Porous AlN ceramic substrates by reaction sintering

A novel approach was undertaken in producing porous AlN microelectronics tapes with high thermal conductivity and low dielectric constant. This method essentially utilised polymer micro-spherical powders that were used as a sacrificial mould to introduce controlled porosity into the green tapes during pyrolysis. The Al₂O₃-rich porous green tapes were then reaction sintered at 1680 °C for 12 h to achieve porous AlN tapes. This work builds upon the previously developed novel reaction sintering process that densified and converted Al₂O₃-rich tapes (Al₂O₃–20 wt.% AlN–5 wt.% Y₂O₃) to AlN tapes at a relatively low sintering temperature of 1680 °C. The sintering behaviour of the porous tapes was investigated, and the effects of the microspheres particle size and volume addition were studied. The microspheres successfully contributed to the significant reduction of tape density by porosity, and this contributed to lowering its dielectric constant. Dielectric constant of the AlN tapes were reduced to about 6.8–7.7 whilst thermal conductivity values were reasonable at about 46–60 W/m K. Coefficient of thermal expansion (CTE) values showed a linear trend according to phase composition, with the porous AlN tapes exhibiting CTE values of (4.4–4.8)×10⁻⁶ °C⁻¹, showing good CTE compatibility with silicon, at 4.0×10⁻⁶ °C⁻¹. The added porosity did not significantly affect the CTE values.     

Thermoelectric properties of Ni- and Zn-doped Nd2CuO4

The electrical resistivity, Seebeck coefficient, and thermal conductivity of Nd₂(Cu_0.98M_0.02)O₄ (M: Ni and Zn) have been measured in the temperature range from room temperature to about 1000 K. Ni- and Zn-doping decreases the electrical resistivity and the absolute values of the Seebeck coefficient. The thermal conductivity decreases with increasing temperature, showing phonon conduction, and also decreases by doping. The power factor of Nd₂(Cu_0.98Ni_0.02)O₄ reaches 1.02×10⁻⁴ W m⁻¹ K⁻² and the figure of merit is 1.35×10⁻⁵ K⁻¹ at 320 K. The relatively low figure of merit compared with that of the state-of-the-art thermoelectric materials is due to the high thermal conductivity.     

Bulk and lattice thermal expansion in Ce1−xSrxO2−x (0.0≤x≤0.10)

In this communication, we report on the bulk and lattice thermal expansion studies on a number of compounds, within the homogeneity range of solid solutions, in a series with the general composition Ce_1−xSr_xO_2−x (0.0≤x≤0.10). The XRD pattern of each product was refined to determine the solid solubility of SrO into the lattice of CeO₂, and the homogeneity range. The composition with maximum solid solubility limit of SrO in CeO₂ lattice, under the slow cooled conditions, was delineated as Ce_0.91Sr_0.09O_1.91 (i.e. 9 mol.% of SrO). The bulk thermal expansion measurements from ambient to 1123 K, as investigated by a dilatometer, revealed that the _l (293 to 1123 K) values for the compositions within the homogeneity range increase from 11.58×10⁻⁶ to 12.13×10⁻⁶ K⁻¹ on increasing the Sr²⁺ content from 0 mol.% (i.e. CeO₂) to 9 mol.%, i.e. the upper solubility limit of SrO into the lattice of CeO₂. A similar trend was observed in the lattice thermal expansion coefficients _a (293 to 1473 K) as obtained by a high temperature-XRD.     

Thermal and electrical properties of perovskite-type strontium molybdate

Polycrystalline samples of perovskite-type strontium molybdate, SrMoO₃, have been prepared and the thermal and electrical properties have been measured from room temperature to about 1000 K. The electrical resistivity is of an order of magnitude of 10⁻⁵ to 10⁻⁶ (Ω m) in the whole temperature range. The Seebeck coefficient is around 4–9 μV K⁻¹. At room temperature, the thermal conductivity is about 30 W m⁻¹ K⁻¹, and it decreases with increasing temperature.     

New low thermal expansion ceramics: Sintering and thermal behavior of Ln1/3Zr2(PO4)3-based composites

Materials with the general formula M_xZr₂(PO₄)₃ are known to possess low coefficients of thermal expansion (CTE). The present work investigates the thermal properties of new composite materials issued from the decomposition at high temperature of Ln_1/3Zr₂(PO₄)₃ (Ln=La, Gd). The decomposition process was studied and showed that the resulting powder was a LnPO₄, Zr₂P₂O₉ and ZrO₂ mixture. Composite materials made of that mixture were sintered and characterized. The effect of sintering aids such as ZnO was considered. Final densities of the composites were about 90% of theoretical density and these materials presented low CTE in the 10⁻⁶ °C⁻¹ range.     

