The influence of microstructure on the thermal conductivity of aluminium nitride

Starting from three different commercial powders, AIN materials were densified by pressureless sintering under various temperature and time values in order to investigate the influence of microstructure on thermal conductivity. The influence of the sintering aids (3 wt% Y₂O₃ and 2 wt% CaC₂) and of the forming processes (cold isostatic pressing and thermocompression of tape cast pieces) were also been evaluated. Thermal conductivity increased with the purity level of the starting powder and with an increasing the sintering temperature and soaking time. The highest thermal conductivity values (196 Wm^–1 K^–1) were obtained with the purest powder and high temperature (1800 °C) sintering over long periods (6 h). No influence on thermal conductivity was detected from the forming technique.     

Microstructure and properties of spark plasma sintered AlN ceramics

Spark plasma sintering (SPS) is a newly developed technique that enables poorly sinterable aluminum nitride (AlN) powder to be fully densified. It is addressed that pure AlN sintered by SPS has relatively low thermal conductivity. In this work, SPS of AlN ceramic was carried out with Y₂O₃, Sm₂O₃ and Li₂O as sintering aids. Effects of additives on AlN densification, microstructure and properties were investigated. Addition of sintering aids accelerated the densification, lowered AlN sintering temperature and was advantageous to improve properties of AlN ceramic. Thermal conductivity and strength were found to be greatly improved with the present of Sm₂O₃ as sintering additive, with a thermal conductivity value about 131 Wm⁻¹K⁻¹ and bending strength about 330 MPa for the 2 wt% Sm₂O₃-doped AlN sample SPS at 1,780 °C for 5 min. XRD measurement revealed that additives had no obvious effect on the AlN lattice parameters. Observation by SEM showed that AlN ceramics prepared by SPS method manifested quite homogeneous microstructure. However, AlN grain sizes and shapes, location of secondary phases varied with the additives. The thermal conductivity of AlN ceramics was mainly affected by the additives through their effects on the growth of AlN grain and the location of liquid phases.     

Thermal conductivity of calcium-doped aluminium nitride ceramics

Aluminium nitride ceramics were prepared with the addition of up to 12wt% of calcium oxide as a sintering aid. Both the oxygen and the calcium content of the samples decreased during sintering with increasing sintering temperature and soaking time. Higher amounts of calcium oxide resulted in higher thermal conductivities, with values up to 142 W m^–1 K^–1. Moderate sintering temperatures, short temperature soaking times and the use of inexpensive Ca-based sintering additives should enable the production of aluminium nitride ceramics with sufficiently high thermal conductivity at relatively low cost.     

High-temperature thermoelectric properties of the sintered Bi2Sr2Ca1 − xYxCu2Oy (x = 0 – 1)

Electrical conductivity and Seebeck coefficient were measured in a temperature range of 320–1073 K for sintered samples of Bi₂Sr₂Ca_{1 – x} Y _x Cu₂O _y (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0). It has been found that the conduction behavior changes from n-type metallic to p-type semiconducting with increasing yttrium concentration. The power factors were in a range of 1.7–3.0 × 10^–5 Wm^–1 K^–2 for the sample with x = 0.8, being maximized by the optimization of the yttrium concentration. The thermal conductivity for the sample with x = 0.8 was 0.73 Wm^–1 K^–1 at 310 K, and decreased with increasing temperature. The values of thermoelectric figure of merit were estimated to be in a range of 3.4–4.8 × 10^–5 K^–1 at temperatures of 320–673 K for the sample with x = 0.8.     

Effects of binary additives B2O3–Y2O3 on the microstructure and thermal conductivity of aluminum nitride ceramics

Aluminum nitride (AIN) ceramics, with binary additives B₂O₃-Y₂O₃, were sintered at temperatures from 1700 to 1850 °C. The microstructure and sintering characteristics were studied by XRD, HREM, SEM and TEM/EDS, which showed that Y₂O₃ gave different yttrium aluminates through the reaction with Al₂O₃ under different conditions. With the increase of sintering temperature, the yttrium-to-aluminum atomic ratio Y/Al decreased in the secondary phases of the sintered bodies. It was discovered that B₂O₃ could dissolve in the yttrium aluminates, forming some ordered structure with a superlattice. After sintering at 1850 °C for 4 h, a specimen with a fine microstructure and a thermal conductivity of 190 Wm^–1K^–1 was obtained.     

