Alumina Optical Surface Heat Shield for Use in Near-Solar Environment

Experiments indicate that coating a heat shield with alumina can significantly reduce spacecraft temperature during operation near the sun. A thin alumina (Al₂O₃) coating applied to carbon–carbon (C–C) reflects the majority of the visible solar irradiance while reemitting absorbed energy in the infrared. Testing on Al₂O₃-coated C–C coupons using visible and NIR lasers (from ambient to 1773 K) show that the solar-absorptance-to-IR emittance ratio (α_S/ɛ_IR) of the Al₂O₃-coated heat shield was 0.6 or less. Compared with an uncoated carbon–carbon heat shield, the coated version is at least 12% cooler, enabling thermal insulation mass reductions, improved scientific measurements, and the use of less exotic thermal protection materials.     

Preparation of Porous Glass-Ceramics with a Skeleton of NASICON-Type Crystal CuTi2(PO4)3

A novel porous glass-ceramic with a skeleton of CuTi₂(PO₄)₃ was prepared by controlled crystallization of a glass and subsequent chemical leaching of the resulting dense glass-ceramic. A volume-crystallized dense glass-ceramic composed of CuTi₂(PO₄)₃ and Cu₃(PO₄)₂ whose surface was covered by a CuO thin layer was prepared by reheating a glass with a nominal composition of 50CuO·20TiO₂30P₂O₅ (in mol%) glass in air. When the resultant glass-ceramic was leached with dilute H₂SO₄, Cu₃(PO₄)₂ and CuO phases were dissolved out selectively, leaving a crystalline CuTi₂(PO₄)₃ skeleton. The specific surface area and the average pore radius of the porous glass-ceramic obtained were approximately 45 m₂g_-1 and 9 nm, respectively. The porous glass-ceramic showed catalytic activity in the conversion reaction of propene into acrolein.     

Microporous Glass-Ceramics in NASICON-Type Copper(II) Titanium Phosphate

A novel porous glass-ceramic with a skeleton of a NASICON-type copper(II) titanium phosphate was prepared via the controlled crystallization of a glass and the subsequent chemical leaching of the resulting dense glass-ceramic. A volume-crystallized dense glass-ceramic comprised of CuTi₂(PO₄)₃ and Cu₃(PO₄)₂, whose surface was covered by a thin layer of CuO, was prepared by reheating a glass with a nominal composition of 50CuO20TiO₂30P₂O₅ (in mol%) in air. When the resulting glass-ceramic was leached with dilute HCl, the Cu₃(PO₄)₂ and CuO phases were dissolved out selectively, and a cuprous NASICON crystal of CuTi₂(PO₄)₃ was converted to its cupric type, CuTi₄(PO₄)₆, which was left as a skeleton of the porous materials. The specific surface area and the average pore radius of the porous glass-ceramic obtained were ∼70 m²/g and ∼7 nm, respectively. The porous glass-ceramic showed high catalytic activities for the dehydration of 2-propanol.     

Single-Calcination Synthesis of Pyrochlore-Free 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 and Pb(Mg1/3Nb2/3)O3 Ceramics Using a Coating Method

A coating approach for synthesizing 0.9Pb(Mg_1/3Nb_2/3)O₃–0.1PbTiO₃ (0.9PMN–0.1PT) and PMN using a single calcination step was demonstrated. The pyrochlore phase was prevented by coating Mg(OH)₂ on Nb₂O₅ particles. Coating of Mg(OH)₂ on Nb₂O₅ was done by precipitating Mg(OH)₂ in an aqueous Nb₂O₅ suspension at pH 10. The coating was confirmed using optical micrographs and zeta-potential measurements. A single calcination treatment of the Mg(OH)₂-coated Nb₂O₅ particles mixed with appropriate amounts of PbO and PbTiO₃ powders at 900°C for 2 h produced pyrochlore-free perovskite 0.9PMN–0.1PT and PMN powders. The elimination of the pyrochlore phase was attributed to the separation of PbO and Nb₂O₅ by the Mg(OH)₂ coating. The Mg(OH)₂ coating on the Nb₂O₅ improved the mixing of Mg(OH)₂ and Nb₂O₅ and decreased the temperature for complete columbite conversion to ∼850°C. The pyrochlore-free perovskite 0.9PMN–0.1PT powders were sintered to 97% density at 1150°C. The sintered 0.9PMN–0.1PT ceramics exhibited a dielectric constant maximum of ∼24 660 at 45°C at a frequency of 1 kHz.     