Fabrication and electrical and thermal properties of Ti2InC, Hf2InC and (Ti,Hf)2InC

In this paper we report on the characterization of predominantly single phase, fully dense Ti₂InC (Ti_1.96InC_1.15), Hf₂InC (Hf_1.94InC_1.26) and (Ti,Hf)₂InC ((Ti_0.47,Hf_0.56)₂InC_1.26) samples produced by reactive hot isostatic pressing of the elemental powders. The a and c lattice parameters in nm, were, respectively: 0.3134; 1.4077 for Ti₂InC; 0.322, 1.443 for (Ti,Hf)₂InC; and 0.331 and 1.472 for Hf₂InC. The heat capacities, thermal expansion coefficients, thermal and electrical conductivities were measured as a function of temperature. These ternaries are good electrical conductors with a resistivity that increases linearly with increasing temperatures. At 0.28 μΩ m, the room temperature resistivity of (Ti,Hf)₂InC is higher than the end members (0.2 μΩ m), indicating a solid solution scattering effect. In the 300 to 1273 K temperature range the thermal expansion coefficients are: 7.6×10⁻⁶ K⁻¹ for Hf₂InC, 9.5×10⁻⁶ K⁻¹ for Ti₂InC, and 8.6×10⁻⁶ K⁻¹ for (Ti,Hf)₂InC. They are all good conductors of heat (20 to 26 W/m K) with the electronic component of conductivity dominating at all temperatures. Extended exposure of Ti₂InC to vacuum (10⁻⁴ atm) at 800 °C, results in the selective sublimation of In, and the conversion of Ti₂InC to TiC_x.     

Computer-aided thermodynamic study of solid Co---Pd alloys by Knudsen cell mass spectrometry, and calculation of the phase diagram

F.c.c. solid Co---Pd alloys have been investigated thermodynamically by means of computer-aided Knudsen cell mass spectrometry. Thermodynamic evaluation has been performed by applying the “digital intensity ratio” method. The thermodynamic excess properties can be described algebraically by means of thermodynamically adapted power series with two adjustable parameters, i.e. C₁^G (−20 810 + 9.608T) J mol⁻¹) and C₂^G (−30 720 + 6.78T) J mol⁻¹). At 1470 K, f.c.c. solid Co---Pd alloys are characterized by negative molar excess Gibbs energies G^E, exothermic molar heats of mixing (H^E) and small negative molar excess entropies S^E. At 1470 K, the minimum G^E value is −4600 J mol⁻¹ (61.9 at.% Pd), the minimum H^E value is −9400 J mol⁻¹ (59.5 at.% Pd) and the minimum S^E value is −3.3 J mol⁻¹ K⁻¹ (55.9 at.% Pd). The thermodynamic activities of Co show small positive deviations from the ideal case for the Co-rich alloys (x_Pd < 0.34), and negative deviations from Raoults' law for alloys with higher Pd contents. The Pd activities a_Pd show negative deviations from the ideal case for all compositions. The phase diagram has been computed by means of a generally applicable procedure for the calculation of the equilibrium compositions of coexisting phases. This was achieved using the results of this work, thermodynamic data from earlier mass spectrometric studies on the liquid phase, and literature data for the heat capacities and enthalpies of Co and Pd.     

Studies on the structural and ionic transport properties at elevated temperatures of La1−xMnO3±δ synthesized by a wet chemical method

Structural transformation and ionic transport properties are investigated on wet-chemically synthesized La_1−xMnO₃ (x=0.0–0.18) compositions. Powders annealed in oxygen/air at 1000–1080 K exhibit cubic symmetry and transform to rhombohedral on annealing at 1173–1573 K in air/oxygen. Annealing above 1773 K in air or in argon/helium at 1473 K stabilized distorted rhombohedral or orthorhombic symmetry. Structural transformations are confirmed from XRD and TEM studies. The total conductivity of sintered disks, measured by four-probe technique, ranges from 5 S cm⁻¹ at 298 K to 105 S cm⁻¹ at 1273 K. The ionic conductivity measured by blocking electrode technique ranges from 1.0×10⁻⁶ S cm⁻¹ at 700 K to 2.0×10⁻³ S cm⁻¹ at 1273 K. The ionic transference number of these compositions ranges from 3.0×10⁻⁵ to 5.0×10⁻⁵ at 1273 K. The activation energy deduced from experimental data for ionic conduction and ionic migration is 1.03–1.10 and 0.80–1.00 eV, respectively. The activation energy of formation, association and migration of vacancies ranges from 1.07 to 1.44 eV.     

