Effect of oxidation on flexural strength and thermal properties of AlN ceramics with residual stress and impedance spectroscopy analysis of defects and impurities

The effect of oxidation in air on the phase composition, microstructure, flexural strength and thermal property of AlN ceramics was investigated. Oxidation was found to produce a continuous oxide layer on the surface of AlN samples. The flexural strength and thermal conductivity of AlN ceramics significantly improved after oxidation at 1000 °C and 1100 °C. Residual stress in the AlN ceramic matrix was enhanced by oxidation. The enhanced residual compressive stresses inhibited crack propagation and reduced interfacial thermal resistance, thereby improving the flexural strength and thermal conductivity of AlN ceramics. Electrochemical impedance spectroscopy was further used to analyze the defects in AlN ceramics. The increase in fitting grain resistance revealed a decrease in aluminum vacancy concentration in oxidized AlN sample, which resulted in high thermal conductivity. Therefore, oxidation at a certain temperature is pretty effective to obtain excellent performance for AlN ceramics.     

Effect of nano aluminum nitride filler on mechanical,thermal, and dielectric properties of the glass/mullite composites for low-temperature co-fired ceramic applications

Mullite/glass/nano aluminum nitride (AlN) filler (1–10 wt% AlN) composites were successfully fabricated for the low-temperature co-fired ceramics applications that require densification temperatures lower than 950°C, high thermal conductivity to dissipate heat and thermal expansion coefficient matched to Si for reliability, and low dielectric constant for high signal transmission speed. Densification temperatures were ≤825°C for all composites due to the viscous sintering of the glass matrix. X-ray diffraction proved that AlN neither chemically reacted with other phases nor decomposed with temperature. The number of closed pores increased with the AlN content, which limited the property improvement expected. A dense mullite/glass/AlN (10 wt%) composite had a thermal expansion coefficient of 4.44 ppm/°C between 25 and 300°C, thermal conductivity of 1.76 W/m.K at 25°C, dielectric constant (loss) of 6.42 (0.0017) at 5 MHz, flexural strength of 88 MPa and elastic modulus of 82 GPa, that are comparable to the commercial low temperature co-fired ceramics products.     

High-strength AlN ceramics by low-temperature sintering with CaZrO3–Y2O3 co-additives

Aluminum nitride (AlN) ceramics with the concurrent addition of CaZrO₃ and Y₂O₃ were sintered at 1450-1700 °C. The degree of densification, microstructure, flexural strength, and thermal conductivity of the resulting ceramics were evaluated with respect to their composition and sintering temperature. Specimens prepared using both additives could be sintered to almost full density at relatively low temperature (3 h at 1550 °C under nitrogen at ambient pressure); grain growth was suppressed by grain-boundary pinning, and high flexural strength over 630 MPa could be obtained. With two-step sintering process, the morphology of second phase was changed from interconnected structure to isolated structure; this two-step process limited grain growth and increased thermal conductivity. The highest thermal conductivity (156 Wm⁻¹ K⁻¹) was achieved by two-step sintering, and the ceramic showed moderate flexural strength (560 MPa).     

Balancing thermal conductivity and strength of hot-pressed AlN ceramics via pre-sintering and annealing process

The heat dissipation requirements of the new generation of semiconductors are placing higher demands on the overall performance of aluminum nitride (AlN) ceramics. This has led to an increasing emphasis on AlN ceramics that combine thermal conductivity and strength. AlN ceramics are often strengthened by hot-press sintering, but their thermal conductivity is typically modest. In this study, pre-sintering and annealing processes are introduced to optimize the thermal conductivity of hot-pressed AlN ceramics to avoid the detrimental effects of oxygen impurities in the AlN lattice. The effect of the oxide layer on the surface of commercial AlN particles is investigated, including density, phase composition, microstructure, and fracture behavior. The effect of annealing on the improvement of thermal conductivity and flexural strength is also verified. Electron paramagnetic resonance (EPR) analysis is performed to examine the concentration of intercrystalline defects under various conditions. Finally, AlN ceramics with a thermal conductivity of 204 W m⁻¹ K⁻¹ and a flexural strength of 376 MPa are obtained.     