The study of AlN ceramics sintered at superhigh pressure with belt-type press technology

The effects of Y₂O₃ content, sintering time, sintering temperature, sintering pressure on thermal conductivity of AlN ceramics had been studied. X-ray diffraction (XRD), scanning electron microscope (SEM), laser conductometer and laser granularity dimension analysis measurer were respectively used to measure the phases, microstructure, thermal conductivity and particle size distribution of the samples. These studies reveal that the Y₂O₃ is an effective sintering addtive, and the best conditions of sintering are that the pressure is 5.15× 10⁹ Pa, the temperature is 1700∘C and the sintering time is 115 min. Under these conditions, the sintered body has reasonable structure and its thermal conductivity is 200 w/(m⋅k).     

Potential use of only Yb2O3 in producing dense Si3N4 ceramics with high thermal conductivity by gas pressure sintering

Yb₂O₃ is an efficient sintering additive for enhancing not only thermal conductivity but also the high-temperature mechanical properties of Si₃N₄ ceramics. Here we report the fabrication of dense Si₃N₄ ceramics with high thermal conductivity by the gas pressure sintering of α-Si₃N₄ powder compacts, using only Yb₂O₃ as an additive, at 1900 °C under a nitrogen pressure of 1 MPa. The effects of Yb₂O₃ content, sample packing condition and sintering time on the densification, microstructure and thermal conductivity were investigated. Curves of the density plotted against the Yb₂O₃ content exhibited a characteristic ‘N’ shape with a local minimum at 3 mol% Yb₂O₃ and nearly complete densification below and above this concentration. The effects of the sample packing condition on the densification, microstructure and thermal conductivity strongly depended on the Yb₂O₃ content. The embedded condition led to more complete densification but also to a decrease in thermal conductivity from 119 to 94 W m^-1 K⁻¹ upon 1 mol% Yb₂O₃ addition. The sample packing condition had little effect on the density and thermal conductivity (102–106 W m⁻¹ K⁻¹) at 7 mol% Yb₂O₃. The thermal conductivity value was strongly related to the microstructure.     

Microstructure and thermal conductivity of spark plasma sintering AlN ceramics

Abstract

Dense aluminium nitride ceramics were prepared by spark plasma sintering at a lower sintering temperature of 1700°C with Y₂O₃, Sm₂O₃ and Dy₂O₃ as sintering additives respectively. The effects of three kinds of sintering additives on the phase composition, microstructure and thermal conductivity of AlN ceramics were investigated. The results showed that those sintering additives not only facilitated the densification via the liquid phase sintering mechanism, but also improved thermal conductivity by decreasing oxygen impurity. Sm₂O₃ could effectively improve thermal conductivity of AlN ceramics compared with Y₂O₃ and Dy₂O₃. Observation by scanning electron microscopy showed that AlN ceramics prepared by spark plasma sintering method manifested quite homogeneous microstructures, but AlN grain sizes and shapes and location of secondary phases varied with the sintering additives. The thermal conductivity of AlN ceramics was mainly affected by the additives through their effects on the growth of AlN grain and the location of secondary phases.     

New ternary nitride ceramics: CaSiN2

The synthesis of CaSiN₂ powder, starting from metal nitrides, is described. Fully dense CaSiN₂ ceramics can be sintered from the prepared powder at 1700 °C. The samples were sintered in a closed Mo vessel to prevent evaporation of calcium nitride. The phase composition, and the chemical and mechanical properties of the as-prepared ceramics are described. The thermal conductivity at room temperature was evaluated as 2.4 Wm^–1 K^–1. A reasonable strength of 179 MPa and a fairly good fracture toughness of about 2.1 MPam^1/2 were found. A hardness of 9.6 GPa and a Young's modulus of 174 GPa were measured. The value of the relative dielectric constant was measured as 13.3. The bandgap for CaSiN₂ at room temperature was estimated from diffuse-reflectance spectra to be 4.5 eV. Considerable improvement in the properties are expected when the processing conditions which is well within reach are optimized.     

