Grain boundary blocking effects in Sm/Yb-doped AlN ceramics

The effect of microstructural changes on the electrical and thermal properties of AlN ceramics is studied in terms of cation size and nature of sintering aids (i.e. Sm₂O₃ and Yb₂O₃) in AlN ceramics. It is revealed that the addition of Yb₂O₃ to Sm-bearing AlN ceramics results in 80 % reduction of thermal conductivity with an increase of the grain boundary resistivity that is one order of magnitude larger than for the sample without Yb₂O₃. Additionally, the grain boundary/grain resistivity ratio is significantly increased, when the Sm₂O₃ sintering aid is employed instead of Yb₂O₃, for which the secondary phases at the grain boundaries and the triple junctions are responsible for the increase in the electrical resistivity. The microstructural investigations confirm the tendency of the secondary phase to segregate at the triple junctions in Sm-containing AlN ceramics while it is grain boundaries that are favored as segregation site in the case of Yb.     

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.     

Influence of ball milling contamination on properties of sintered AlN substrates

The AlN substrate was fabricated by the tape casting process, and its thermal conductivity and electrical conductivity were investigated for various ball milling times and types of milling media. The oxygen content was measured after ball milling, de-binding process, and sintering. The oxygen content after the de-binding process was 1.2–2.3 wt%, similar to that after milling. After the de-binding process, the specimens were sintered at 1850 ℃ for 3 h in nitrogen atmosphere. The thermal conductivity of the sintered specimens decreased from 158 W m⁻¹ K⁻¹ to 100 W m⁻¹K⁻¹ with increasing milling time. Simultaneously, the electrical conductivity decreased from approximately 10⁻⁷ Ω⁻¹ cm⁻¹ to 10⁻⁹ Ω⁻¹ cm⁻¹ at 500 °C when Al₂O₃ or ZrO₂ balls were used, whereas the electrical conductivity did not decrease when Si₃N₄ balls were used.     

Mechanical properties and thermal conductivity of Si3N4 ceramics with YF3 and MgO as sintering additives

Si₃N₄ ceramic was densified by hot pressing sintering at 1750 °C for 1 h under the uniaxial pressure of 20 MPa in N₂ atmosphere with YF₃ and MgO as sintering additives. The thermal conductivities of SN-YF specimen were both higher than that of Si₃N₄ ceramic sintered with Y₂O₃ and MgO before and after annealing treatment. The grain size and aspect ratio in SN-YF specimen were both bigger than those in the SN-YO specimen, which was beneficial for the creation of high thermal conductive path. On the other hand, the improvement of thermal conductivity by the addition of YF₃ might be attributed to the reduction of the grain boundary phase due to the evaporation of SiF₄, and the resultant reduction of the lattice oxygen due to the reduction of SiO₂ in the grain boundary phase. The {0001} direction of grains had the probability of growing along the hot pressing direction in the SN-YF specimen, which was beneficial for the improvement of thermal conductivity while the {0001} direction grew along the X₀-Y₀ plane in the SN-YO specimen. The mechanical properties of SN-YF specimen were comparable to those of SN-YO specimen.     

Effect of hot-pressing sintering on thermal and electrical properties of AlN ceramics with impedance spectroscopy and dielectric relaxations analysis

The effects of hot-pressing sintering on the phase composition, microstructure, thermal and electrical properties of AlN ceramics with CeO₂–CeF₃ additives were studied. During hot-pressing sintering, high pressure reduced the grain boundary phase CeAlO₃ and decreased the concentration of oxygen in AlN ceramics. The hot-pressing sintered AlN samples had a much higher thermal conductivity of 191.9 W/m·K than pressureless sintered ones because of the great reduction of grain boundary phases and oxygen impurities in AlN ceramic. As the carbon content in hot-pressing sintered sample was very high, carbon contamination led to the decrease in electrical resistivity and changes in polarization mechanisms for AlN ceramics. The relaxation peak in the dielectric temperature spectrum with an activation energy of 0.64 eV for hot-pressing sintered samples was caused by electrons from free carbon at low temperature. Overall, hot-pressing sintering can effectively increase the thermal conductivity and change the electrical properties of AlN ceramics.     

