TIOx/Al2O3 Multilayer Ceramic Thin Films

Titanium oxide/aluminum oxide films have been deposited using molecular beam epitaxy methods and characterized by reflection high-energy electron diffraction and transmission electron microscopy techniques. Growth on silicon substrates below 973 K resulted in primarily amorphous multilayers. At 1323 K, the deposition of titanium in an oxygen atmosphere on (0001) Al₂O₃ substrates resulted in films of Ti₂O₃. These films consisted of small domains, up to 60 nm, slightly misoriented from a [1120] ∥ [1120] orientation relationship. Two variants of Ti₂O₃ were observed due to multiple positioning during growth. Closing the titanium shutter during growth resulted in an oriented TiO₂ film.     

Inadequacies of Viscosity Theories for a Vitreous KNO3-Ca(NO3)2 Melt

The viscosity of a 0.60KNO₃-0.40Ca(NO₃)₂ melt was measured from 10^9.6 to 10¹⁴ P by a beam-bending method. In this range, the viscosity exhibited Arrhenius behavior, with an activation enthalpy of 138 kcal/mol. These data joined smoothly with capillary and rotational viscometer data from 10⁻² to 10⁸ P previously reported for this system. The temperature dependence of shear sound wave velocities at 75.2 MHz was measured, and the temperature dependence of the shear modulus from 60° to 120°C was calculated for this melt. The Fulcher equation, In _n=A+B/(T-T₀ ), described the temperature dependence of the viscosity of this melt poorly, indicating severe deficiencies in the viscosity theories which predict an equation of this form.     

Boron Nitride-Based Overcoat Thick Films for MoSi2 Planar Heating Elements

This work first reports a boron nitride-based dielectric system that is designed for MoSi₂–based planar heating elements patterned on a regular 96% alumina substrate. The dielectric system is expected to function as an overcoat layer mainly to protect the printed heating elements from environments and to reduce thermal stress induced during thermal heating through improved heat dissipation. The boron nitride (BN) pastes mixed with a low softening glass of calcium barium aluminoborosilicate were screen printed onto MoSi₂ thick films and then fired at a temperature of 900°C. The addition of BN was found to increase the thermal conductivity considerably without detrimental chemical reactions with glass constituents. For instance, the thick film containing 30 wt% BN was regarded as a promising composition from the supporting evidences of good adhesion with MoSi₂, an increased thermal conductivity of ∼31 W·(m·K)⁻¹, and a high electrical resistance of 4.7 × 10¹⁰Ω.     

Constant-K1 Double-Cantilever-Beam Test for Ceramic Materials

A constant- K ₁, double-cantilever-beam (DCB) test is described wherein a computer is used to adjust the load continuously as crack growth occurs. DCB samples of float glass were used to experimentally verify the procedure.     

Bimodal Sintering of Al2O3/Al2O3 Platelet Ceramic Composites

The sintering behavior of an Al₂O₃ compact containing uniformly dispersed Al₂O₃ platelets has been investigated. The results reveal a significant decrease in the sintering rate as well as the formation of voids and cracklike defects in the presence of nonsinterable platelets. The addition of a small amount (2 vol%) of tetragonal-ZrO₂ particles enhances the sintering rate, increases end-point density (∼99.5% of theoretical density) and prevents formation of sintering defects.     

Microstructural Evolution in a ZrO2 Wt% Y2O3 Ceramic

Several unusual microstructural features, i.e., 90° tetragonal ZrO₂ twins containing antiphase domain boundaries, tetragonal ZrO₂ precipitates in a colony morphology, and precipitate-free zones at the perimeter of cubic ZrO₂ grains containing fine tetragonal ZrO₂ precipitates, were observed in a single ZrO₂-12 wt% Y₂O₂ ceramic annealed at 1550°, 1400°, and 1250°C, respectively. The type of phase transformation responsible for each microstructural feature is described.     

