Low-thermal expansion polycrystalline tantalum tungstate ceramics

The synthesis of thermal-shock-resistant materials from the system Ta₂O₅WO₃ was investigated. Ta₂WO₈ had a very low unit-cell thermal expansion coefficient (+0.5 X 10^–6° C^–1). Ta₃₀W₂O₈₁ also had a relatively low coefficient (+4.0 X 10^–6 ° C^–1) and a thermal durability over 1600° C. The thermal expansion curves of these polycrystalline ceramics were lowered because of microcracks caused by the large thermal expansion anisotropy of the crystal axes and were accompanied by hysteresis loops. The densification of Ta₂WO₈ ceramic was promoted by the addition of some metal oxides, and the strong ceramic of Ta₃₀W₂O₈₁ was obtained by controlling grain growth.     

Thermal and dielectric properties of zirconyl phosphate compact

Experimental results are presented on the measurements of thermal expansion (up to 1500°C), thermal conductivity (up to 1000°C), dielectric constant (up to 450 °C) and tan (up to 800 °C) of zirconyl phosphate compacts obtained by sintering at 1600°C. The thermal expansion coefficient of the samples at the temperature below 1100°C was less than 1.7 × 10^–6°C^–1. The samples showed a definite shrinkage at temperatures of 1110 and 1470°C due to the phase transformations. The expansion at 1500°C was less than that at 1100°C probably because of the phase transformation. The thermal conductivity at room temperature was a very small value (0.0046 to 0.0065 cal s^–1 cm°C^–1 cm^–2). The dielectric constant was close to 9. The value of tan° (–0.0001) measured is one of the lowest values for ceramic materials.     

Synthesis and characterization of (Sr1−x′K2x)Zr4(PO4)6 ceramics

Single phase (Sr_1–x K_2x )Zr₄(PO₄)₆, where x lies between 0.0 and 1.0, ceramic powder with a submicron scale particle size has been synthesized successfully at calcination temperatures as low as 650–750°C by a sol-gel technique. The formation of the powder strongly depends on calcination temperature, but is independent of solution pH in the studied range. Dilatometric measurement shows an ultra-low linear coefficient of thermal expansion of 0.1×10^–6°C^–1 when x=0.5 at temperature intervals of 25–1000°C. Thermal conductivity and flexural strength of the materials were determined at ambient temperature to be 1.0 Wm^–1K^–1 and as high as 280 MPa, respectively, indicating that this material can be an excellent candidate in many applications, especially those subjected directly to severe environments.     

Thermal expansion of TiAl + TiB2 alloys and model calculations of stresses and expansion of continuous fiber composites

Thermal expansion values for three TiAl alloys with different additions of TiB₂ can be represented using a third-order equation at temperatures between 20 and 800°C. Expansion values were obtained on both heating and cooling temperature cycles. The total expansion at 800°C is between 0.917 and 0.931% for three different samples. The expansivity increases from about 10×10^–6°C^–1 at 80°C to 14×10^–6°C^–1 at 750°C. A five-coaxial cylinder elastic model for multizone-coated continuous fiber composites is developed for predicting stresses and thermal expansion of composites. Either isotropic or transversely isotropic material properties can be assigned to the various cylinder zones.Paper presented at the Tenth International Thermal Expansion Symposium, June 6–7, 1989, Boulder, Colorado, U.S.A.     

Thermal expansion of the cubic (3C) polytype of SiC

Thermal expansion of the cubic beta or (3C) polytype of SiC was measured from 20 to 1000° C by the X-ray diffraction technique. Over that temperature range, the coefficient of thermal expansion can be expressed as the second order polynominal: ₁₁=3.19×10^–6+ 3.60×10^–9 T–1.68×10^–12 T ² (1/° C). It increases continuously from about 3.2×10^–6/° C at room temperature to 5.1×10^–6/° C at 1000° C, with an average value of 4.45 × 10^–6/° C between room temperature and 1000° C. This trend is compared with other published results and is discussed in terms of structural contributions to the thermal expansion.     

