintering of Al2O3–Ni nanocomposites using Ni nanoparticles produced by rotary chemical vapour deposition

Al₂O₃–Ni nanocomposites were fabricated by spark plasma sintering (SPS) using Ni nanoparticle produced by rotary chemical vapour deposition. Carbon-free Ni nanoparticles were prepared by reacting NiCp₂ with O₂ to form NiO and then reducing to Ni by H₂ for 30 min at 823 K. The highest Ni content and grain size were 7.8 wt.% and 47.7 nm, respectively, using a NiCp₂ supply rate (R_s) of 1.67 × 10⁻⁶ kg s⁻¹. At a sintering temperature (T_SPS) of 1573 K, the hardness of Al₂O₃–3.8 wt.% Ni was 20.5 GPa, around 1 GPa higher than that of monolithic Al₂O₃ sintered at the same temperature. The tensile strength of Al₂O₃–4.6 wt.% Ni was 170 MPa, 60 MPa higher than that of Al₂O₃ sintered at 1573 K.     

Role of interface on electrical conductivity of carbon nanotube/alumina nanocomposite

Interface of multiwalled carbon nanotube (MWCNT)/alumina (Al₂O₃) nanocomposites have been studied using TEM. At low sintering temperature (T_sin=1500 °C), a 3–5 nm thick amorphous interface region was noticed. Nanocomposite sintered at 1700 °C possessed a well-defined graphene layer coating on matrix grains as the interface between CNT and Al₂O₃. A mechanism of such layered interface formation has been proposed. No traceable chemical reaction product was observed at the interface even after sintering at 1700 °C. It was noticed that while DC electrical conductivity (σ_DC) of 1500 °C sintered 2.4 vol% MWCNT/Al₂O₃ nanocomposite was only~0.02 S/m, it raised to ~21 S/m when sintering was done at 1700 °C. Such 10³ times increase in σ_DC of present nanocomposite at a constant CNT loading was not only resulted from the exceptionally high electron mobility of CNT but the well-crystallized graphene interface on insulating type Al₂O₃ grains also significantly contributed in the overall increase of electrical performance of the nanocomposite, especially, when sintering was done at 1700 °C.     

Ethanol steam reforming reactions over Al2O3 · SiO2-supported Ni-La catalysts

Nickel-based catalysts supported on Al₂O₃ · SiO₂ were prepared with modification of the second metal involving La, Co, Cu, Zr or Y, of which the catalytic behaviors were assessed in the ethanol steam reforming reaction. Activity test indicated that addition of La resulted in higher selectivity of hydrogen and lower selectivity of carbon monoxide, compared with Co-doped nickel catalyst. Influences of lanthanum amounts on catalytic performance were studied over 30NixLa/Al₂O₃ · SiO₂ (x = 5, 10, 15), and characterizations by XRD, TPR and XPS indicated that low amount of lanthanum additives (5%) was superior to inhibit the crystal growth of nickel as well as beneficial to the reduction of nickel oxide. Finally 100 h test for the optimal catalyst 30Ni5La/Al₂O₃ · SiO₂ indicated its good long-term stability to provide high hydrogen selectivity and low carbon monoxide formation, as well as good resistance to coke deposition at low temperature.     

Characterization of Mg1−xNixAl2O4 solid solutions prepared by combustion synthesis

Mg_1−xNi_xAl₂O₄ (x = 0, 0.25, 0.5, 0.75 and 1) solid solutions have been prepared by combustion synthesis. After annealing the combustion synthesized powders at 1000 °C for 3 h single-phase Mg_1−xNi_xAl₂O₄ was obtained over the entire range of compositions. The lattice parameter of Mg_1−xNi_xAl₂O₄ gradually increased from 8.049 Å (NiAl₂O₄) to 8.085 Å (MgAl₂O₄), which certified the formation of the spinel solid solutions. All samples prepared by combustion synthesis had blue color shades, denoting the inclusion of Ni²⁺ in the spinel structure in octahedral and tetrahedral configuration. The crystallite size of Mg_1−xNi_xAl₂O₄ was in the range of 35-39 nm and the specific surface area varied between 5.8 and 7.0 m²/g.     