Effects of doping Al-metal powder on thermal,mechanical and dielectric properties of AlN ceramics

In this work, the influence of Al-metal powder addition upon that thermal, mechanical and dielectric properties of aluminium nitride (AlN) ceramic was studied. The findings show that adding Al-metal powder improves not only the mechanical and thermal properties of the AlN ceramic but also has no negative impact on its dielectric properties. Based on Y₂O₃ as sintering aid, the AlN ceramic with 1.0 wt% Al doping were 14.35% higher thermal conductivity, 11.73% higher flexural strength and 59.50% higher fracture toughness than those doped without Al, respectively. This study showed that the addition of Al-metal powder may favor the purifying of the AlN lattice and the formation of homogenous and isolated second phase, which would increase the AlN–AlN interfaces and improve the thermal conductivity. Furthermore, the grain boundaries of AlN ceramics might be strengthened by the isolated second phases due to the thermal mismatch between the second phases and AlN grains, thus strengthening and toughening the AlN ceramic doped with Al. However, the large additive amount of Al powder (>1.0 wt%) was not help the isolation and homogenization of the second phase, giving a deterioration in an AlN ceramic's mechanical and thermal properties. These results suggest that the introduction of an appropriate dose of aluminium metal powder is a simple method that can be used to improve the AlN ceramic's mechanical and thermal properties simultaneously.     

Structural,thermal and mechanical properties of aluminum nitride ceramics with CeO2 as a sintering aid

AlN ceramics have been prepared with CeO₂ as a sintering aid at a sintering temperature of 1900 °C. The effect of CeO₂ contents on the microstructure, density, thermal conductivity and hardness was investigated. Addition of CeO₂ exerted a significant effect on the densification of AlN ceramics and hence on the microstructure. Thermal conductivity of AlN ceramics increased with CeO₂ content and was greater than that of Y₂O₃-doped AlN ceramics at a similar sintering temperature. The resulting AlN ceramics with 1.50 wt% of CeO₂ had the highest relative density of 99.94%, thermal conductivity of 156 W m⁻¹ K⁻¹ and hardness of 72.46 kg/mm².     

Effects of aligned carbon nanotube microcolumns on mechanical and thermal properties of C/SiC composites prepared by LA-CVI methods

Herein, C/SiC-CNTs composites were prepared by laser assisted chemical vapor infiltration (LA-CVI) method combined with vacuum impregnation. Density, mechanical property and thermal conductivity of as-prepared composites were then investigated by various analytical methods. Scanning electron microscopy (SEM) revealed good dispersion of CNTs in C/SiC-CNTs between composites layers and directional heat transfer channels. This formed unique three-dimensional connected networks, reinforcing multi-scale composites matrix. Average density and bending strength of composites were estimated to 2.35 g cm⁻³ and 598 MPa, respectively, which is 20.5% and 27.2% higher than those of CVI-C/SiC composites. The comparison between theoretical thermal conductivity and experiments revealed that the overall thermal conductivity of LA-CVI-C/SiC-CNTs composites (150.42 W m⁻¹ K⁻¹) was nearly 25 times higher than that of CVI-C/SiC composites.     

Microstructure evolution of Si3N4 ceramics with high thermal conductivity by using Y2O3 and MgSiN2 as sintering additives

Silicon nitride (Si₃N₄) ceramics were prepared by gas-pressure sintering using Y₂O₃–MgSiN₂ as a sintering additive. The densification behavior, phase transition, and microstructure evolution were investigated in detail, and the relevance between the microstructure and the performance (including thermal conductivity and mechanical properties) was further discussed. A significant change from a bimodal to a homogeneous microstructure and a decreased grain size occurred with increasing Y₂O₃–MgSiN₂ content. When the small quantity of preformed β-Si₃N₄ nuclei grew preferentially and rapidly in a short time, an obvious bimodal microstructure was obtained in the sample with 4 mol% and 6 mol% Y₂O₃–MgSiN₂. When more β-Si₃N₄ nuclei grew at a relatively rapid rate, the sample with 8 mol% Y₂O₃–MgSiN₂ showed a microstructure consisting of numerous abnormally grown β-Si₃N₄ grains and small grains. When more β-Si₃N₄ nuclei grew simultaneously and slowly, there was a homogeneous microstructure and smaller grains in the sample containing 10 mol% Y₂O₃–MgSiN₂. Benefitting from the completely dense, significant bimodal microstructure, low grain boundary phase, and excellent Si₃N₄–Si₃N₄ contiguity, the sample containing 6 mol% Y₂O₃–MgSiN₂ exhibited great comprehensive performance, with a maximum thermal conductivity and fracture toughness of 84.1 W/(m⋅K) and 8.97 MPa m^1/2, as well as a flexural strength of 880.2 MPa.     

Thermal conductivities and mechanical properties of AlN ceramics fabricated by three dimensional printing

AlN ceramics were successfully fabricated through a joint process of digital light processing (DLP) 3D printing technology and heat treatment at 1780 °C∼1845 °C. DLP is an addictive manufacturing process, enabling the near net shape fabrication. The AlN grains in this work developed well and there were small amounts of grain-boundary phases at the three-grain junctions. The particle size of AlN became larger and the densification increased with increasing sintering temperature. The pores of AlN ceramics also decreased, which led to the increase of thermal conductivity and flexural strength. The optimal thermal conductivity and flexural strength of AlN ceramic reached 155 W/(m·K) and 265 ± 20 MPa when sintered at 1845 °C.     

