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%.     

Sintering chemical reactions to increase thermal conductivity of aluminium nitride

Chemical reactions to increase thermal conductivity by decreasing oxygen contents during AlN sintering with an Y₂O₃ additive in a reducing nitrogen atmosphere with carbon were investigated. They were: Al₂O₃ + N₂ + 3CO ⇋ 2AlN + 3CO₂, Al₂Y₄O₉ + N₂ + 3CO ⇋ 2AlN + 2Y₂O₃ + 3CO₂ and Y₂O₃ + N₂ + 3CO ⇋ 2YN + 3CO₂. Some of the CO₂ gas reduced to CO gas in the presence of carbon by a chemical reaction: CO₂ + C ⇋ 2CO. These reactions were confirmed by examining oxygen contents, the grain boundary phases of the sintered AlN, and the trapped CO and CO₂ gases in the sintered bodies. These reducing reactions proceed with increasing sintering temperature and periods, and hence the thermal conductivity is increased.     

Low temperature sintering of aluminum nitride with millimeter-wave heating

Rapid sintering of Yb₂O₃-added AlN was performed by applying the 28 GHz millimeter-wave heating method. It was found that full densification over 97%T.D. was attained by sintering at 1600°C for 20 min. The densification temperature was decreased by about 300°C, compared with those in the conventional method by an electric furnace. A high thermal conductivity over 180 W/(m · K) was obtained in the sample sintered at 1700°C for 40 min, even under non-reducing atmosphere. The main factor resulting in the rapid and low temperature sintering was attributed to efficient selective absorption of the millimeter-wave into Yb₂O₃ additive.     

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).     

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.     

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.     

CaO-Y2O3添加剂对AlN陶瓷显微结构及性能的影响

研究了掺杂ＣａＯ－Ｙ２Ｏ３热压烧结和常压烧结ＡｌＮ陶瓷的性能和显微结构．结果表明：热压烧结ＡｌＮ陶瓷的第二相为Ｙ３Ａｌ５Ｏ１２，常压烧结ＡｌＮ陶瓷的第二相为Ｙ３Ａｌ５Ｏ１２和Ｃａ３Ｙ２Ｏ６；热压烧结ＡｌＮ的第二相体积百分数和晶格氧含量均低于常压烧结；热压烧结ＡｌＮ陶瓷的微观结构良好，其热导率达到２００Ｗ／ｍ·Ｋ．     

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.     

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.     

Joining of AlN and graphite disks using interlayer tapes by spark plasma sintering

AlN and graphite disks were successfully joined using a polymer plasticized ceramic tape as the interlayer by spark plasma sintering (SPS). The tape contains either composite powders of AlN and graphite or AlN powders without graphite. Both tapes contained 5 mass% Y₂O₃ as the sintering aid of AlN. The joining was carried out at 1700–1900 °C and 30 MPa for 5 min. No other reaction phase except for Al₂Y₄O₉ was identified in the joints. The maximum tensile strength of the joints was obtained when the AlN–graphite composite interlayer tape was used. The joining mechanism is attributed not to the chemical bonding, but to the physical bonding of the Al₂Y₄O₉ phase, which is solidified from the molten Al–Y–O squeezing into the porous graphite under pressure during SPS.     

Migration of liquid phase in low temperature sintering of AlN

In the process of low-temperature sintering of AlN ceramics, the reaction of the sintering aids YF₃ and CaF₂ with superficial Al₂O₃, inherently contained in AlN lattice, results in formation of liquid phase. Nevertheless, the uniformly dispersed liquid phase is prone to migrate from the bulk to the surface of the samples, opposing densification. The analysis of the experimental results indicates that fresh liquid phase can continuously arrive from the bulk to the surface due to chemical reactions and crystallization which occur at the surface as well as wettalibilty and capillarity phenomena. The surface is depleted of liquid phase since the latter is consumed due crystallization and carbothermal reduction reactions with the elements of the atmosphere of the furnace N₂ and C, resulting in formation of a dense layer of crystals of Al₂Y₄O₉, CaYAl₃O₇ and Y₂O₃, grown perpendicularly to the surface. The chemical and structural features of this newly formed crystalline surface layer generate a significant difference of the wetting regimes and the capillary forces between the surface and the bulk, favouring pumping of the liquid from the bulk to the surface.     

Preparation, sintering and fracture behavior of Al2O3/LaAl11O18 ceramic composites

Al₂O₃/25 vol% LaAl₁₁O₁₈ composites were prepared by pressureless sintering at 1550°C with composite powders obtained by copercipiated method using La(NO₃) · 6H₂O and Al(NO₃)₃ · 9H₂O as starting materials. The enhanced reactive activity of Al₂O₃ and chemically homogeneous mixing of the constituents made LaAl₁₁O₁₈ phase to be formed at low temperature in composite powders. AlF₃ additive was used to reduce the transformation temperature of transition alumina. The LaAl₁₁O₁₈ grains in the composite powder obtained at 1500°C showed rodlike morphology distributed homogeneously in Al₂O₃ powder. The samples sintered at 1550°C for 4 h with CAS (CaO-Al₂O₃-SiO₂) sintering aid can obtain a high relative density. The effects of the sintering time on the grain growth of Al₂O₃ and the fracture toughness of the composites were studied and the results showed that LaAl₁₁O₁₈ grains reduced the growth of Al₂O₃ grains and the rodlike grains increased the fracture toughness. The improvement in fracture toughness of the composites was mainly attributed to the mechanism of crack deflection.     

