Thermal and electrical properties of additive-free rapidly hot-pressed SiC ceramics

The thermal and electrical properties of newly developed additive free SiC ceramics processed at a temperature as low as 1850 °C (RHP0) and SiC ceramics with 0.79 vol.% Y₂O₃-Sc₂O₃ additives (RHP79) were investigated and compared with those of the chemically vapor-deposited SiC (CVD-SiC) reference material. The additive free RHP0 showed a very high thermal conductivity, as high as 164 Wm⁻¹ K⁻¹, and a low electrical resistivity of 1.2 × 10⁻¹ Ω cm at room temperature (RT), which are the highest thermal conductivity and the lowest electrical resistivity yet seen in sintered SiC ceramics processed at ≤1900 °C. The thermal conductivity and electrical resistivity values of RHP79 were 117 Wm⁻¹ K⁻¹ and 9.5 × 10⁻² Ω cm, respectively. The thermal and electrical conductivities of CVD-SiC parallel to the direction of growth were ∼324 Wm⁻¹ K⁻¹ and ∼5 × 10⁻⁴Ω⁻¹ cm⁻¹ at RT, respectively.     

Process induced alignment of carbon nanotube decreases longitudinal thermal conductivity of Al2O3 based porous composites

Alumina (Al₂O₃) based porous composites, reinforced with zirconia (ZrO₂), 3 and 8 mol% Y₂O₃ stabilized ZrO₂ (YSZ) and 4 wt% carbon nanotube (CNT) are processed via spark plasma sintering. The normalized linear shrinkage during sintering process of Al₂O₃-based composite shows minimum value (19.2–20.4%) for CNT reinforced composites at the temperature between 1650 °C and 575 °C. Further, the combined effect of porosity, phase-content and its crystallite size in sintered Al₂O₃-based porous composite have elicited lowest thermal conductivity of 1.2 Wm⁻¹K⁻¹ (Al₂O₃-8YSZ composite) at 900 °C. Despite high thermal conductivity of CNT (∼3000 Wm⁻¹K⁻¹), only a marginal thermal conductivity increase (∼1.4 times) to 7.3–13.4 Wm⁻¹K⁻¹ was observed for CNT reinforced composite along the longitudinal direction at 25 °C. The conventional models overestimated the thermal conductivity of CNT reinforced composites by up to ∼6.7 times, which include the crystallite size, porosity, and interfacial thermal resistance of Al₂O₃, YSZ and, CNT. But, incorporation of a new process induced CNT-alignment factor, the estimated thermal conductivity (of <6.6 Wm⁻¹K⁻¹) closely matched with the experimental values. Moreover, the high thermal conductivity (<76.1 Wm⁻¹K⁻¹) of the CNT reinforced porous composites along transverse direction confirms the process induced alignment of CNT in the spark plasma sintered composites.     

Effects of yttria and magnesia on densification and thermal conductivity of sintered reaction-bonded silicon nitrides

A variety of combinations of Y₂O₃ and MgO were used as additives in preparing Si₃N₄ ceramics by the sintering of reaction-bonded silicon nitride (SRBSN) method. By varying the amount of Y₂O₃ in the range of 0-5 mol% and that of MgO in the range of 0-8 mol%, the effects of Y₂O₃ and MgO additives on nitridation and sintering behaviors as well as thermal conductivity were studied. It was found that appropriate amount and combination of Y₂O₃ and MgO additives were essential for attaining full densification and achieving high thermal conductivity. The sample doped with 2.5 mol% of Y₂O₃ and 5 mol% of MgO attained a thermal conductivity of 128 Wm⁻¹K⁻¹ when sintered at 1900°C for 6 hours, and the sample doped with 2 mol% of Y₂O₃ and 4 mol% of MgO achieved a thermal conductivity of 156 Wm⁻¹K⁻¹ when sintered for 24 hours.     