Densification and properties of AlN ceramic bonded carbon

To obtain light and tough materials with high thermal conductivity, AlN ceramic bonded carbon (AlN/CBC) composites were fabricated at temperatures from 1600 to 1900 °C in a short period of 5 min by the spark plasma sintering technique. All AlN/CBCs (20 vol% AlN) have unique microstructures containing carbon particles of 15 μm in average size and continuous AlN boundary layers of 0.5-3 μm in thickness. With an increase in sintering temperature, AlN grains grow and anchor into carbon particles, resulting in the formation of a tight bonding layer. The AlN/CBC sintered at 1900 °C exhibited a light weight (2.34 g/cm³), high bending strength (100 MPa), and high thermal conductivity (170 W/mK).     

Phase and microstructure optimization of grain boundary oxides and its effect on the thermal conductivity of Y2O3-doped AlN ceramics

AlN green bodies with variable O and C contents were employed to fabricate Y₂O₃-doped AlN ceramics of different grain-boundary phase compositions and microstructures via debinding in air and N₂, respectively. The microstructural evolution and grain-boundary oxide migration and their effects on the properties of the ceramics were explained. Finally, modified models were built to predict the thermal conductivity of these AlN ceramics with complex microstructures. During sintering, the oxide melt migrates to the ceramic surface driven by the differences between the surface energy and solid/liquid interface energy of the melt. The phase compositions and distributions of the grain-boundary oxides vary with sintering temperature. In addition, the amorphous layers were detected experimentally. All of these factors have great effects on ceramics properties. AlN ceramics were shown to have a thermal conductivity as high as 221.64 W/(m·K), which agrees with the value predicted via modified models.     

Enhanced mechanical and thermal properties of AlN ceramics via a chemical precipitation process

A uniform dispersion of sintering additives is crucial to improve the thermal and mechanical properties of AlN ceramics. In this study, the Y₂O₃-coated AlN composite powder was successfully prepared by the chemical precipitation (CP) process, thereby improving the homogenization of Y₂O₃ in AlN green compacts. The precipitation coating behavior of Y₂O₃ precursor was investigated by FTIR and TG-DSC, and the corresponding reaction equation was proposed. The results of TEM, XRD, and XPS for the CP processed AlN powder indicated that a uniform amorphous Y₂O₃ layer was fully wrapped on the surface of AlN powder. The microstructures and phases of the sintered AlN samples prepared via the CP and conventional ball-milling (BM) processes, respectively, were compared. The CP process can result in decreasing oxygen content in AlN grains, facilitating the formation of the desirable isolated second phases, and strengthening the grain and grain boundary of AlN ceramic. As a result, the thermal conductivity, bending strength and fracture toughness of the CP processed AlN ceramic are 9.43%, 10.56%, and 18.50% higher than those of the BM processed sample, respectively, illustrating the CP process is a pretty effective way to simultaneously improve the thermal and mechanical properties of AlN ceramics.     

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.     

Effects of granule compaction procedures on defect structure, fracture strength and thermal conductivity of AlN ceramics

The effect of granule compaction procedures on defect structure, fracture strength and thermal conductivity was examined for AlN ceramics using the same starting granules. For this study, changing the order of the cold isostatic pressing (CIP) and dewaxing procedure was performed, which changed the compaction behavior of the granule bed. The structural examination of green and sintered bodies showed that the change of granule strength strongly influenced the size and concentration of the granule related defects in sintered bodies. A large difference of the fracture strength associated with the change of granule strength was noted, and it was ascribed to the difference between the defect structures in the sintered bodies. On the other hand, the thermal conductivity was kept almost constant (> 150 W/m K) against the process alteration.     

Effects of SmF3 addition on aluminum nitride ceramics via pressureless sintering

Aluminum nitride (AlN) ceramics with dense structure, high thermal conductivity, and exceptional mechanical properties were fabricated by pressureless sintering with a novel non-oxide sintering additive, samarium fluoride (SmF₃). The results showed that the use of a moderate amount of SmF₃ promoted significant densification of AlN and removed the oxygen impurity. This led to the formation of fine and isolated secondary phase that cleaned the grain boundaries and increased the contact between AlN grains, remarkably enhancing thermal conductivity. Furthermore, SmF₃ also exhibited grain refinement and grain boundary strengthening effects similar to traditional sintering additive, samarium oxide (Sm₂O₃), leading to high mechanical properties in SmF₃-doped AlN samples. The most optimal characteristics (thermal conductivity of 190.67 W·m⁻¹·K⁻¹, flexural strength of 403.86 ± 18.27 MPa, and fracture toughness of 3.71 ± 0.19 MPa·m^1/2) were achieved in the AlN ceramic with 5 wt% SmF₃.     