Sinterability of magnesium silicon nitride powder with yttrium oxide addition coated using the homogeneous precipitation method

The sinterability of magnesium silicon nitride (MgSiN₂) powder with yttrium oxide (Y₂O₃) addition was examined using the hot-pressing technique (31 MPa and N₂ atmosphere) at 1550°C for 90 min; the MgSiN₂ powder had been coated with 0–4 mass% of Y₂O₃ addition by a (urea-based) homogeneous precipitation method. Relative densities of the hot-pressed MgSiN₂ compacts (ceramics) with and without Y₂O₃ addition were 99.6% apart for the MgSiN₂ceramic with 4 mass% Y₂O₃ addition (98.4%). The thermal conductivities of the MgSiN₂ ceramics with 0–1 mass% Y₂O₃ addition were in the range of 20–21 W · m^–1 · K^–1 whilst the Vickers hardness was 19.7 GPa for the pure MgSiN₂ ceramic and decreased slightly with Y₂O₃ addition. Average fracture toughness values were in the range of 1.2–1.6 MPa · m^1/2 with significant trend being noted with regards to the ceramic containing 0.5 mass% of Y₂O₃. It was concluded that the use of homogeneous precipitation processing resulted in significant advantages regarding the densification, homogeneous microstructure, and fracture toughness despite the amount of Y₂O₃ addition being as low as 0.5 mass%.     

Preparation and properties of ALCON (Al28C6O21N6) ceramics

The synthesis of Al₂₈C₆O₂₁N₆ powder (ALCON), starting from the binary compounds is described. The powder is resistant to oxidation in air up to 760°C. From the prepared powder, fully dense ceramics have successfully been prepared using hot pressing. The as-prepared ceramics had a thermal conductivity of 20 W m^–1 K^–1. Experiments showed that it is also possible to prepare ALCON ceramics by reactive hot-pressing, starting from Al₂O₃, AlN and Al₄C₃. Further optimization is expected to raise the thermal conductivity significantly. The strength, about 300 MPa, is similar to that of AlN. The thermal expansion coefficient of 4.8 × 10^–6K^–1 closely matches that of silicon, making application of ALCON ceramics as heat sinks an interesting possibility.     

The use of yttrium (III) isopropoxide to improve thermal conductivity of polycrystalline aluminum nitride (AlN) ceramics

Instead of Y₂O₃ powders, yittrium isopropoxide (YIP) was used as a sintering additive to sinter high thermal conductivity polycrystalline aluminum nitride (AlN). The reasons for using sintering additive in sol-gel form are due to the fact that the particle sizes are uniform in the nano scale and also they promote a better coating of AlN grains, being more effective during sintering process. The binder burn out was carried in two different atmospheres, N₂ (N₂ BBO) and air (air BBO). The thermal conductivity of dense polycrystalline aluminum nitride samples with the addition of Y₂O₃ (YIP formulation) ranging from 1.0 to 10.0 wt% with N₂ BBO and air BBO was measured by the laser-flash technique. The results of measured thermal conductivity exhibited higher values than those reported for samples of same yttria formulation (Y₂O₃ powder) and sintered conditions.     

Thermal conduction mechanism of aluminium nitride ceramics

Extremely large grain size AIN ceramics were produced by HIP sintering at an ultra-high temperature of 2773 K without reducing the oxygen content in order to determine experimentally whether the factor controlling thermal conductivity is either grain boundaries or the internal structure of the grains. The room-temperature thermal conductivity of the HIPed AIN with a grain size of 40 m was 155 Wm^–1 K^–1, and was almost equal to that of the normally sintered AIN with a grain size of 4 m. Therefore, thermal conductivity at room temperature is independent of AIN grain size, or the number and amount of grain-boundary phase for reasonably well-sintered AIN ceramics. The calculated phonon mean free path of sintered bodies was 10–30 nm at room temperature, which is too small to compare with the AIN grain size. Consequently, it is shown that the thermal conductivity of sintered AIN is controlled by the internal structure of the grains, such as oxygen solute atoms.     