Thermal conductivity and heat capacity of α- and β-BaB<Subscript>2</Subscript>O<Subscript>4</Subscript> single crystals

The thermal conductivity of β- and α-BaB₂O₄ single crystals has been measured at temperatures from 50 to 300 K by a steady-state axial flow technique. The 300-K thermal conductivity of the β-polymorph along and across its c axis is 1.64 ± 0.08 and 1.24 ± 0.06 W/(m K), respectively, and that of the α-polymorph along its c axis is 1.65 ± 0.08 W/(m K). Swirls and twin boundaries have an insignificant effect on the thermal conductivity of α-BaB₂O₄ crystals. The heat capacity of α-BaB₂O₄ measured in the range 56–300 K using adiabatic calorimetry differs little from that of the β-polymorph.     

Influence of yttrium dopant on the synthesis of ultrafine AlN powders by CRN route from a sol–gel low temperature combustion precursor

Y-doped ultrafine AlN powders were synthesized by a carbothermal reduction nitridation (CRN) route from precursors of Al₂O₃, C and Y₂O₃ prepared by a sol–gel low temperature combustion technology. The Y dopant reacted with alumina and thus forming yttrium aluminate of AlYO₃, Al₃Y₅O₁₂ and Al₂Y₄O₉, which formed a liquid at about 1400 °C and promoted the transformation of Al₂O₃ to AlN and the growth of AlN particles. Compared with the conventional solid CRN process, Y dopant reduced the synthesis temperature by 150 °C, and Al₂O₃ transformed to AlN completely at 1450 °C. The content of Y dopant had little effect on the synthesis temperature of AlN whereas it influenced the phase of Y compounds in the products. As the Y/Al molar ratio was in the range of 0.007648–0.022944, the particle sizes of Y-doped AlN powders synthesized at 1450 °C were 150–300 nm.     

Transparent polycrystalline ruby ceramic by spark plasma sintering

Fine-grained and transparent polycrystalline ruby ceramics (Cr₂O₃-doped Al₂O₃) were successfully prepared by spark plasma sintering (SPS). The effect of Cr₂O₃ concentration on the grain size, hardness, fracture toughness and thermal conductivity of ruby ceramics was investigated systematically. For 0.05 wt.% Cr₂O₃, high in-line transmittance of 85% at 2000 nm can be reached, further increase of Cr₂O₃ concentration leads to the decrease in transmittance. High hardness of 23.95-25.05 GPa can be achieved due to the fine grain size in all ruby ceramics. The fracture toughness of 1.9-2.29 MPa m^1/2 indicates that no improvement in fracture toughness over pure Al₂O₃ can be obtained by Cr₂O₃ doping in these submicron grained ruby ceramics. High thermal conductivity of 28-29.8 W/(m K) at room temperature, close to that of single crystal sapphire, can be achieved. The change in grain size for different Cr₂O₃ concentrations is the major reason for the change in mechanical and thermal properties, but not for the change in optical properties.     

Low temperature co-fired AlN multilayer substrates

A process for low temperature co-fired AlN multilayer substrates is introduced. Some key factors about this technology are delineated and discussed. A two-step burnout process may solve the contradiction between tungsten oxidation and carbon removal. Sintering with additives appears to improve densification at low temperature. DyN was found as a second phase in AlN ceramics, which suggests that Dy₂O₃ efficiently removes oxygen from the AlN lattice. The microstructure of AlN ceramics is ideal for achieving high thermal conductivity. Analysis of the AlN-W interface showed there were no second phases, but there was probably an intricate interlocking structure between the grains of tungsten and AlN. Co-firing at 1650°C for 4 h produced an AlN multilayer substrate with a thermal conductivity of up to 130 W m⁻¹ K⁻¹. This revised version was published online in July 2006 with corrections to the Cover Date.     

Analysis of local heat transfer properties of tape-cast AlN ceramics using photothermal reflectance microscopy

Photothermal reflectance microscopy was applied to the analysis of local thermal diffusivity on tape-cast AlN ceramics. The materials were obtained from three different commercial powders, two sintering temperatures (1750 and 1800 °C), and 3 wt % Y₂O₃ sintering aid. Owing to the high spatial resolution of the technique (30 m in the present case), measurements in different positions on the sample surface were carried out. In this way a study of the homogeneity of thermal properties was performed.     

Cost-effective fabrication of porous α-SiAlON bonded β-SiAlON ceramics

Porous sialon ceramics have been cost-effectively prepared by pressureless sintering from a mixture of elongated SHS β-sialon powders with an α-sialon precursor composition composed of α-Si₃N₄, AlN, Y₂O₃ and Al₂O₃. The obtained porous sialon ceramics exhibited low shrinkage and homogeneous pore size distribution. The results of X-ray diffraction and scanning electron microscopy showed that a uniform microstructure with elongated and intermingled β-SiAlON grains, which were strongly connected by α-SiAlON phase, has been obtained.     

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 influence of the molar ratio of Al2O3 to Y2O3 on sintering behavior and the mechanical properties of a SiC–Al2O3–Y2O3 ceramic composite

The influence of the molar ratio of Al₂O₃ to Y₂O₃ (i.e. M_Al2O3/M_Y2O3) on sintering densification, microstructure and the mechanical properties of a SiC–Al₂O₃–Y₂O₃ ceramic composite were studied. It was shown that the optimal value of M_Al2O3/M_Y2O3 was 3/2, not 5/3, which is customarily considered the optimal molar ratio for the formation of YAG (Y₃Al₅O₁₂) phase. When M_Al2O3/M_Y2O3 is 5/3, materials existed in two phases of YAG and very little YAM phases. The sintering mechanism of the solid phase occurred at 1850 °C. When M_Al2O3/M_Y2O3 was 3/2, materials existed in the two phases YAG (Y₃Al₅O₁₂) and YAM (Y₄Al₂O₉). The formation of the low melting point eutectic liquid phase (YAG + YAM) increased sintering densification. Flexure strength, hardness and relative density were all higher.