Synergistic effect of binary fluoride sintering additives on the properties of silicon nitride ceramics

A variety of combinations of YF₃ and MgF₂ were used as sintering aids in the fabrication of Si₃N₄ ceramics via gas pressure sintering (GPS). The synergistic effects of YF₃ and MgF₂ on the liquid viscosity, mechanical properties, thermal conductivities, and grain growth kinetics of the Si₃N₄ ceramics were investigated. The results showed that appropriately adjusting the YF₃/MgF₂ ratio could decrease liquid viscosity, reducing the diffusion energy barrier of the solute atom and promoting mass transfer. Meanwhile, the chemical bonding strength in the grain boundary complexions formed by the metal cations also influenced grain boundary migration. Samples doped with 4 mol% YF₃ and 2 mol% MgF₂ achieved the lowest grain growth exponent (n = 2.9) and growth activation energy (Q = 616.7 ± 16.5 kJ mol^?1) as well as the highest thermal conductivity (83 W m^?1 K^?1) and fracture toughness (8.82 ± 0.13 MPa m^1/2).     

Fabrication and thermal conductivity of AlN/BN ceramics by spark plasma sintering

Aluminum nitride/boron nitride (AlN/BN) ceramics with 15–30 vol.% BN as secondary phase were fabricated by spark plasma sintering (SPS), using Yttrium oxide (Y₂O₃) as sintering aid. Effects of Y₂O₃ content and the SPS temperature on the density, phase composition, microstructure and thermal conductivity of the ceramics were investigated. The results revealed that with increasing the amount of starting Y₂O₃ in AlN/BN, Yttrium-contained compounds were significantly removed after SPS process, which caused decreasing of the residual grain boundary phase in the sintered samples. As a result, thermal conductivity of AlN/BN ceramics was remarkably improved. By addition of Y₂O₃ content from 3 wt.% to 8 wt.% into AlN/15 vol.% BN ceramics, the thermal conductivity increased from 110 W/m K to 141 W/m K.     

Fabrication of high thermal conductivity silicon nitride ceramics by pressureless sintering with MgO and Y2O3 as sintering additives

The fabrication of silicon nitride (Si₃N₄) ceramics with a high thermal conductivity was investigated by pressureless sintering at 1800 °C for 4 h in a nitrogen atmosphere with MgO and Y₂O₃ as sintering additives. The phase compositions, relative densities, microstructures, and thermal conductivities of the obtained Si₃N₄ ceramics were investigated systemically. It was found that at the optimal MgO/Y₂O₃ ratio of 3/6, the relative density and thermal conductivity of the obtained Si₃N₄ ceramic doped with 9 wt% sintering aids reached 98.2% and 71.51 W/(m·K), respectively. EDS element mapping showed the distributions of yttrium, magnesium and oxygen elements. The Si₃N₄ ceramics containing rod-like grains and grain boundaries were fabricated by focused ion beam technique. TEM observations revealed that magnesium existed as an amorphous phase and that yttrium produced a new secondary phase.     

Thermal conductivity and mechanical properties of Si3N4 ceramics with binary fluoride sintering additives

Silicon nitride (Si₃N₄) ceramics were fabricated by gas pressure sintering (GPS) using four sintering additives: Y₂O₃–MgO, Y₂O₃–MgF₂, YF₃–MgO, and YF₃–MgF₂. The phase composition, grain growth kinetics, mechanical properties, and thermal conductivities of the Si₃N₄ ceramics were compared. The results indicated that the reduction of YF₃ on SiO₂, induced a high Y₂O₃/SiO₂ secondary phase ratio, which improved the thermal conductivity of the Si₃N₄ ceramics. The depolymerization of F atom reduces the diffusion energy barrier of solute atom and weakens the viscous resistance of anion group, which was beneficial to grain boundary migration. Besides exhibiting a lower grain growth exponent(n = 2.5)and growth activation energy (Q = 587.94 ± 15.35 kJ/mol), samples doped with binary fluorides showed excellent properties, including appreciable thermal conductivity (69 W m⁻¹ K⁻¹), hardness (14.63 ± 0.12 GPa), and fracture toughness (8.75 ± 0.18 MPa m^1/2), as well as desirable bending strength (751 ± 14 MPa).