Effects of two-step sintering on thermal and mechanical properties of aluminum nitride ceramics by impedance spectroscopy analysis

The effects of two-step sintering on the microstructure, mechanical and thermal properties of aluminum nitride ceramics with Yb₂O₃ and YbF₃ additives were investigated. AlN samples prepared using different sintering methods achieved almost full density with the addition of Yb₂O₃–YbF₃. Compared with the one-step sintering, the grain sizes of AlN ceramics prepared by the two-step sintering were limited, and the higher flexural strength and the larger thermal conductivity were obtained. Moreover, the electrochemical impedance spectroscopy of AlN ceramic was associated with thermal conductivity by analyzing the defects and impurities in AlN ceramics. The fitting grain resistance and the activation energy for the grain revealed the lower concentrations of aluminum vacancy in the two-step sintered AlN ceramics, which resulted in the higher thermal conductivity. Thus, mechanical and thermal properties for AlN ceramics were improved with Yb₂O₃ and YbF₃ additives sintered using two-step regimes.     

Effect of carbon content on electrical,thermal, and mechanical properties of porous SiC ceramics with B4C and C additives

The electrical, thermal, and mechanical properties of porous SiC ceramics with B₄C-C additives were investigated as functions of C content and sintering temperature. The electrical resistivity of porous SiC ceramics decreased with increases in C content and sintering temperature. A minimal electrical resistivity of 4.6 × 10^?2 Ω·cm was obtained in porous SiC ceramics with 1 wt% B₄C and 10 wt% C. The thermal conductivity and flexural strength increased with increasing sintering temperature and showed maxima at 4 wt% C addition when sintered at 2000 °C and 2100 °C. The thermal conductivity and flexural strength of porous SiC ceramics can be tuned independently from the porosity by controlling C content and sintering temperature. Typical electrical resistivity, thermal conductivity, and flexural strength of porous SiC ceramics with 1 wt% B₄C-4 wt% C sintered at 2100 °C were 1.3 × 10^?1 Ω·cm, 76.0 W/(m·K), and 110.3 MPa, respectively.     

Vibration Assisted Hot‐Press Sintering of AlN Ceramics

AlN ceramics is very difficult to be sintered due to its strong covalent bonds and low self‐diffusion. In this work, a new hot‐press sintering system assisted by vibration was used to densify AlN ceramics. During hot‐pressing process an additional vibration caused by pressure fluctuation is imposed on the sample. The well‐densified AlN ceramics had been obtained at 1750°C under 15 MPa, or at 1800°C under 10 MPa which were much milder than traditional hot‐press conditions and would be beneficial to prolong working life of the graphite mold. The samples made by this method have a bending strength about 320 MPa. After annealing, it shows a thermal conductivity of 217 W/mK.     

Properties of AlN–TiN composite ceramics

Abstract

Results are presented of a study dealing with an AlN–TiN composite material for high temperature applications. Hardness, microhardness, compressive strength, electrical resistance, and thermal conductivity of the material were measured at room temperature and flexural strength was measured at temperatures from 20 to 1800°C. The composite material containing 40 wt-% AlN and 60 wt-% TiN and hot pressed at 1850–1950°C exhibits an increase in strength of 20% with a rise in temperature, which permits it to be used at elevated temperatures.     

AC Impedance Spectroscopy of CaF2‐doped AlN Ceramics

The electrical conductivity of CaF₂‐doped aluminum nitride (AlN) ceramics was characterized at high temperatures, up to 500°C, by AC impedance spectroscopy. High thermal conductive CaF₂‐doped AlN ceramics were sintered with a second additive, Al₂O₃, added to control the electrical conductivity. The effects of calcium fluoride (CaF₂) on microstructure and related electrical conductivity of AlN ceramics were examined. Investigation into the microstructure of specimens by TEM analysis showed that AlN ceramics sintered with only CaF₂ additive have no secondary phases at grain boundaries. Addition of Al₂O₃ caused the formation of amorphous phases at grain boundaries. Addition of Al₂O₃ to CaF₂‐doped AlN ceramics at temperatures 200°C–500°C revealed a variation in electrical resistivity that was four orders of magnitude larger than for the specimen without Al₂O_3. The amorphous phase at the grain boundary greatly increases the electrical resistivity of AlN ceramics without causing a significant deterioration of thermal conductivity.     