Enhanced oxidation resistance of low-carbon MgO–C refractories with Al3BC3–Al antioxidants: A synergistic effect

The synergistic effects of Al₃BC₃–Al antioxidants on optimizing the oxidation resistance of low-carbon MgO–C refractories were investigated. The results indicated that the oxidation index and rate constant of low-carbon MgO–C refractories with optimized Al₃BC₃–Al additions were 13% and 1.10 × 10⁻⁴ cm² min⁻¹ at 1400°C for 3 h, respectively, which is much lower than that of Al or Al₃BC₃ containing ones. Single Al₃BC₃ is not a suitable antioxidant for low-carbon MgO–C refractories; however, if Al₃BC₃ was initially protected and Al reacted as the antioxidant, enhanced oxidation resistance at high temperature can be achieved. The formation of dense MgO–MgAl₂O₄–Mg₃B₂O₆ layer contributed to superior oxidation resistance, and the temperature for the generation of this layer was as low as 1100°C due to liquid and vapor phase–assisted reactions with Al₃BC₃–Al. Furthermore, a self-repairing function was achieved at 1600°C with the combination of Al₃BC₃–Al additions in spite of the faster oxidation rate.     

Thermodynamic and Kinetic Effects of Oxygen Removal on the Thermal Conductivity of Aluminum Nitride

High thermal conductivity, low dielectric constant, high electrical resistivity, low density, and a thermal expansion coefficient that matches well with that of silicon are the principal attributes of AIN that have attracted much attention over the past decade. It is also now well established that oxygen as an impurity lowers the thermal conductivity of AIN. Processing techniques have been developed which not only facilitate pressureless densification of AIN but also enhance its thermal conductivity. The present work explores the thermodynamics and the kinetics of oxygen removal and the resultant enhancement of thermal conductivity. Polycrystalline AIN ceramics were fabricated with Y₂O₃, Dy₂O₃, Yb₂O₃, CaO, BaO, or MgO as additives. Samples were sinter/annealed at 1850°C for up to 1000 min. The AIN grain size of sintered samples ranged between 2 and 9 μm. The samples typically contained two or three phases with the predominant phase being AIN. Secondary phases in Y₂O₃-doped AIN consisted of yttrium aluminates which were along three grain junctions and along grain facets. The presence of Y₃Al₅O₁₂, YAIO₃, and Y₄Al₂O₉, as well as Y₂O₃, depending upon the Y₂O₃/Al₂O₃ ratio, was revealed by X-ray diffraction. Thermal conductivity increased with the amount of additive and annealing time. Thermal conductivity also depended on the type of additive. Samples with thermal conductivity up to 200 W/(m · K) were fabricated. The variation in thermal conductivity with the type and the amount of the additive is explained on the basis of the thermodynamics of oxygen removal. In particular, the higher thermal conductivity of CaO-doped, in comparison with MgO-doped, samples is rationalized on the basis that the free energy of formation, ΔG°, of CaAl₂O₄ is less than that of MgAl₂O₄. It is proposed that the higher the |ΔG°|, with ΔG° < 0, the higher is the resultant thermal conductivity. An increase in the thermal conductivity with annealing time is attributed to the kinetics of oxygen removal from AIN grains.     

A study of phase evolution and crystal growth for nano-sized monoclinic Y4Al2O9 as a novel thermal barrier coatings

Nano-sized monoclinic Y₄Al₂O₉ was produced by sol-gel process as a novel potential candidate material for thermal barrier coatings. The thermal behavior, structural evolution of the products and the morphological characteristics of the compacted bodies were investigated by Thermogravimetric analysis and differential scanning calorimeter (TG-DSC), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and Field emission scanning electron microscopy (FESEM). Qualitative analyses indicate that monoclinic Y₄Al₂O₉ was formed at about 1000 °C, and exhibited good phase stability throughout the annealing temperature ranging from 1000 °C to 1400 °C. The thermophysical properties of Y₄Al₂O₉ ceramics were also evaluated compared with 8YSZ and La₂Zr₂O₇. The determined activation energy of crystal growth is about 72.71 ± 0.31 kJ mol⁻¹. Meanwhile, Y₄Al₂O₉ represents low thermal conductivity (1.71 W m⁻¹ K⁻¹), moderate thermal expansion coefficient (8.73 × 10⁻⁶ K⁻¹), and high sintering-resistance ability. Such results reveal that nano-sized Y₄Al₂O₉ is favorable for the application of TBCs.     