Thermoelectric properties of rare earth doped SrTiO3

The thermoelectric properties of Sr_0.9R_0.1TiO₃ (R=Y, La, Sm, Gd, Dy) have been measured from room temperature to 1073 K. The electrical conductivities and Seebeck coefficients are independent of the kind of rare earth elements in the temperature range, so the figure of merits are influenced by the difference in the thermal conductivities. The thermal conductivities decrease with doping according to the rare earth atomic mass and ionic radius. Sr_0.9Dy_0.1TiO₃ shows the highest figure of merit of the investigated samples, reaching 3.84×10⁻⁴ K⁻¹ at 573 K.     

Effects of heat treatment on the properties of powder injection molded AlN ceramics

The effects of two different heat-treatment atmospheres,nitrogen atmosphere and reducing nitrogen atmosphere with carbon,on the properties of Y2O3-doped aluminum nitride (AlN) ceramics were investigated.The AlN powder as a raw material was synthesized by self-propagating high-temperature synthesis (SHS) and compacts were fabricated by employing powder injection molding technique.The polymer-wax binder consisted of 60 wt.% paraffin wax (PW),35 wt.% polypropylene (PP),and 5 wt.% stearic acid (SA).After the removal of binder,specimens were sintered at 1850℃ in nitrogen atmosphere under atmospheric pressure.To improve the thermal conductivity,sintered samples were reheated.The result reveals that the heat-treatment atmosphere has significant effect on the properties and secondary phase of AlN ceramics.The thermal conductivity and density of AlN ceramics reheated in nitrogen gas are 180 W·m-1 K-1 and 3.28 g,cm-3 and the secondary phase is yttrium aluminate.For the sample reheated in reducing nitrogen atmosphere with carbon,the thermal conductivity and density are 173 W.m-1.K-1 and 3.23 g·cm-3,respectively,and the secondary phase is YN.     

High frequency, high temperature ultrasonic transducers

Piezoelectric films of 100% (002) oriented AIN were deposited on platinum-coated quartz, sapphire and LMN ceramics via a CVD process. The growth rate achieved was > 20 nm s⁻¹ at 1020–1040 K. These films had the highest figure of merit (125) and dielectric strength ( >2 × 10⁷ V cm⁻¹) of any known piezoelectric material. The relative dielectric constant is 8.6 and the thickness coupling coefficient, K_t, 20%. The films exhibit ultrasonic response for temperatures 1430 K. 30 MHz compressional-wave transducers were developed on quartz delay-rods with signal strength comparable to ZnO devices. Non-cooled, high temperature ultrasonic devices were developed using the oriented AIN films.     

Effect of laser field and thermal stress on diffusion in laser doping of SiC

The electromagnetic field of lasers and non-equilibrium doping conditions enable laser doping of SiC with increased dopant diffusivity. Chromium, which acts as a double acceptor, has been laser-doped in SiC wafers. A thermal model is utilized to determine the temperature distribution at various depths of the wafer and a diffusion model is presented including the effects of Fickian diffusion, laser electromagnetic field and thermal stresses due to localized laser heating on the mass flux of dopant atoms. The dopant diffusivity is calculated as a function of temperature at different depths of the wafer based on measured dopant concentration profile. The maximum diffusivities achieved in this study are 4.61 × 10⁻¹⁰ cm² s⁻¹ at 2898 K and 6.92 × 10⁻¹² cm² s⁻¹ at 3046 K for 6H-SiC and 4H-SiC, respectively. The maximum concentration is found to be 2.29 × 10¹⁹ cm⁻³ for 6H-SiC, which is two orders of magnitude higher than the reported value (3 × 10¹⁷ cm⁻³ solid solubility limit).     