Thermal stabilization of aluminium titanate and properties of aluminium titanate solid solutions

Aluminium titanate has a near zero thermal expansion coefficient (=0.8×10^–6 °C^–1) in the range 20 to 1000 °C, nevertheless it decomposes below 1200 °C.The thermal stabilization of Al₂TiO₅ without altering its thermal expansion has been considered by partial substitution in the structure compound of Al³⁺ ions by Fe³⁺ ions.The solid solutions prepared by solid state reaction are in agreement with the general formula Al(1–x)₂Fe_2x TiO₅(0<x<0.2)The iron ions present in the crystal structure of Al₂TiO₅ act on its lattice parameters and bring about a catalytic effect in the formation of materials.Solid solutions show a strong thermal stability and a thermal expansion coefficient specially for the solid solution (x=0.1) which is not far from the Al₂TiO₅ value even after annealing for 300 h at 1000 °C.The mechanical properties of such materials corresponding to that solid solution present strength values lower than Al₂TiO₅ ones. After annealing, however, these are improved later due to a microcrystallization.     

Thermal properties of MoSi2 and SiC whisker-reinforced MoSi2

The heat capacity, thermal conductivity and coefficient of thermal expansion of MoSi₂ and 18 vol % SiC whisker-reinforced MoSi₂ were investigated as a function of temperature. The materials were prepared by hot isostatic pressing between 1650 and 1700 °C, the hold time at temperature being 4 h. The heat capacity of MoSi₂ showed an increase from about 0.44 Wsg^–11K^–1 at room temperature to 0.53 at 700 °C. Whisker reinforcement increased heat capacity by about 10%. Thermal conductivity exhibited a decreasing trend from 0.63 Wcm^–1 K^–1 at room temperature to 0.28 Wem^–1 K^–1 at 1400°C. Whiskers reduced conductivity by about 10%. The thermal expansion coefficient increased from 7.42 °C^–1 between room temperature and 200 °C to 9.13 °C^–1 between room temperature and 1200 °C. There was a 10% decrease resulting from the whiskers. The measured data are compared with literature values. The trends in the data and their potential implications for high-temperature aerospace applications of MoSi₂ are discussed.     

Phonon scattering of point defect aggregates of Mg in LiF

The quantitative analysis of thermal conductivity for a large temperature interval is shown to be a method very well adapted to the study of resonant scattering of phonons by defects of size comparable with the phonon wavelength. The state of Mg in LiF has been studied by thermal conductivity measurements between 0.45 and 100° K as a function of concentration (between 6×10^–5 and 2.3×10^–3 ) and thermal treatments. In the case of low concentrations (C<2×10^–4 ) the dipoles Mg ²⁺-cation vacancy aggregated in trimers act as point defects. There exists no resonant mode of the cation vacancy, because of the tight binding between Mg ²⁺ and the cation vacancy. The process of precipitation of either the metastable phase Li ₆ MgF ₈ or MgF ₂ from a solid solution has been studied in the case of the sample withC=2.3×10^–4 Mg. The numerical analysis has allowed us to calculate the size and the number of precipitates after each annealing. This size is remarkably well defined and depends only on the annealing temperature. The quantity of Mg is always very small. In the higher doped samples (C=8.4×10^–4 and 2.3×10^–3 ) the influence of dislocations and grain boundaries is predominant.     

The high-temperature thermal expansion of BiPbSrCaCuO superconductor and the oxide components (Bi2O3, PbO,CaO, CuO)

The thermal expansion of superconducting Bi_1.6Pb_0.4Sr₂Ca₂Cu₃Ox (BiPbSrCaCuO) and its oxide components Bi₂O₃, PbO, CaO and CuO have been studied by high-temperature dilatometric measurements (30–800°C). The thermal expansion coefficient for the BiPbSrCaCuO superconductor in the range 150–830°C is =6.4×10^–6K^–1. The temperature dependences of L/L of pressed Bi₂O₃ reveals sharp changes of length on heating (T ₁=712°C), and on cooling (T ₂=637°C and T ₃=577°C), caused by the phase transition monoclinic-cubic (T ₁) and by reverse transitions via a metastable phase (T ₂ and T ₃). By thermal expansion measurements of melted Bi₂O₃ it is shown that hysteresis in the forward and the reverse phase transitions may be partly caused by grain boundary effect in pressed Bi₂O₃. The thermal expansion of red PbO reveals a sharp decrease in L/L, on heating (T ₁=490°C), related with the phase transition of tetragonal (red, a=0.3962 nm, c=0.5025 nm)-orthorhombic (yellow, a=0.5489 nm, b=0.4756 nm, c=0.5895 nm). The possible causes of irreversibility of the phase transition in PbO are discussed. In the range 50–740°C the coefficient of thermal expansion of pressed Bi₂O₃ (_m=3.6 × 10^–6 and _c=16.6×10^–6K^–1 for monoclinic and cubic Bi₂O₃ respectively), the melted Bi₂O₃ (_m=7.6×10^–6 and _c=11.5×10^–6K^–1), PbO (_t=9.4×10⁶ and _or=3.3×10^–6K^–1 for tetragonal and orthorhombic PbO respectively), CaO (=6.1×10^–6K^–1) and CuO (=4.3×10^–6K^–1) are presented.     