Effects of YH2 addition on pressureless sintered AlN ceramics

A new type of non-oxide sintering additive of YH₂ was introduced for the fabrication of AlN ceramics with high thermal conductivity and flexural strength. The effects of YH₂ addition (0–5 wt%) on the phase composition, densification, microstructure, thermal conductivity and flexural strength of pressureless sintered AlN ceramics were investigated and compared with those Y₂O₃-added samples (1–5 wt%). The addition of 1 wt% YH₂ led to an in-situ reduction reaction with oxygen impurities, the formation of Y₂O₃ and finally the formation of yttrium aluminate, which in turn improved densification and microstructure. A high flexural strength (408.69 ± 28.23 MPa) was achieved. The addition of 3 wt% YH₂ increased the average grain size and purified the lattice. All these effects are believed to help achieve a high thermal conductivity of 184.82 ± 1.75 W·m^?1·K^?1. Although the thermal conductivity was close to the value of 3 wt% Y₂O₃-added sample, its strength was much increased to 381.53 ± 43.41 MPa. Meanwhile, it demonstrated a good combination of the thermal conductivity and flexural strength than the values reported in some literature. However, further increasing the YH₂ addition to 5 wt% resulted in a high N/O ratio that inhibited the densification behavior of AlN ceramics. The current study showed that AlN ceramics with excellent thermal and mechanical properties could be obtained by the introduction of a suitable YH₂ additive.     

Porous ceramics with near-zero shrinkage and low thermal conductivity from hazardous secondary aluminum dross

Herein, a simple, versatile, and low-cost approach has been proposed to realize the green utilization of secondary aluminum dross, the hazardous solid waste, namely directly sintering dry-pressed green bodies from secondary aluminum dross to fabricate porous ceramics according to high-temperature foaming process spontaneously without adding spare foaming agents. Aluminum nitride (AlN) in secondary aluminum dross was employed to realize high-temperature foaming due to its oxidation, which makes traditional AlN and salts removal process needless. Moreover, near-zero shrinkage or even expansion during sintering of porous ceramics have occurred because in-situ foaming process together with the oxidation of Al particles well offset the sintering shrinkage. After sintering at 1400°C for 2 h, porous ceramics composed of α-Al₂O₃ and spinel phases with open porosity of 37.91%, sintering expansion rate of 1.13%, flexural strength of 45.67 MPa, and thermal conductivity of 0.97 W/(m·K) have been prepared. Cenospheres as pore-forming agents have been added to further improve the porosity, and alumina-based porous ceramics with open porosity of 28.39%–43.20% and flexural strength of 15.80–52.48 MPa have been obtained. This effective solution for recycling secondary aluminum dross could supply high-performance porous ceramics, which is expected to be applied in the fields of light-weight structural components and thermal insulations.     

Application of polypropylene carbonate for the tape casting of silicon nitride ceramics

QPAC40 (polypropylene carbonate), with a little decomposition residue, is commonly used as a binder in aluminum nitride (AlN) tape casting. In this paper, we tried to explore its application in silicon nitride (Si₃N₄) tape casting. By studying the influence of dispersant, binder, plasticizer/binder ratio, and solid loading on slurry and green tape properties, the optimum formulation of the tape casting of Si₃N₄ slurry was determined, and the green tape with a uniform structure and relative density up to 63.16% was prepared. Si₃N₄ ceramics were obtained by debinding at 600°C for 1 h in vacuum and gas-pressure sintering at 1830°C for 2 h in N₂. The thermal conductivity and flexural strength of Si₃N₄ ceramics were 56.28 ± 1.21 W/(m·K) and 1130.67 ± 23.58 MPa, respectively. These results indicated that QPAC40 can be used to prepare Si₃N₄ sheets through tape casting.     