Calorimetric investigation on the Pb---Sm and Sn---Sm alloys

The integral enthalpy of formation of the Sm---Pb and Sm---Sn melts at 1203 K, h^f, was determined by direct reaction calorimetry (drop method) in the Pb and Sn rich sides with the help of a high-temperature Tian-Calvet calorimeter. The results can be fitted respectively with reference to the mole fraction of samarium, x, as follows:

h^f/kJ mol⁻¹=x(1−x)(−109.8−372.0.7x) with0> X_Sm >0.27

and

h^f/kJ mol⁻¹=x(1−x)(−277.0−105.4.x) with0> X_Sm >0.27

for the Sm---Pb and Sm---Sn melts respectively. They yield the following partial enthalpies of samarium at infinite dilution: −109.8 and −277.0 kJ mol⁻¹ respectively.

Such negative values suggest the existence of a strong short-range order in the liquid state. The stoichiometry and the thermal stability of these associations needs additional thermodynamic determinations concerning mainly the free enthalpy of formation. It will be determined by Knudsen-effusion combined with mass spetrometry in a further work.     

Preparation and bulk thermal expansion studies in M1−xCexSiO4 (M = Th, Zr) system, and stabilization of tetragonal ThSiO4

Two series of compositions with the general formula M_1−xCe_xSiO₄ (M = Th, Zr; x = 0.0–0.5; 1.0) were prepared by a standard solid state route and characterized by powder XRD. About 10 mol% of ceria could be dissolved in the lattice of ThSiO₄. A striking observation was the stabilization of tetragonal modification of ThSiO₄, which is metastable, by ceria substitution. There was no solubility of ceria in zircon (ZrSiO₄) lattice. The average linear thermal expansion coefficient (293–1123 K) of ZrSiO₄, ThSiO₄ and Th_0.9Ce_0.1SiO₄ are 4.65 × 10⁻⁶, 4.97 × 10⁻⁶ and 5.14 × 10⁻⁶ K⁻¹, respectively.     

Standard enthalpies of formation of some carbides, silicides and germanides of cerium and praseodymium

The standard enthalpies of formation of some congruent-melting compounds in the binary systems Re---X, where Re Ce, Pr or La and X C, Si or Ge have been determined by direct-synthesis calorimetry at 1473 ± 2 K. The following values of ΔH_f^o are reported: CeC₂, −25.4 ± 1.4 kJ (mol atom)⁻¹; CeSi₂, −60.5 ± 2.0 kJ (mol atom)⁻¹; CeSi, −71.1 ± 3.3 kJ (mol atom)⁻¹; Ce₅Ge₃, −73.4 ± 2.3 kJ (mol atom)⁻¹; CeGe_1.6, −75.6 ± 1.9 kJ (mol atom)⁻¹; PrC₂, −29.4 ± 1.6 kJ (mol atom)⁻¹; PrSi₂, −61.5 ± 1.7 kJ (mol atom)⁻¹; PrSi, −78.1 ± 1.9 kJ (mol atom)⁻¹; Pr₅Ge₃, −70.4 ± 2.3 kJ (mol atom)⁻¹; PrGe_1.6, −81.7 ± 1.7 kJ (mol atom)⁻¹; LaSi₂, −56.8 ± 2.5 kJ (mol atom)⁻¹. The results are compared with earlier experimental data, with predicted values from Miedema's semiempirical model, and with available data obtained for Sn and Pb compounds by Borzone et al., by Palenzona and by Palenzona and Cirafici.     

Near-infrared to visible photon upconversion in Mn and Yb containing materials

Near-infrared (NIR) laser excitation into the Yb^{3+ 2}F_7/2→²F_5/2 absorption transition around 10,200 cm⁻¹ at 12 K leads to red and green upconversion emission in MnCl₂:Yb³⁺ and Zn₂SiO₄:Yb³⁺; Mn²⁺, respectively. The photon upconversion (UC) emission is centered around 15,240 cm⁻¹ for MnCl₂:Yb³⁺ and around 19,050 cm⁻¹ for Zn₂SiO₄:Yb³⁺; Mn²⁺ and is ascribed to the Mn^{2+ 4}T₁→⁶A₁ transition in both compounds. The shift of the Mn²⁺ emission energy is due to the different coordination and ligand strength. Pulsed measurements indicate a sequence of ground-state absorption (GSA) and excited-state absorption (ESA) steps for the upconversion process. We conclude that the UC process in both compounds occurs by an exchange mechanism involving Yb³⁺ and Mn²⁺ ions. Zn₂SiO₄:Yb³⁺; Mn²⁺ is the first example of a Yb³⁺–Mn²⁺ upconversion system to show visible (VIS) by eye Mn²⁺ UC emission at room temperature.     