Anisotropic thermal expansion of stoichiometric lithium niobate crystals grown along the normal direction of facets

In this paper, a stoichiometric lithium niobate (SLN) crystal with the size up to 20 × 20 × 18 mm³ was grown along the normal direction of the (0 1 2) facet from the 16 mol% K₂O fluxed melt by the top-seeded solution growth method. The anisotropic thermal expansion of the SLN crystal and congruent lithium niobate (CLN) crystal was measured along different directions by using a Shimadzu thermomechanical analyzer. As compared with CLN, the SLN crystal exhibited slightly larger thermal expansion along the Z-axis and slightly smaller expansion along the X-axis. Both the SLN and CLN crystals showed strong anisotropy in the thermal expansion. The thermal expansion coefficient of SLN along the X-axis (16.7 × 10⁻⁶ °C⁻¹ at 300 °C) is much larger than that along the Z-axis (2.5 × 10⁻⁶ °C⁻¹ at 300 °C). Based on the experimental data and polynomial fitting results, we calculated the thermal expansion coefficients for different directions. In the case of growing the SLN crystal along the normal direction of (0 1 2) facet, we studied the radial anisotropic thermal expansion and discussed the cracking problem of the crystal according to its actual growth morphology. It is found that the cracks of SLN can be suppressed by growing the crystal along the W-axis due to its reduced radial anisotropy in the thermal expansion.     

Preparation, thermal expansion, high pressure and high temperature behavior of Al2(WO4)3

The titled compound Al₂(WO₄)₃ was synthesized by a conventional solid state reaction and characterized by powder XRD. It crystallizes in an orthorhombic (Pbcn, No. 60) lattice, with unit cell parameters as 12.582(2), 9.051(1), 9.128(2) Å, and V = 1039.5(3) (Å)³. The compound was found to show negative thermal expansion (NTE) behavior in the temperature range of 25 to 850°C. The average linear NTE coefficient (₁), in this temperature range, was –1.5 × 10^–6 K^–1. The effect of pressure at ambient temperature, was studied by a Bridgman Anvil (BA) apparatus, to reveal that there is no irreversible phase transition up to 8 GPa. The effect of high pressure and high temperature on this compound was studied by a Toroid Anvil (TA) apparatus. This compound has a limited stability under high pressure and temperature, as it undergoes a decomposition to AlWO₄ and WO_3–x with a partial oxygen loss. As an off-shoot of this work, certain new modifications of WO_3–x under pressure and temperature were observed, viz., monoclinic, tetragonal and an orthorhombic modifications at 5 GPa/1400°C, 3 GPa/900°C and 1.8 GPa/1030°C, respectively. The detailed XRD studies of the products are presented here.     

Carbon fibre-reinforced silicon nitride composite

The processing of silicon nitride reinforced with carbon fibre was studied. The problems of physical and chemical incompatibility between carbon fibre and the silicon nitride matrix were solved by addition of a small amount of zirconia to the matrix and by low-temperature hot-pressing. The composite material possesses a much higher toughness than hot-pressed silicon nitride. Its work of fracture increased from 19.3 J m^–2 for unreinforced Si₃N₄, to 4770 J m^–2; its fracture toughness,K _lc , increased from 3.7 MN m^–3/2 for unreinforced material, to 15.6 MN m^–3/2. The strength remains about the same as unreinforced Si₃N₄ and the thermal expansion coefficient is only 2.51×10^–6 ° C^–1 (RT to 1000° C). It is anticipated that this composite may be promising because of its mechanical and good thermal shock-resistance properties.     