Lightweight porous silica-alumina ceramics with ultra-low thermal conductivity

Thermal protection has always been an important issue in the energy, environment and aerospace fields. Porous ceramics produced by the particle-stabilized foaming method have become a competitive material for thermal protection because of their low density and low thermal conductivity. However, the study of porous ceramics for composite systems using particle-stabilized foaming method was relatively rare. Here, silica-alumina composite porous ceramics were prepared by particle-stabilized foaming method, which was achieved by tailoring the surface charges of silica and alumina through adjustment of the pH. Porous ceramics exhibited porosity as high as 97.49% and thermal conductivity (25 °C) as low as 0.063 W m^?1 K^?1. The compressive strength of porous ceramics sintered at 1500 °C with a solid content of 30 wt% could reach 0.765 MPa. Based on the light weight and excellent thermal insulation properties, the composite porous ceramic could be used as a potential thermal insulation material in the spacecraft industry.     

Secondary phases,microstructures and properties of AlN ceramics sintered by adding nitrate sintering additives

AlN ceramics were sintered at a temperature range from 1650 to 1800°C through adding the Ca and Y nitrate sintering additives. Secondary phases, microstructures and properties of the AlN ceramics were studied. When the AlN ceramics are sintered at 1650 or 1675°C, CaO and Y₂O₃ from the sintering additives react with Al₂O₃ in the AlN powder to generate CaAl₄O₇ and Y₃Al₅O₁₂. Part of Y₃Al₅O₁₂ reacts with CaO and Al₂O₃ to form CaYAl₃O₇ at 1700°C. At 1800°C, CaYAl₃O₇ decomposes into CaAl₄O₇ and Y₃Al₅O₁₂. Finally, CaAl₄O₇ volatilises and only Y₃Al₅O₁₂ remains. As the sintering temperature increases, the AlN grains grow continuously and the bending strength and thermal conductivity of the AlN ceramics increase first and then decrease. The AlN ceramics sintered at 1700°C are fully dense and have the highest bending strength and thermal conductivity of 373·7 MPa and 136·7 W m^?1 K^?1 in this work.     

Direct bonding of silicon carbide ceramics sintered with yttria

SiC ceramics sintered with yttria were successfully joined without an interlayer by conventional hot pressing at lower temperatures (2000–2050 °C) compared to those of the sintering temperatures (2050–2200 °C). The joined SiC ceramics sintered with 2000 ppm Y₂O₃ showed almost the same thermal conductivity (˜198 Wm⁻¹ K⁻¹), fracture toughness (3.7 ± 0.2 MPa m^1/2), and hardness (23.4 ± 0.8 GPa) as those of the base material, as well as excellent flexural strength (449 MPa). In contrast, the joined SiC ceramics sintered with 4 wt% Y₂O₃ showed very high thermal conductivity (˜204 Wm⁻¹ K⁻¹) and excellent flexural strength (˜505 MPa). Approximately 16–22% decreases in strength compared to those of the base SC materials were observed in both joined ceramics, due to the segregation of liquid phase at the interface. This issue might be overcome by preparing well-polished and highly flat surfaces before joining.     

AlN with high strength and high thermal conductivity based on an MCAS-Y2O3-YSZ multi-additive system

The additive composition of an AlN ceramic substrate material was optimized to achieve high strength and thermal conductivity. MgO-CaO-Al₂O₃-SiO₂ (MCAS) glass and Y₂O₃ were used as basic additives for improved sintering properties and thermal conductivity, thereby allowing for AlN to be sintered at a relatively low temperature of 1600 °C without pressurization. Yttria-stabilized zirconia (YSZ) was added (0–3 wt%) to further improve the strength of the AlN ceramic. YSZ and Y₂O₃ reacted with AlN to produce ZrN, Y₄Al₂O₉, and Y₃Al₅O₁₂ secondary phases. The formation of these yttrium aluminate phases improved the thermal conductivity by removing oxygen impurities, while ZrN formed at the AlN grain boundaries provided resistance to grain boundary fractures for improved strength. Overall, the AlN ceramic with 1 wt% MCAS, 3 wt% Y₂O₃, and 1 wt% YSZ exhibited excellent thermal and mechanical properties, including a thermal conductivity of 109 W/mK and flexural strength of 608 MPa.     