Mechanical properties and expansion coefficient of Mo-Cu composites with different Ni contents

Mo-Cu composites were fabricated by powder metallurgy with addition of various Ni contents.The effect of Ni contents on mechanical and thermal properties of Mo-Cu composites was investigated.The results show that mechanical and thermal properties of Mo-Cu composites are greatly affected by the addition of Ni contents.The composite powders with Ni addition exhibits high sinterability.The sintering temperature is greatly decreased and the comprehensive properties of Mo-Cu composites are obviously improved.Mo-Cu composites with a content of 1.5 wt.％ Ni have relative density 99.2％,bending strength 1057.9 MPa,hardness 72.5 HRA,electronic resistivity 1.28× 10 -7Ω.m-1,thermal conductivity 139 W·m-1·K-1,and lower coefficient of thermal expansion 7.4×10-6 K 1.Mo-Cu composites have homogeneous and fine microstructure.The fracture mechanism is ductile fracture.     

Thermal stability and electronic specific heat of GaN

The thermal stability of GaN single crystals obtained by Li-based flux was investigated by DTA–TG, XRD, Raman and infrared spectroscopy. The results evidence that pure GaN becomes unstable above 900 °C under N₂ of 0.1 MPa. The specific heat of GaN was determined at temperatures ranging from 1.9 K to 80 K. Its electronic specific heat coefficient is 0.47 mJ K⁻² mol⁻¹ and the Debye temperature is 278 K.     

Synthesis and characterization of 0.3 Vf TiC–Ti3SiC2 and 0.3 Vf SiC–Ti3SiC2 composites

In this work, two composite compositions—one with 30% (v/v) SiC, the other with 30% (v/v) TiC, balance Ti₃SiC₂—were synthesized and characterized. Fully dense samples were fabricated by hot isostatically pressing Ti, SiC and C powders for 8 h at 1500 or 1600 °C and a pressure of 200 MPa. Both TiC and SiC lower grain boundary mobility in Ti₃SiC₂. Coarsening of the SiC particles was also observed. At comparable grain sizes, all composites tested were weaker in flexure than the unreinforced Ti₃SiC₂ matrix, with the reduction in strength being the worst for the SiC composites. This reduction in strength is most probably due to thermal expansion mismatches between the matrix and reinforcement phases. The composite samples were exceptionally damage tolerant; in one case a 100 N Vickers indentation (in a 1.5-mm thick bar) did not reduce the flexural strength as compared to an unindented or as-fabricated samples. The same is true for thermal shock resistance; quenching samples from 1400 °C in room temperature water, resulted in strength reductions that were 12% at best and 50% at worst. In the 25–1000 °C temperature range, the thermal expansion coefficients of the two composites were indistinguishable at 8.2×10⁻⁶ K⁻¹. The Vickers hardness values depended on load; at 100 N, the hardnesses were ≈15 GPa; at 300 N, they asymptote to 7–8 GPa. For the most part, very few cracks emanate from the corners of the Vickers indents even at loads as high as 500 N. In the few cases where cracks did initiate, fracture toughness values were crudely estimated to lie in the 5–7.5 MPa √m range.     

Aqueous zinc–polyaniline secondary battery

An aqueous zinc–polyaniline secondary battery was constituted by the polyaniline synthesized in a mixed solution containing 0.60 mol dm⁻³ aniline, 1.20 mol dm⁻³ 1-ethyl-3-methylimidazolium-ethyl sulfate (EMIES) and 2.0 mol dm⁻³ H₂SO₄, Zn foil and an electrolytic solution containing 2.0 mol dm⁻³ ZnCl₂ and 3.0 mol dm⁻³ NH₄Cl with pH 6.0. The capacity and energy densities of the polyaniline are 141.2 A h kg⁻¹ and 169.4 W h kg⁻¹ for discharge process at 0.5 mA cm⁻², respectively, which are much better than those of the polyaniline synthesized in HCl at the same current densities. The battery was successively charged/discharged at constant current densities, the columbic efficiency was 95.5% at 150th cycle, and the energy density of the battery was lower by only 6.0% at 150th cycle than at 1st cycle.