Mechanical and Biological Performance of Calcium Phosphate Coatings on Porous Bone Scaffold

Composite coatings, consisting of calcium phosphate (CaP) ceramics and phosphate-based glass (P-glass), were obtained on a strong ZrO₂ porous scaffold to improve biocompatibility by combining mechanical properties and biological activity. Powder mixtures of hydroxyapatite (HA) and P-glass in varying composition and content were dip-coated on a ZrO₂ porous scaffold and heat-treated above 800°C for 2 h in air. During thermal treatment, substantial reaction and crystallization occurred, resulting in coating phases of HA, tricalcium phosphate (TCP), dicalcium phosphate (DCP), and surrounding glass. The CaP-glass coating layer was highly dense and uniform and adhered firmly to the ZrO₂ scaffold. The adhesion strength of the coating layer as tested on a nonporous disk increased with increasing glass addition and decreasing CaO content in glass. The highest strength was about 40 MPa, an improvement of twice as high as that of pure HA coating. The osteoblastic cells grew and spread actively through the coated scaffolds. The differentiation of cells on the CaP coatings was much higher than that on ZrO₂ substrate and comparable to or slightly higher than that on pure HA coating.     

Differential Thermal Analysis Investigation of the High-Low Cristobalite Inversion Under Hydrostatic Pressure to 7 Kbar

The high-low inversion in polycrystalline cristobalite, synthesized from quartz at 1500°C, was investigated by differential thermal analysis to 7 kbar in hydrostatic apparatus. A region of anomalous curvature ( d²T/dp² >0) exists to ∼1 kbar; at higher pressure, the low→high and high→low transition temperatures vary linearly with pressure, with slopes of ∼51.₁ and 53. ₆ deg kbar⁻¹, respectively. Extrapolated 1-bar intercepts are ∼232° and ∼209°C, respectively. It is concluded that high cristobalite is less compressible than low cristobalite near the inversion. The hysteresis between the high→low and low→high transition temperatures decreases with increasing pressure.     

Thermal Stability of Hexaaluminate Film Coated on SiC Substrate for High-Temperature Catalytic Application

A coating of barium hexaaluminate (Ba_0.75Al_11.0O_17.25) on an α-SiC substrate and the thermal stability of the formed film were investigated for a high-temperature catalytic application. The film prepared by sol coating consisted of BaAl₂Si₂O₈ and α-Al₂O₃ phases and always contained many cracks or exfoliations after heating at 1200C. A hexaaluminate porous film was successfully formed by slurry coating without void formation at the interface between the film and the substrate and exfoliation due to the formation of the intermediate layer after heating at 1200°C. The microstructure of the film remained unchanged, even after heating at 1300°C.     

Growth of Tabular α-Al2O3 Grains on Porous Alumina Substrate

Gradient, porous alumina ceramics were prepared with the characteristics of microsized tabular α-Al₂O₃ grains grown on a surface with a fine interlocking feature. The samples were formed by spin-coating diphasic aluminosilicate sol on porous alumina substrates. The sol consisted of nano-sized pseudo-boehmite (AlOOH) and hydrolyzed tetraethyl orthosilicate [Si(OC₂H₅)₄]. After drying and sintering at 1150°–1450°C, the crystallographic and chemical properties of the porous structures were investigated by analytical electron microscopy. The results show that the formation of tabular α-Al₂O₃ grains is controlled by the dissolution of fine Al₂O₃ in the diphasic material at the interface. The nucleation and growth of tabular α-Al₂O₃ grains proceeds heterogeneously at the Al₂O₃/glass interface by ripening nano-sized Al₂O₃ particles.     