Spark plasma sintering technique for reaction sintering of Al2O3/Ni nanocomposite and its mechanical properties

Al₂O₃/Ni nanocomposites were prepared by spark plasma sintering (SPS) using reaction sintering method and the mechanical properties of the obtained nanocomposites are reported. The starting materials of Al₂O₃–NiO solid solution were synthesized from aluminum sulfate and nickel sulfate. These Al₂O₃–NiO powders were changed into Al₂O₃ and Ni phases during sintering process. The obtained nanocomposites showed high relative densities (>98%). SEM micrographs showed homogeneously dispersed Ni grains in the matrix. The 3-point strength and the fracture toughness of the composites significantly improved from 450 MPa in the monolithic α-Al₂O₃ to 766 MPa in the 10 mol% (2.8 vol.%) Ni nanocomposite and from 3.7 to 5.6 MPa m^1/2 in 13 mol% (3.7 vol.%) Ni nanocomposite. On the other hand, Young's modulus and Vickers hardness of the nanocomposites were mostly same as those of the monolithic α-Al₂O₃.     

Comparative study of Li[Co1−zAlz]O2 prepared by solid-state and co-precipitation methods

Li[Co_1−zAl_z]O₂ (0 ≤ z ≤ 0.5) samples were prepared by co-precipitation and solid-state methods. The lattice constants varied smoothly with z for the co-precipitated samples but deviated for the solid-state samples above z = 0.2. The solid-state method may not produce materials with a uniform cation distribution when the aluminum content is large or when the duration of heating is too brief. Non-stoichiometric Li_x[Co_0.9Al_0.1]O₂ samples were synthesized by the co-precipitation method at various nominal compositions x = Li/(Co + Al) = 0.95, 1.0, 1.1, 1.2, 1.3. XRD patterns of the Li_x[Co_0.9Al_0.1]O₂ samples suggest the solid solution limit is between Li/(Co + Al) = 1.1 and 1.2. Electrochemical studies of the Li[Co_1−zAl_z]O₂ samples were used to measure the rate of capacity reduction with Al content, found to be about −250 ± 30 (mAh/g)/(z = 1). Literature work on Li[Ni_1/3Mn_1/3Co_1/3−zAl_z]O₂, Li[Ni_1−zAl_z]O₂ and Li[Mn_2−yAl_y]O₄ demonstrates the same rate of capacity reduction with Al/(Al + M) ratio. These studies serve as baseline characterization of samples to be used to determine the impact of Al content on the thermal stability of delithiated Li[Co_1−zAl_z]O₂ in electrolyte.     

Crystallographic and electrochemical characteristics of TiZrNiCu quasicrystal ball-milled with La0.9Zr0.1Ni4.5Al0.5 alloy

Icosahedral quasicrystalline Ti₄₅Zr₃₅Ni₁₇Cu₃ alloy was ball-milled with 30 mass% La_0.9Zr_0.1Ni_4.5Al_0.5 alloy (LaNi₅ phase), the effect of the milling time on crystallographic and electrochemical characteristics of the alloy powder was investigated. The amount of amorphous phase increased with increasing milling time from 60 to 360 min, and the LaNi₅ phase cannot be observed when milling time was 240 min or more. The maximum discharge capacity and high-rate dischargeability of milled alloy electrodes were obviously higher than those of the alloy electrode before milling. The cycling capacity retention rate after 40 cycles increased from 52.8% (t = 60 min) to 62.9% (t = 360 min).     