Study of alumosilicate porcelains: Sol-gel preparation, characterization and erosion evaluated by gravimetric method

In this paper, the sol-gel synthesis and characteristic properties of kalsilite-type alumosilicates (KAlSiO₄ and K_0.5Na_0.5AlSiO₄) are reported. The polycrystalline powders were characterized by thermal analysis (TG/DTA), powder X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). Single-phase kalsilite oxides have been obtained after annealing precursor gels for 5 h in the temperature range of 750-850 °C. It was demonstrated that crystallinity of the samples slightly depends on the temperature of annealing. From the results obtained, it could be concluded that the KAlSiO₄ solids are composed of the volumetric plate-like grains with no regular size (from 5 μm to 30 μm at 750 °C and around 5-50 μm at 850 °C). Larger crystallites for mixed potassium-sodium kalsilite have formed (from 10 μm to 80 μm at 750 °C and >100 μm at 850 °C) in comparison with potassium kalsilite samples). The erosion of obtained dental porcelain samples stored in saliva, beer and Coca-Cola was compared.     

Thermal expansion of Li2O-ZnO-Al2O3-SiO2 glasses and corresponding glass-ceramics

The thermal expansion behaviour of some glasses and glass-ceramics within the system Li₂ZnSiO₄-LiAlSi₂O₆ is described. The effect of TiO₂ and ZrO₂ additions is also evaluated. The expansion coefficient () of the glasses increases with an increase of the Li₂ZnSiO₄ component in the glass composition. TiO₂ and ZrO₂ were found to decrease the thermal expansion of the glasses investigated. The dilatometric transition and softening points of the glasses showed the reverse behaviour. The thermal expansion of the glass-ceramics exhibited a wide range, depending upon the type and relative proportions of the crystalline phases present. The values of the glasses ranged between 73.6 and 97.4×10^–7C^–1 in the temperature range 20–450C and those for the crystalline products ranged from 36.1 and 102.6 × 10^–7 in the temperature range 20–450C.     

Properties of high reinforcement-content aluminum matrix composite for electronic packages

Aluminum matrix composites reinforced by a high volume fraction of ceramic particles provide a novel solution to electronic packaging technology, because of their high thermal conductivity, compatible and tailorable coefficient of thermal expansion (CTE) with chips or substrates, low weight, enhanced specific stiffness, and low cost. In this paper, SiC-particle-reinforced aluminum matrix composites are fabricated by the cost-effective squeeze-casting technology, and their microstructure characteristics, thermo-physical, and mechanical properties are investigated. The reinforcement volume fraction is as high as 70% and composites with linear CTE of 6.9–9.7×10^–6 °C^–1 and thermal conductivity of 120–170 W m^–1 °C^–1 are produced. The composites can be electric-discharge machined, ground, and electric-spark drilled. An electroless nickel layer is plated on the composite by the conventional procedures. Finally, their potential applications in electronic packaging and thermal management are illustrated via prototype examples.     

Thermal expansion of niobium in the range 1500–2700 K by a transient interferometric technique

The linear thermal expansion of niobium has been measured in the temperature range 1500–2700 K by means of a transient (subsecond) interferometric technique. The basic method involves rapidly heating the specimen from room temperature up to and through the temperature range of interest in less than 1 s by passing an electrical current pulse through it and simultaneously measuring the specimen temperature by means of a high-speed photoelectric pyrometer and the shift in the fringe pattern produced by a Michelson-type interferometer. The linear thermal expansion is determined from the cumulative shift corresponding to each measured temperature. The results for niobium may be expressed by the relation (l-l ₀)/l ₀=5.4424×10^–3–8.8553×10^–6 T+1.2993×10^–8 T ² –4.4002×10^–12 T ³+6.3476×10^–16T⁴ where T is in K and l ₀ is the specimen length at 20°C. The maximum error in the reported values of thermal expansion is estimated to be about 1% at 2000 K and not more than 2% at 2700 K.Paper presented at the Ninth International Thermal Expansion Symposium, December 8–10, 1986, Pittsburgh, Pennsylvania, U.S.A.     

Negative thermal expansion in Th2O(PO4)2

High temperature X ray diffraction performed on recently discovered orthorhombic Th₂O(PO₄)₂ shows a continuous linear thermal contraction (−1.6 × 10⁻⁶ °C⁻¹) in 20–600 °C range and a near-zero expansion at higher temperatures resulting from a dual structural deformation involving oxygen oscillations and inter-cations repulsions. Although similar mechanisms were observed in isotypic Zr₂O(PO₄)₂ (+1.5 × 10⁻⁶ °C⁻¹) and U₂O(PO₄)₂ (−1.4 × 10⁻⁶ °C⁻¹), those observed in Th₂O(PO₄)₂ are particularly intense because of the high ionic radius of tetravalent thorium.     