High-Temperature Active Oxidation of Chemically Vapor-Deposited Silicon Carbide in CO─CO2 Atmosphere

Active oxidation behavior of CVD-SiC in CO─CO₂ atmospheres was investigated using a thermogravimetric technique in the temperature range between 1823 and 1923 K. The gas pressure ratio, P _CO2/ P _CO, was controlled between 10⁻⁴ and 10⁻¹ at 0.1 MPa. Active oxidation rates (mass loss rates) showed maxima at a certain value of P _CO2/ P _CO, ( P _CO2/ P _CO )^*, In a P _CO2/ P _CO region lower than the ( P _CO2/ P _CO)^* a carbon layer was formed on the SiC surface. In a P _CO2/ P _CO region higher than the ( P _CO2/ P _CO)^*, silica particles or a porous silica layer was observed on the SiC surface.     

Interactions between Ruthenia-Based Resistors and Cordierite–Glass Substrates in Low-Temperature Co-fired Ceramics

Low-temperature co-fired ceramics (LTCCs) that are composed of a RuO₂-based resistor and a cordierite–glass substrate have been sintered at temperatures of 850° and 900°C. The microstructure of the resistor/substrate interface has been investigated using scanning and transmission electron microscopy, and its correlation to the overall resistance has been discussed. X-ray diffractometry has revealed that lead ruthenate pyrochlore (Pb₂Ru₂O_6.5) in peak-fired thick-film resistors (TFRs) disappears and the co-fired samples contain only RuO₂ in the resistor film when sintered at 900°C. The overall resistance of the LTCC resistors is increased by a factor of ∼3 when temperature is increased from 850°C to 900°C. The cordierite–glass composition of the initial substrate reacts with glass in the resistor film. The greatly extended layer of the resistor/substrate interface that contains the conductor particles is either broad or diffuse, which contrasts the abrupt interface that often is observed in conventional TFRs. This layer contains predominantly faceted platelike crystals of anorthite, in addition to other phases (such as diopside, sapphirine, and cristobalite) that apparently crystallize during co-firing as vitrification and chemical reactions between glass compositions of the substrate and the resistor occur. The increase in the resistance of the LTCC resistors is attributed to the interruption of the conducting path by platelike anorthite crystals that are produced in the resistor/substrate interface when subjected to co-firing.     

Effect of Trace A12O3 on Transformation of Quartz to Cristobalite

The effect of additions of 0.22, 0.44, 0.88, and 1.76% A1₂O₃ (Si⁴⁺/A1³⁺ ratio of 200:1, 100:1, 50:1, and 25:1) on the transformation of Brazilian quartz to cristobalite was studied at 1500°, 1530°, and 1570°C. The smaller percentages of A1₂O₃ (0.22 and 0.44%) catalyzed the transformation of quartz and the formation of cristobalite considerably. The rates of transformation of quartz with 0.88 and 1.76% A1₂O₃ were slower than with 0.22 or 0.44%, indicating a critical A1³⁺/Si⁴⁺ ratio where the catalytic effect was found to be maximum. This appeared to occur at about 0.5% A1₂O₃. The transformation rate of quartz indicated that the reaction was first order. Cristobalite, however, showed two different rates; the initial rapid growth was followed by a slower rate. The point of changeover was found to be at about 30 ± 5% cristobalite. The critical nature of the A1³⁻/Si⁴⁺ ratio at about 0.01 (or A1₂O₃/SiO₂± 0.005) may have some bearing on the properties of silica refractories with more or less than 0.5% A1₂O₃.     