Solid Solution Effects on the Thermal Properties in the MgAl2O4–MgGa2O4 System

Solid solution effects on thermal conductivity within the MgO–Al₂O₃–Ga₂O₃ system were studied. Samples with systematically varied additions of MgGa₂O₄–MgAl₂O₄ were prepared and the laser flash technique was used to determine thermal diffusivity at temperatures between 200°C and 1300°C. Heat capacity as a function of temperature from room temperature to 800°C was also determined using differential scanning calorimetry (DSC). Solid solution in the MgAl₂O₄–MgGa₂O₄ system decreases the thermal conductivity up to 1000°C. At 200°C thermal conductivity decreased 24% with a 5 mol% addition of MgGa₂O₄ to the system. At 1000°C, the thermal conductivity decreased 13% with a 5 mol% addition. Steady‐state calculations showed a 12.5% decrease in heat flux with 5 mol% MgGa₂O₄ considered across a 12 inch thickness.     

Thermal and electrical properties of epoxy composites at high alumina loadings and various temperatures

Epoxy microcomposites with high loading micro alumina (Al₂O₃, 100–400 phr) were prepared by casting method and their thermal and electrical properties were studied at temperatures from 25 to 150 °C. The electric resistance device and the dielectric electrode device were designed to measure the electrical properties of the composites. Thermogravimetric analysis (TGA) and scanning electron microscopic proves the homodispersion of Al₂O₃ microparticles in epoxy. TGA indicates that the temperature of 5 % weight loss of epoxy/Al₂O₃ (100 phr) composite is 366 °C, 34 °C higher than that of pure epoxy. Differential scanning calorimetry shows that the glass transition temperature of epoxy/Al₂O₃ composite (400 phr) increases to 114.7 °C, 9.2 °C higher than that of pure epoxy. Thermal conductivity test demonstrated that with increasing Al₂O₃ content at 25 °C, thermal conductivity of epoxy/Al₂O₃ composites increased to 1.382 W/(m K) which is 5.62 times that of pure epoxy. Electrical tests demonstrate that by increasing of Al₂O₃ content and temperature, the electric resistance and dielectric properties of the composites show great dependencies on them. Resistivities of all the specimens decreased with the increasing of temperature owing to the increasing molecular mobility in the higher temperature. Resistivity of pure epoxy at 25 °C is about 9.56 × 10¹⁶ Ω cm, about one order of magnitude higher than that of pure epoxy at 125 °C and two orders of magnitude higher than that of pure epoxy at 150 °C. These results can give some advice to design formulations for practical applications in power apparatus.     

Synergistic thermal conductivity enhancement of PC/ABS composites containing alumina/magnesia/graphene nanoplatelets

Graphene nanoplatelets (GNPs) have attracted considerable attention in the field of thermal management materials due to their unique structure and exceptional thermal conductive properties. In this work, we demonstrate a significant synergistic effect of GNPs, alumina (Al₂O₃), and magnesia (MgO) in improving the thermal conductivity of polycarbonate/acrylonitrile‐butadiene‐styrene polymer alloy (PC/ABS) composites. The thermal conductivity of the composites prepared through partial replacement of Al₂O₃ and MgO with GNPs could increase dramatically compared with that without GNPs. The maximum thermal conductivity of the composite is 3.11 W mK⁻¹ at total mass fraction of 70% with 0.5 wt% GNPs loading. It increases 60% compared with that without GNPs (1.95 W mK⁻¹). The synergistic effect results from the compact packing structure formed by Al₂O₃/MgO and the bridging of GNPs with Al₂O₃/MgO, thus promoting the formation of effective thermal conduction pathways within PC/ABS matrix. More importantly, together with the intrinsically high thermal conductivity of GNPs, boosted and effective pathways for phonon transport can be created, thus decrease the thermal resistance at the interface between fillers and PC/ABS matrix and increase the thermal conductivity of composites. POLYM. COMPOS., 38:2221–2227, 2017. © 2015 Society of Plastics Engineers     

Thermodynamic properties of aluminum titanate-mullite composite ceramics containing heat stabilizer