Soft chemical synthesis and characterization of lithium nickel oxide electrode materials

Soft chemistry was used to prepare ordered nanophase Li_0.6NiO₂ electrode materials by completing the oxidation of Ni²⁺ to Ni³⁺ and/or Ni⁴⁺ species with H₂O₂ oxidant during solution reactions at 50–60 °C and evaporation at 105–150 °C rather than during sintering. Both elemental analysis and electron spectroscopy for chemical analysis (ESCA) results indicate that oxidation was completed. The deconvoluted ESCA spectra of nickel ions exhibited a semi-quantitative ratio of Ni⁴⁺Ni³⁺=6040 which presented no significant change with increase of sintering time. After sintering for up to 11 h at 700°C, ordered Li_0.61Ni_0.96O_2.0 ceramics were formed (R3m, a ₀=0.2837 nm, c ₀=1.417 nm). Distribution of the crystallite size was in the range of 80–200 nm. As sintering times were increased, the crystallite shapes exhibited a more distinct morphology, and the ordering degree of the cations was enhanced, while the conductivity was sharply enhanced up to 2.0×10^{–1 –1} cm^–1 at 30 °C. Compared to conventional ceramic and solution methods, the ordered nanophase Li_0.61 Ni_0.96O_2.0 ceramics was obtained at 700 °C with shorter sintering times ( 11 h).     

Thermal expansion of strontium tungstate

Accurate lattice parameters of strontium tungstate, an isotype of scheelite, have been determined as a function of temperature by the X-ray powder method in the temperature range 28 to 355° C. Both the lattice parameters are found to increase with temperature. Using these data, the two coefficients of thermal expansion, _a along the a-axis and _a along the c-axis, have been calculated. The temperature dependence of the coefficients could be expressed by the following equations: _a =5.88×10^–6–25.63×10^–10 T + 59.49×10^–12 T ² _c =13.20×10^–6–18.18×10^–10T+71.45×10^–12 T ². Here T is the temperature in °C.     

Thermal expansion of epoxy-fiberglass composite specimens

The thermal expansion behavior of three epoxy-fiberglass composite specimens was measured from 20 to 120°C (70 to 250°F) using a fused quartz push-rod dilatometer. Billets produced by vacuum-impregnating layers of two types of fiberglass cloth with an epoxy were core-drilled to produce cylindrical specimens. These were used to study expansion perpendicular and parallel to the fiberglass layers. This type of composite is used to separate the copper conductors that form a helical field coil in the Advanced Toroidal Facility, a plasma physics experiment operated by the Fusion Energy Division at Oak Ridge National Laboratory. The coil is operated in a pulsed mode and expansion data were needed to assess cracking and joint stresses due to expansion of the copper-composite system. The dilatometer is held at a preselected temperature until steady state is indicated by stable length and temperature data. Before testing the composite specimens, a reliability check of the dilatometer was performed using a copper secondary standard. This indicated thermal expansion coefficient () values within ±2% of expected values from 20 to 200°C. The percentage expansion of the composite specimen perpendicular to the fiberglass layers exceeded 0.8% at 120°C, whereas that parallel to the fiberglass layers was about 0.16%. The expansion in the perpendicular direction was linear to about 70°C, with an value of over 55×10^–6 °C^–1. Anomalous expansion behavior was noted above 70°C. The expansion in the direction parallel to the fiberglass layers corresponds to an value of about 15×10^–6 °C^–1. The lower values in the parallel direction are consistent with the restraining action of the fiberglass layers. The values decreased with the specimen density and this is consistent with literature data on composite contraction from 20 to –195°C.Nomenclature Thermal expansion coefficient, °C^–1 - L L(T ₂)–L(T ₁), cm - T T ₂–T ₁, °C - L ₀ Length at room temperature, cm - L(T _i ) Length at temperature T _i , cm - T _i Temperature, °C - T ₀ Room temperature, °C Paper presented at the Ninth International Thermal Expansion Symposium, December 8–10, 1986, Pittsburgh, Pennsylvania, U.S.A.