Porous Glass-Ceramic in the CαO–TiO2–P2O5 System

A porous glass-ceramic in the CaO–TiO₂—P₂O₅ system has been prepared by crystallization and subsequent chemical leaching of the corresponding glass. By applying a two-step heat treatment to 45CaO · 25TiO₂· 30P₂O₅ glasses containing a few mol% of Na₂O, volume crystallization results in the formation of dense glass-ceramics composed of CaTi₄(PO₄)₆ and β-Ca₃(PO₄)₂ phases. By leaching the resultant glass ceramics with HCI, β-Ca₃(PO₄)₂ is selectively dissolved out, leaving a crystalline CaTi₄(PO₄)₆ skeleton. The surface area and mean pore radius of the porous glass-ceramics were approximately 40 m²/g and 13 nm, respectively.     

Effects of High Water-Vapor Pressure on Oxidation of Silicon Carbide at 1200°C

The oxidation of SiC at 1200°C in a slowly flowing gas mixture of either air or air + 15 vol% H₂O at 10 atm (1 MPa) was studied for extended times to examine the effects of elevated water-vapor pressure on oxidation rates and microstructural development. At a water-vapor pressure of 1.5 atm (150 kPa), distinct SiO₂ scale structures were observed on the SiC; thick, porous, nonprotective cristobalite scales formed above a thin, nearly dense vitreous SiO₂ layer, which remained constant in thickness with time as the crystalline SiO₂ continued to grow. The pore morphology of the cristobalite layer differed depending on the type of SiC on which it was grown. The crystallization and growth rates of the cristobalite layer were significantly accelerated in the presence of the high water-vapor pressure and resulted in rapid rates of SiC surface recession that were on the order of what is observed when SiO₂ volatility is rate controlling at high gas-flow velocities (30 m/s). The recession process can be described by a paralinear kinetic model controlled by the conversion of dense vitreous SiO₂ to porous, nonprotective SiO₂.     

Fracture Toughness and Spalling Behavior of High-Al2O3 Refractories

The fracture energies and spalling resistance of high-Al₂O₃ refractories were studied. The fracture energies, γ _WOF and γ _NBT , were measured by the work-of-fracture and the notched-beam-test methods, respectively. Spalling resistance, as measured by the relative strength retained in a water quench, correlated well with the thermal-stress resistance parameter applicable to stable crack propagation under conditions of thermal shock, (γ _WOF /α² E ₀). Many of the refractories exhibited high ratios of γ_WOF to γ_NBT; such high ratios were shown analytically to maximize the parameter ( R ¹¹¹¹= E _0γWOF/S₁²) which describes the resistance to catastrophic spalling. The increase of crack length with increasing quenching temperature difference (Δ T ) was somewhat less than that predicted theoretically; the discrepancy was attributed to an increase of crack density with Δ T . In general, the results show that fracture energy is important in establishing the spalling resistance of high-Al₂O₃ refractories.     

Shock Synthesis of a Graphitic Boron-Carbon-Nitrogen System

Fine graphitelike boron-carbon-nitrogen particles were produced via vaporization and condensation of a powdered mixture of amorphous boron nitride/carbon black (a-BN/CB) via shock compression. Electron microscopy showed that the particles were made of a graphitic layer sequence with a composition of (BN)_0.33C_0.67. The hexagonal lattice parameters of g-(BN)_0.33C_0.67 were a ₀= 0.2475 ± 0.0001 nm and c ₀= 0.676 ± 0.002 nm.     

High-Temperature Mechanical Properties of Ceramic Materials: V, (Zn0.65, Mg0.35)2SiO4

The composition (0.65Zn,0.35Mg)₂ SiO₁ was investigated. Its thermal expansion was 32 × 10^-7/°C from room temperature to 1000°C. Modulus of rupture was approximately 7000 psi between room temperature and 800°C, whereas Young's modulus held at approximately 11 × 10° psi over the same range. The substitution of 0.35 m oles Mg⁺⁺ for Zn⁺⁺ in Zn₂Si0₄ causes little change in many of the physical properties, but the solid solution sinters much more readily than pure Zn₂Sio₄. The willemite solid solution studied has very good thermal shock resistance between room temperature and 1000°C.     