Low-temperature hot-press sintering of AlN ceramics with MgO–CaO–Al2O3–SiO2 glass additives for ceramic heater applications

Aluminum nitride (AlN) is used a ceramic heater material for the semiconductor industry. Because extremely high temperatures are required to achieve dense AlN components, sintering aids such as Y₂O₃ are typically added to reduce the sintering temperature and time. To further reduce the sintering temperature, in this study, a low-melting-temperature glass (MgO–CaO–Al₂O₃–SiO₂; MCAS) was used as a sintering additive for AlN. With MCAS addition, fully dense AlN was obtained by hot-press sintering at 1500 °C for 3 h at 30 MPa. The mechanical properties, thermal conductivity, and volume resistance of the sintered AlN–MCAS sample were evaluated and compared with those of a reference sample (AlN prepared with 5 wt% Y2O3 sintering aid sintered at 1750 °C for 8 h at 10 MPa). The thermal conductivity of AlN prepared with 0.5 wt% MCAS was 91.2 W/m?K, which was 84.8 W/m?K lower than that of the reference sample at 25 °C; however, the difference in thermal conductivity between the samples was only 14.2 W/m?K at the ceramic-heater operating temperature of 500 °C. The flexural strength of AlN–MCAS was 550 MPa, which was higher than that of the reference sample (425 MPa); this was attributed to the smaller grain size achieved by low-temperature sintering. The volume resistance of AlN–MCAS was lower than that of the reference sample in the range of 200–400 °C. However, the resistivity of the proposed AlN–MCAS sample was higher than that of the reference sample (500 °C) owing to grain-boundary scattering of phonons. In summary, the proposed sintering strategy produces AlN materials for heater applications with low production cost, while achieving the properties required by the semiconductor industry.     

Pressureless sintered silicon carbide matrix with a new quaternary additive for fully ceramic microencapsulated fuels

This study suggests a new additive composition based on AlN–Y₂O₃–Sc₂O₃–MgO to achieve successful densification of SiC without applied pressure at a temperature as low as 1850 °C. The typical sintered density, flexural strength, fracture toughness, and hardness of the SiC ceramics sintered at 1850 °C without applied pressure were determined as 98.3%, 510 MPa, 6.9 MPa·m^1/2, and 24.7 GPa, respectively.Fully ceramic microencapsulated (FCM) fuels containing 37 vol% tristructural isotropic (TRISO) particles could be successfully sintered at 1850 °C using the above matrix without applied pressure. The residual porosity of the SiC matrix in the FCM fuels was only 1.6%. TRISO particles were not damaged during processing, which included cold isostatic pressing under 204 MPa and sintering at 1850 °C for 2 h in an argon atmosphere. The thermal conductivity of the pressureless sintered FCM pellet with 37 vol% TRISO particles was 44.4 Wm^?1 K^?1 at room temperature.     

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.     

The Preparation and Cure Kinetics Researches of Thermal Conductivity Epoxy/AlN Composites

The aluminum nitride (AlN) was employed to prepare epoxy/AlN composites by blending-casting moulding method, two different coupling agents were used to functionalize the surface of AlN. The thermal conductivity and mechanical properties of the composites were investigated. And the cure kinetics of the EP/AlN composites was studied by means of isothermal DSC. Results revealed that the thermal conductivity of EP improved remarkably with the addition of AlN, a higher thermal conductivity of 1.05 W/mK can be achieved with 42 vol% AlN, about 5 times higher than that of native epoxy resin. And the flexural and impact strength of the EP/AlN composites were optimal with 3.3 vol% AlN. The curing process of the EP/AlN composites contained autocatalytic mechanism, the whole process was according with the Kamal model. The presence of AlN did not change the cure reaction mechanism, and had little effecting on the activation energy, but decreased the rate constants k_l and k₂.