Using Al₂O₃ and TiO₂ as raw materials, adding MgO as heat stabilizer and mullite as enhancer, aluminum titanate-mullite multiphase ceramics were successfully prepared by solid phase synthesis. The effects of MgO and mullite were systematically studied on the phase composition, microstructure, thermal stability, sintering properties, and mechanical properties of aluminum titanate ceramics. The results showed that the introduction of Mg²⁺ can partially replace Al³⁺ to form Mg_xAl_2(1-x)Ti_(1+x)O₅ solid solution, improved the thermal stability of aluminum titanate ceramics, and promoted the formation and growth of grains, which reduced the sintering temperature. The crack deflections caused by mullite particles improved the mechanical properties. The filling effect of mullite particles and the formation of silica in mullite raw materials were conducive to ceramic densification. The statistics of Mg4M10 sample were as follows: the porosity was only 2.9%, the flexural strength was as high as 64.15 MPa, and the thermal expansion coefficient was 1.35 × 10⁻⁶ K⁻¹ (RT-700°C), encouraging the application of ceramics with high thermal mechanical properties.     

Ionic conductivity behavior by activated hopping conductivity (AHC) of barium aluminoborosilicate glass–ceramic system designed for SOFC sealing

Non-conducting BaO-B₂O₃-Al₂O₃-SiO₂ parent glasses designed for solid oxide fuel cell (SOFC) sealing applications were prepared using the melt-quenching technique. The glass formation region was determined according to phase equilibrium relations and was found to be in the composition range 70BaO-(x)Al₂O₃-(10−x)B₂O₃-20SiO₂ where 3.0 < x < 6.0 wt%. The conductivity values obtained conductivity ranged from 10⁻⁵ to 10⁻¹⁰ S/cm at temperatures between 600 and 850 °C. The batch compositions presented a threshold of dc conductivity near 70BaO wt% with a quasi linear behavior with the decrease of the BaO content. Different values of conduction activation energy were observed at temperatures above the glass transition temperature (T_g) (up to 700 °C), which were attributed to the thermal bond-breaking of non-bridging oxygen (NBO) defects. The experimental results of the electrochemical characterization by impedance spectroscopy of glass–ceramic interfaces with yttria-stabilized zirconia (YSZ) acting as solid ionic conductor electrolyte are presented and discussed.     

Ultra-flexible Al2O3 fibers: A novel catalyst support material for sustainable catalysis

Flexible aluminum oxide (Al₂O₃) fibers were prepared by the blow spinning method and their potential as a high-temperature catalyst support was investigated. The synthesized Al₂O₃ fibers exhibited remarkable flexibility in both mechanical compression and recovery tests, which remained intact in a wide temperature range from −196 °C to 1200 °C. Moreover, their low thermal conductivity of 0.030 W K⁻¹∙m⁻¹, demonstrated an outstanding thermal insulation. Subsequently, nickel nanoparticles were uniformly distributed on the surface of the Al₂O₃ fibers as a self-supporting catalyst using a conventional impregnation method. The resulting self-supporting Ni/Al₂O₃ catalyst demonstrated remarkable thermo-catalytic performance and re-activation capability at high temperatures for thermocatalytic reaction of dry reforming of methane (DRM). Our findings highlight the potential of pure Al₂O₃ flexible fibers as a versatile material for various industrial applications, including high-temperature catalysis.     

Ion-exchange characteristics of 12CaO·7Al2O3 for halide and hydroxyl ions

Substitution characteristics of the halide ions F⁻ Cl⁻ for the OH⁻ ions in the crystal lattice of 12CaO·7Al₂O₃ solid solution were investigated. Single phases of composition 11CaO·7Al₂O₃·CaF₂ and 11CaO·7Al₂O₃·CaCl₂ were formed at 900 °C or above. The OH⁻ ions in 12CaO·7Al₂O₃ solid solution, i.e. 11CaO·7Al₂O₃·Ca(OH)₂, could be replaced wholly or partially by F⁻ or Cl⁻ ions from the corresponding calcium halide, forming 11CaO·7Al₂O₃·Ca(OH,F)₂ and 11CaO·7Al₂O₃·Ca(OH,Cl)₂ solid solutions above 500 °C and above 700 °C, respectively. Lattice constants of 12CaO·7Al₂O₃ solid solution changed continuously with the proportion of F⁻ ions or Cl⁻ ions. The F⁻ ions in 11CaO·7Al₂O₃·CaF₂ could be wholly or partially substituted by Cl⁻ ions from CaCl₂ at 900 °C or more, forming the solid solution 11CaO·7Al₂O₃·Ca(F,Cl)₂. The Cl⁻ ions in 11CaO·7Al₂O₃·CaCl₂ could be partially replaced F⁻ ions from CaF₂ at 1000 °C or above, apparently due to slow chloride loss by evaporation.     