Preparation and Electrical Conductivity of BaZr1 – xRxO3 – α(R = Sc, Y, Ho, Dy, Gd, In)

The influence of process parameters on the density of BaZr_0.9Y_0.1O₃proton-conducting ceramics was investigated. Dense ceramics (94–96% of theoretical density) were obtained by synthesis from coprecipitated zirconium and yttrium hydroxides and barium carbonate, followed by sintering at 1700°C. The conductivity of BaZr_0.93R_0.07O_{3 –} (R = Sc, Y, Ho, Dy, Gd, In) was measured as a function of temperature and oxygen partial pressure and was found to decrease in the order Y > Ho > Sc > Dy, In > Gd. In air, these materials are hole–ion conductors. At 800°C, BaZr_0.93Y_0.07O_{3 –} has an ionic transference number of 0.16 and ionic conductivity of 3.6 × 10^–4S/cm.     

Development of as-fired aluminium nitride substrates with smooth surface and high thermal conductivity

As-fired aluminium nitride (AIN) substrates with smooth and uniform surface have been developed by green sheet and firing technology. The effect of setting for firing on surface roughness was investigated. AIN substrates were fabricated by pressureless sintering of green sheets piled up and sandwiched between AIN plates in an AIN crucible. The thermal conductivity, surface roughness and bending strength of the substrate sintered at 1770 °C for 2 h under a pressure of 1 MPa nitrogen were 194 Wm^–1 K^–1, 0.15 (m and 353 MPa, respectively.     

Potential use of only Yb2O3 in producing dense Si3N4 ceramics with high thermal conductivity by gas pressure sintering

Abstract

Yb₂O₃ is an efficient sintering additive for enhancing not only thermal conductivity but also the high-temperature mechanical properties of Si₃N₄ ceramics. Here we report the fabrication of dense Si₃N₄ ceramics with high thermal conductivity by the gas pressure sintering of α-Si₃N₄ powder compacts, using only Yb₂O₃ as an additive, at 1900 °C under a nitrogen pressure of 1 MPa. The effects of Yb₂O₃ content, sample packing condition and sintering time on the densification, microstructure and thermal conductivity were investigated. Curves of the density plotted against the Yb₂O₃ content exhibited a characteristic ‘N’ shape with a local minimum at 3 mol% Yb₂O₃ and nearly complete densification below and above this concentration. The effects of the sample packing condition on the densification, microstructure and thermal conductivity strongly depended on the Yb₂O₃ content. The embedded condition led to more complete densification but also to a decrease in thermal conductivity from 119 to 94 W m^-1 K^?1 upon 1 mol% Yb₂O₃ addition. The sample packing condition had little effect on the density and thermal conductivity (102–106 W m^?1 K^?1) at 7 mol% Yb₂O₃. The thermal conductivity value was strongly related to the microstructure.     

An assessment of expressions for the apparent thermal conductivity of cellular materials