Uniform Coating of Nanometer-Scale BaTiO3 Layer on Spherical Ni Particles via Hydrothermal Conversion of Ti-Hydroxide

A uniform BaTiO₃ nano layer was coated on spherical Ni particles for multilayer ceramic capacitor applications via a Ti-hydroxide coating using the controlled hydrolysis of a TiCl₄ butanol solution containing (C₂H₅)₂NH (diethylamine, DEA) and its subsequent hydrothermal reaction at various [Ba(OH)₂], residual [DEA], and hydrothermal temperatures. The hydrothermal conversion was successful at [Ba(OH)₂]≥0.065 M (Ba/Ti≥1.3) and T ≥150°C, and the residual DEA in the Ti-hydroxide coating layer not only affected the formation of the BaTiO₃ phase but also resulted in a rough surface morphology. When a minimal amount of DEA was involved in the formation of Ti-hydroxide, a uniform BaTiO₃ coating with a clean surface morphology could be attained, which was confirmed by elemental mapping of the coated powder and the observation of hollow spheres after removing the Ni core. The BaTiO₃ coating was very effective not only in preventing Ni oxidation but also in shifting the starting point of Ni densification to a higher temperature.     

Positron Lifetime Study of the Crystal Evolution and Defect Formation Processes in a Scintillating Glass

The crystal evolution and defect formation in scintillating glasses as a consequence of thermal annealing were studied by annihilation lifetime spectroscopy and UV-Vis absorption spectroscopy. The annihilation lifetime spectra and UV-Vis spectra were recorded on glass 50SiO₂–45ZnO–5BaF₂ before and after annealing at 580°C for 16, 32, and 48 h, respectively. The results show that the three lifetime components (τ₁, τ₂, and τ₃) and the corresponding intensities ( I ₁, I ₂, and I ₃) change systematically with increasing annealing time. This reflects the crystal evolution and defect formation in the glass matrix. The continued crystal evolution was also revealed by the UV-Vis spectra, as the absorption edge of the material shifted to a lower energy with prolonged annealing.     

Kinetics of Barium Titanate Synthesis

Reaction curves were obtained at various temperatures and concentrations for the formation of BaTiO₃ from particulate titania in Ba(OH)₂ solution. Kinetic analyses were performed by constructing mathematical models which took into account the particle size distribution of the reactant titania for both the topochemically-rate-controlled and the diffusion-rate-controlled reactions. At [Ba(OH)₂] > ca. 0.1 M the rate-controlling step is the Ba reaction with TiO₂ at the interface. The measured activation energy is 105.5 kJ/mol. The rates are independent of Ba(OH)₂ concentration, indicating that the TiO₂ interface is saturated. At [Ba(OH)₂] < ca. 0.1 M the rate-determining step shifts to diffusion through the product BaTiO₃ layer, the rates are concentration dependent, and the BaTiO₃ particle sizes are inversely proportional to the Ba(OH)₂ concentrations used.     

Raman Spectra of Molybednum Phosphate Glasses and Some Crystalline Analogues

The Raman spectra of a series of glasses in the system MoO₃-P₂O₅ and the polyerystalline compounds molybdenum metaphosphate (MoO₂(P0₃)₂) and molybdenum pyrophosphate ((MoO₂)₂P₂O₂) are reported. The spectra indicate that traces of P=O and phosphate chains are present only in glasses having less than 50 mol% MoO₃. Comparison of the glass spectra with spectra of crystalline molybdenum phosphates indicates the presence of metaphosphate and orthophosphate structural groups of MoO₃ concentrations of about 50 mol% or less. As the MoO₃ concentration is increased, the bands characteristic of pyrophosphate groups appear in the spectra and become the dominant feature at 76 mol% MoO₃ concentration. Metaphosphate groups are present in the glass even at the highest MoO₃ concentrations measured.