Structural and electrochemical behaviors of metastable Li2/3[Ni1/3Mn2/3]O2 modified by metal element substitution

Layered metastable lithium manganese oxides, Li_2/3[Ni_1/3−xMn_2/3−yM_x+y]O₂ (x = y = 1/36 for M = Al, Co, and Fe and x = 2/36, y = 0 for M = Mg) were prepared by the ion exchange of Li for Na in P2-Na_2/3[Ni_1/3−xMn_2/3−yM_x+y]O₂ precursors. The Al and Co doping produced the T^#2 structure with the space group Cmca. On the other hand, the Fe and Mg doped samples had the O6 structure with space group R-3m. Electron diffraction revealed the 1:2 type ordering within the Ni_1/3−xMn_2/3−yM_x+yO₂ slab. It was found that the stacking sequence and electrochemical performance of the Li cells containing T^#2-Li_2/3[Ni_1/3Mn_2/3]O₂ were affected by the doping with small amounts of Al, Co, Fe, and Mg. The discharge capacity of the Al doped sample was around 200 mAh g⁻¹ in the voltage range between 2.0 and 4.7 V at the current density of 14.4 mA g⁻¹ along with a good capacity retention. Moreover, for the Al and Co doped and undoped oxides, the irreversible phase transition of the T^#2 into the O2 structure was observed during the initial lithium deintercalation.     

Insignificant impact of designed oxygen release from high capacity Li[(Ni1/2Mn1/2)xCoy(Li1/3Mn2/3)1/3]O2 (x + y = 2/3) positive electrodes during the cycling of Li-ion cells

The properties of graphite/Li[(Ni_0.5Mn_0.5)_xCo_y(Li_1/3Mn_2/3)_1/3]O₂ (x + y = 2/3, y = 1/12 and 1/6) Li-ion cells are reported. There is an extended plateau near 4.5 V during the first charging of the cells that corresponds to the simultaneous removal of Li and oxygen from the Li[(Ni_0.5Mn_0.5)_xCo_y(Li_1/3Mn_2/3)_1/3]O₂ (x + y = 2/3, y = 1/12 and 1/6) electrodes. The release of this oxygen directly within a Li-ion cell has been a cause for concern. However, it was found that subsequent to O₂ release, Li-ion cells delivered a high reversible positive electrode specific capacity near 250 mAh/g at C/30 between 2.5 and 4.8 V, the cells did not display increased irreversible capacity relative to counterparts having Li metal negative electrodes and the cells retained 85% of their initial capacity after 70 cycles at C/6 between 2.5 and 4.6 V. Therefore, the O₂ released during the first charge does not significantly impact the electrochemical properties of graphite/Li[(Ni_0.5Mn_0.5)_xCo_y(Li_1/3Mn_2/3)_1/3]O₂ (x + y = 2/3) lithium-ion cells.     

Sintering,microstrusture and hardness of different alumina–zirconia composites

Two commercial 3 mol% yttria-partially stabilized zirconia powders, 0.3 wt% Al₂O₃-doped (Al-doped Y-PSZ) and without Al₂O₃ (Y-PSZ), were used to produce alumina (Al₂O₃)-zirconia (ZrO₂) slip cast composites. The influence of the substitution of Al₂O₃ either by different Al-doped Y-PSZ contents or 50 vol% Y-PSZ on the sintering kinetic at the intermediate stage was investigated. In addition, the microstructure of Al₂O₃ and the different composites at temperatures in the range of 1100–1600 °C was studied and related to the sample hardness. An increase in the sintering rate was observed when Al-doped Y-PSZ increased from 22 to 50 vol% or when 50 vol% Y-PSZ was substituted by 50 vol% Al-doped Y-PSZ. 50 vol% ZrO₂ was the most effective concentration to reduce the rate of Al₂O₃ grain growth in the final sintering stage; the Al₂O₃ grain growth began at lower temperatures and became greater with decreasing the Al-doped Y-PSZ content. On the contrary, the ZrO₂ grain growth slightly increased with increasing the Al-doped Y-PSZ concentration. However, for 50 vol% Al-doped Y-PSZ a smaller ZrO₂ grain size distribution compared with 50 vol% Y-PSZ could be achieved. As the average Al₂O₃ grain size of the sintered samples became greater than about 1 µm a markedly decrease in the hardness was found; this occurred at temperatures higher than 1400 °C and 1500 °C for Al₂O₃ and the composite with 10.5 vol% Al-doped Y-PSZ, respectively.     