Diverse expressions for the thermal conductivity of cellular materials are reviewed. Most expressions address only the conductive contribution to heat transfer; some expressions also consider the radiative contribution. Convection is considered to be negligible for cell diameters less than 4 mm. The predicted results are compared with measured conductivities for materials ranging from fine-pore foams to coarse packaging materials. The dependencies of the predicted conductivities on the material parameters which are most open to intervention are presented graphically for the various models.Nomenclature a Absorption coefficient - C _itv(J mol^–1 K^–1) Specinc heat - E Emissivity - E _L Emissivity of hypothetical thin parallel layer - E _o Boundary surfaces emissivity - f Fraction of solid normal to heat flow - f _s Fraction of total solid in struts of cell - K(m^–1) Mean extinction coefficient - k(Wm^–1 K^–1) Effective thermal conductivity of foam - k _cd(Wm^–1 K^–1) Conductive contribution - k _cr(Wm^–1 K^–1) Convertive contribution - k _g(Wm^–1K^–1) Thermal conductivity of cell gas - k _r(Wm^–1 K^–1) Radiative contribution - k _s(Wm^–1 K^–1) Thermal conductivity of solid - L(m) Thickness of sample - L _g(m) Diameter of cell - L _s(m) Cell-wall thickness - n Number of cell layers - r Reflection coefficient - t Transmission coefficient - T(K) Absolute temperature - T _m(K) Mean temperature - T _N Fraction of energy passing through cell wall - T ₁(K) Temperature of hot plate - T ₂(K) Temperature of cold plate - V _g Volume fraction of gas - V _w Volume fraction of total solid in the windows - w Refractive index - (m) Effective molecular diameter - (Pa s) Gas viscosity - Structural angle with respect to rise direction - (Wm^–2 K^–4) Stefan constant     

Hot-pressed AlN-Cu metal matrix composites and their thermal properties

AlN-Cu metal matrix composites containing AlN volume fractions between 0.1 and 0.5 were fabricated firstly by liquid phase sintering of AlN using Y₂O₃ as a sintering aid and then by hot pressing the powder mixtures of sintered AlN and Cu at 1050°C with a pressure of 40 MPa under flowing nitrogen. With Y₂O₃ additions of 1.5 to 10 wt%, the densification of AlN could be achieved by liquid phase sintering at 1900°C for 3 h and subsequently slow cooling. The sintered AlN showed a maximum thermal conductivity of 166 W/m/K at a Y₂O₃ level of 6 wt%. Dense AlN-Cu composites with AlN contents up to 40 vol% were achieved by hot pressing. The thermal conductivity and the coefficient of the thermal expansion (CTE) of the composites decreased with increasing AlN volume fractions, giving typical values of 235 W/m/K and 12.6 × 10^–6/K at an AlN content of 40 vol%.     

High dielectric AlN/Al2O3 composite powder using a plasma spray approach for microelectronics application

Increasing demand for higher performance dielectric material for multi-layer ceramics packaging has led to the use of the AlN system due to its very high thermal conductivity and coefficient of expansion compatibility with silicon. This paper reports on a novel process method used to produce an AlN/Al₂O₃ composite powder system which can be subsequently tape cast as a dielectric substrate. The mixture of both Al₂O₃ and AlN was first mechanically alloyed and then spray-dried to obtain a suitable agglomerated powder that was subsequently plasma-sprayed, resulting in a fine micrometer level integrated composite powder. The two main criteria used to ascertain the optimal process parameters during plasma spraying were a high gamma/alpha Al₂O₃ phase ratio, which ensured that all the Al₂O₃ phase had melted during plasma spraying, and a minimal reduction in the AlN/Al₂O₃ ratio to ensure minimal change in the AlN during processing. For the plasma-sprayed composite powders, fully sintered ceramic tapes were produced attaining>99.0% of the theoretical density after sintering at 1650°C for 6 h, which yielded a thermal conductivity value of 32.0 W m^–1 K^–1.     

The effect of carbon coating of AIN powder on sintering behavior and thermal conductivity

High thermal conductive AlN ceramics doped with Y₂O₃ were produced by sintering the powders obtained after applying a carbon coating to the surface of AlN powder grains. During sintering at 1800°C for 1 hour, the carbon reacts with the surface of the AlN grains by carbothermal-reduction of Al₂O₃, and also with the Al₂Y₄O₉ intermediate phase to form AlN, Y₂O₃ and CO. By adding 0.56 mass% of carbon, almost all the Al₂Y₄O₉ is reacted and the thermal conductivity increases from 184 W/(m · K) to 224 W/(m · K). Further carbon addition decreases the thermal conductivity and also the final sintered density.