Impact on aggregate/matrix bonding when a refractory contains zinc aluminate instead of spinel and magnesia-chrome

The high hot strength of MgO–Cr₂O₃ refractory is often ascribed to its intimate aggregate/matrix bonding. For a fundamental comparison with it, ∼2 mm aggregates of MgO and Al₂O₃ were separately embedded in ZnAl₂O₄ and MgAl₂O₄ matrices, sintered at 1600°C, and examined. It was found that similarity of thermal expansion coefficient (TEC) between the aggregate and the matrix is critical to achieve good bonding and this is more important than the extent of interdiffusion. The TEC mismatch of ≥5.7 × 10⁻⁶ K⁻¹ caused significant undesirable debonding in MgO aggregate/MgAl₂O₄ matrix sample and MgO/ZnAl₂O₄ despite >736 μm Zn²⁺ diffusion depth in the latter. Direct bonding, as inferred from a thicker interfacial reaction layer and a greater shift of the aggregate/matrix interface before and after firing, was better in MgAl₂O₄/ZnAl₂O₄ combination, followed by tabular Al₂O₃/ZnAl₂O₄ and Al₂O₃/MgAl₂O₄. Powder X-ray diffraction indicated that the volatilization of ZnAl₂O₄ at 1600°C in air was negligible compared to MgO–Cr₂O₃.     

Mechanical and thermal properties of silicon carbide ceramics with yttria–scandia–magnesia

Two different SiC ceramics with a new additive composition (1.87 wt% Y₂O₃–Sc₂O₃–MgO) were developed as matrix materials for fully ceramic microencapsulated fuels. The mechanical and thermal properties of the newly developed SiC ceramics with the new additive system were investigated. Powder mixtures prepared from the additives were sintered at 1850 °C under an applied pressure of 30 MPa for 2 h in an argon or nitrogen atmosphere. We observed that both samples could be sintered to ≥99.9% of the theoretical density. The SiC ceramic sintered in argon exhibited higher toughness and thermal conductivity and lower flexural strength than the sample sintered in nitrogen. The flexural strength, fracture toughness, Vickers hardness, and thermal conductivity values of the SiC ceramics sintered in nitrogen were 1077 ± 46 MPa, 4.3 ± 0.3 MPa·m^1/2, 25.4 ± 1.2 GPa, and 99 Wm⁻¹ K⁻¹ at room temperature, respectively.     

Comparison of Alkali Metal Promoted MgO Catalysts for Their Surface Acidity/Basicity and Catalytic Activity/Selectivity in the Oxidative Coupling of Methane

Alkali metal (viz. Li, Na, K, Rb and Cs) promoted MgO catalysts (with an alkali metal/Mg ratio of 0·1) calcined at 750°C have been compared for their surface properties (viz. surface area, morphology, acidity and acid strength distribution, basicity and base strength distribution, etc.) and catalytic activity/selectivity in the oxidative coupling of methane (OCM) to C₂-hydrocarbons at different temperatures (700–750°C), CH₄/O₂ ratios (4·0 and 8·0) in feed, and space velocities (10320 cm³ g⁻¹ h⁻¹). The surface and catalytic properties of alkali metal promoted MgO catalysts are found to be strongly influenced by the alkali metal promoter and the calcination temperature of the catalysts. A close relationship between the surface density of strong basic sites and the rate of C₂-hydrocarbons formation per unit surface area of the catalysts has been observed. Among the catalysts calcined at 750°C, the best performance in the OCM is shown by Li–MgO (at 750°C). © 1997 SCI.     