Combustion synthesis of (Ti1−xNbx)2AlC solid solutions from elemental and Nb2O5/Al4C3-containing powder compacts

Preparation of the (Ti_1−xNb_x)₂AlC solid solution (formed from the M_n+1AX_n or MAX carbides, where n = 1, 2, or 3, M is an early transition metal, A is an A-group element, and X is C) with x = 0.2-0.8 was investigated by self-propagating high-temperature synthesis (SHS). Nearly single-phase (Ti,Nb)₂AlC was produced through direct combustion of constituent elements. Due to the decrease of reaction exothermicity, the combustion temperature and reaction front velocity decreased with increasing Nb content of (Ti_1−xNb_x)₂AlC formed from the elemental powder compacts. In addition, the samples composed of Ti, Al, Nb₂O₅, and Al₄C₃ were adopted for the in situ formation of Al₂O₃-added (Ti,Nb)₂AlC. The SHS process of the Nb₂O₅/Al₄C₃-containing sample involved aluminothermic reduction of Nb₂O₅, which not only enhanced the reaction exothermicity but also facilitated the evolution of (Ti,Nb)₂AlC. Based upon the XRD analysis, two intermediates, TiC and Nb₂Al, were detected in the (Ti,Nb)₂AlC/Al₂O₃ composite and their amounts were reduced by increasing the extent of thermite reduction involved in the SHS process. The laminated microstructure characteristic of the MAX carbide was observed for both monolithic and Al₂O₃-added (Ti,Nb)₂AlC solid solutions synthesized in this study.     

The effect of Ga addition on the sinterability and microwave dielectric properties of RE3Al5O12 (Tb,Y, Er and Yb) garnet ceramics

The RE₃Al₅O₁₂ (RE=Tb, Y, Er, Yb) ceramics have been prepared by the mixed oxide route and the influence of Ga³⁺ doping on their properties is investigated. The intrinsic Y₃Al₅O₁₂ (YAG) ceramic sintered at 1650 °C for 4 h showed good dielectric properties; (ε_r=10.1, Q_u×f=65,000 GHz, τ_f=−45 ppm/°C). Addition of Ga₂O₃ was found to be beneficial in improving the densification of Tb₃Al₅O₁₂, Er₃Al₅O₁₂ and Yb₃Al₅O₁₂ except Y₃Al₅O₁₂ where Nb₂O₅ is the better choice. Among Ga³⁺ added samples, the composition Yb₃Al₅O₁₂+1 wt% Ga₂O₃ showed good microwave dielectric properties: ε_r=10.3, Q_u×f=50,000 GHz, τ_f=−58 ppm/°C. The Y₃Al₅O₁₂ doped with 1 wt% Nb₂O₅ has ε_r=10.7, Q_u×f=120,000 GHz and τ_f=−45 ppm/°C. The ceramics have good thermal properties (CTE=2–3 ppm/°C, λ=2–12 W/m K).     

Room temperature multiferroic properties of Ni-doped Aurivillus phase Bi5Ti3FeO15

Single-phase Aurivillius Bi₅Ti₃Fe_0.5Ni_0.5O₁₅ (BTFN) ceramics were synthesized by the solid-state reaction method. The substitution of Ni for half Fe ions does not introduce magnetic impurity phase but increases magnetic moment more than two orders. The ferroelectric and magnetic Curie temperatures are determined to be 1100 K and 726 K. The room-temperature multiferroic behavior of the BTFN ceramics were demonstrated by the ferroelectric (2P_r=8.5 μC/cm², 2E_c=74 kV/cm) and ferromagnetic (2M_r=27.86 m emu/g, 2H_c=553 Oe) measurements. The ferromagnetism can be ascribed to the aggregation of magnetic ions at the inner octahedra by Ni doping and the spin canting of magnetic-ion-based sublattices via the Dzyaloshinskii-Moriya interaction. The present work suggests the possibility of doped Bi₅Ti₃FeO₁₅ as a potential room-temperature multiferroic.