Comparison of Two‐Phase Thermal Conductivity Models with Experiments on Dilute Ceramic Composites

Thermal shock resistance of cubic 8 mol% yttria‐stabilized zirconia (YSZ) can be increased by the addition of dilute second phases. This study addresses how these dilute second phases affect the thermal conductivity for two‐phase ceramic composites of 8 mol% YSZ with 10–20 vol% alumina (Al₂O₃) or 10–20 vol% mullite (3Al₂O₃·2SiO₂). Thermal conductivity measurements from 310 K (37°C) to 475 K (202°C) were made using the 3ω method and compared with results from 3D analytical models and a 2D computational microstructure‐based model (Object‐Oriented Finite Element Analysis, OOF2). The linear Rule of Mixtures was the least accurate and significantly overestimated the measured thermal conductivity at low temperatures, with errors in some cases exceeding 100%. Calculations using the Bruggeman and OOF2 models were both much better, and the deviation of less than ±2.5% across all compositions and temperatures is within the range of experimental and modeling uncertainty. The Maxwell Garnett equation was a close third in accuracy (±8%). A sensitivity analysis for each model quantifies how small perturbations in the thermal conductivity of the dispersed second phase influence the effective thermal conductivity of the composite, and reveals that the linear Rule of Mixtures model is physically unrealistic and oversensitive to the thermal conductivity of the dispersed phase.     

Effect of Sintering Additives on Relative Density and Li‐ion Conductivity of Nb‐Doped Li7La3ZrO12 Solid Electrolyte

Lithium ion conductors with garnet‐type structure are promising candidates for applications in all solid‐state lithium ion batteries, because these materials present a high chemical stability against Li metal and a rather high Li⁺ conductivity (10^?3–10^?4 S/cm). Producing densified Li‐ion conductors by lowering sintering temperature is an important issue, which can achieve high Li conductivity in garnet oxide by preventing the evaporation of lithium and a good Li‐ion conduction in grain boundary between garnet oxides. In this study, we concentrate on the use of sintering additives to enhance densification and microstructure of Li₇La₃ZrNbO₁₂ at sintering temperature of 900°C. Glasses in the LiO₂‐B₂O₃‐SiO₂‐CaO‐Al₂O₃ (LBSCA) and BaO‐B₂O₃‐SiO₂‐CaO‐Al₂O₃ (BBSCA) system with low softening temperature (<700°C) were used to modify the grain‐boundary resistance during sintering process. Lithium compounds with low melting point (<850°C) such as LiF, Li₂CO₃, and LiOH were also studied to improve the rearrangement of grains during the initial and middle stages of sintering. Among these sintering additives, LBSCA and BBSCA were proved to be better sintering additives at reducing the porosity of the pellets and improving connectivity between the grains. Glass additives produced relative densities of 85–92%, whereas those of lithium compounds were 62–77%. Li₇La₃ZrNbO₁₂ sintered with 4 wt% of LBSCA at 900°C for 10 h achieved a rather high relative density of 85% and total Li‐ion conductivity of 0.8 × 10^?4 S/cm at room temperature (30°C).     

Factors influencing the PVA polymer-assisted freeze-drying synthesis of Al2O3 nanofibers

Three-dimensional (3D) nanofibrous structured Al₂O₃ was successfully synthesized using the poly (vinyl alcohol) (PVA) polymer-assisted freeze-drying method, and a series of factors that influence fiber performance were investigated in depth. PVA nanofibers were also investigated for the first time. The surface morphology, structure, and other properties of PVA nanofibers, precursor Al₂O₃/PVA nanofibers, and calcined Al₂O₃ nanofibers were characterized by scanning electron microscopy, X-ray diffraction, and nitrogen adsorption measurements. The results showed that Al₂O₃ nanofibers with good performances could be obtained at the optimum conditions where the precursor solution was prepared by boehmite nanoparticles (0.01 wt%) and PVA (0.1 wt%, DP = 500) with a mass ratio of 7: 3, followed by the use of the rapid freezing method at −196 °C under liquid nitrogen in the pre-frozen process; subsequently, calcination was performed at 500 °C for 5 h to form Al₂O₃ nanofibers. The increasing calcination temperature (500 °C–1300 °C) enabled the transformation of the Al₂O₃ crystalline phase from γ-Al₂O₃ to α-Al₂O₃. It also improved the specific surface area from 44.5 m² g⁻¹ for the precursor Al₂O₃/PVA nanofibers to 263.4 m² g⁻¹ for the Al₂O₃ nanofibers calcinated at 500 °C. However, an excessive calcination temperature at 1300 °C was detrimental to the specific surface area, presumably due to sintering or blocking by metal particles. This work provides optimum conditions that make Al₂O₃ nanofibers valuable for further development, and it has the potential for industrial applications.