Design of Ceramic Materials for Chemical Sensors with Novel Properties

Recently, the search for novel functions has received increasing attention in the field of materials. Outstanding possibilities for innovative applications are given by electroceramics. One of the fields which may be improved by a different use of functional ceramics is that of chemical sensors. In fact, the materials conventionally used in this field show problems still to be solved, such as insufficient gas selectivity, inability to detect very low gas concentrations, and changes in sensing properties caused by surface contamination. One possible solution to these problems is the design of materials with novel detection mechanisms. The design of innovative properties may be achieved by integration or hybridization of materials with different properties. In this paper, examples of multiphase materials for humidity and gas sensors are reported, i.e., La₂CuO₄/ZnO p-n heterocontacts, Au/ZnO Schottky barriers, and sol-gel processed thin films of TiO₂ with 10 at. % of K, based, respectively, on the interaction of p -type/ n -type semiconductors, metal/ceramic, and conductor/insulator.     

Core-Shell Structures in ZrO2-Modified BaTiO3 Ceramic

Pure BaTiO₃ exhibits a paraelectric-to-ferroelectric phase transition at 130°C. When stoichiometric BaTiO₃ is combined with 10 mol% ZrO₂, the relative permittivity (ε) changes to a broad, relatively insignificant temperature dependence, and the Curie point, T _c , is not sharply defined. However, the transition sharpens at T = 95°C when these samples are sintered for a longer period of 60 h. SEM, EDAX analysis coupled with TEM observation gives three types of core-shell structures of different microstructural characteristics which are related to the diffuse phase transition. Chemical inhomogeneity, due to Zr⁴⁺ distribution in the core-shell structure, is proposed to account for the diffuse phase transition behavior.     

Preparation of CuAlO2 Films by Wet Chemical Synthesis

CuAlO₂ is a delafossite-type compound and is a known p -type semiconductor. Transparent CuAlO₂ thin films were prepared using a sol–gel technique. The films with an Al/Cu atomic ratio of 1.0 consisted of CuAlO₂, Cu₂O, and CuO after heat treatment at 800°–900°C in nitrogen gas. The electrical resistivity of the film heated at 800°C was 250 Ω·cm.     

Glass-Free Zn2Te3O8 Microwave Ceramic for LTCC Applications

A Zn₂Te₃O₈ ceramic was investigated as a promising dielectric material for low-temperature co-fired ceramics (LTCC) applications. The Zn₂Te₃O₈ ceramic was synthesized using the solid-state reaction method by sintering in the temperature range 540°–600°C. The structure and microstructure of the compounds were investigated using X-ray diffraction (XRD) and scanning electron microscopy methods. The dielectric properties of the ceramics were studied in the frequency range 4–6 GHz. The Zn₂Te₃O₈ ceramic has a dielectric constant (ɛ_r) of 16.2, a quality factor ( Q _u× f ) of 66 000 at 4.97 GHz, and a temperature coefficient of resonant frequency (τ_f) of −60 ppm/°C, respectively. Addition of 4 wt% TiO₂ improved the τ_f to −8.7 ppm/°C with an ɛ_r of 19.3 and a Q _u× f of 27 000 at 5.14 GHz when sintered at 650°C. The chemical reactivity of the Zn₂Te₃O₈ ceramic with Ag and Al metal electrodes was also investigated.     

R-Curve Behavior of In-Situ-Toughened Al2O3:CaAl12O19 Ceramic Composites

The mechanical behavior of reaction-sintered alumina: 30 vol% calcium hexaluminate (Al₂O₃:CaAl₁₂O_19,or A1₂O₃: CA₆) composites was evaluated using the indentation strength in bending technique. A composite in which the hexaluminate (CA₆) phase possessed a platelike morphology showed more-pronounced R -curve behavior than a composite in which the CA₆ phase consisted of equiaxed grains. Toughness curves derived from the indentation-strength data exhibited a "crossover," such that the platelet composite exhibited the lower toughness at small flaw sizes, but the higher toughness at large flaw sizes. Incorporation of the platelet CA₆ resulted in enhanced toughening, compared to single-phase alumina of comparable grain size, thus demonstrating the viability of the in-situ -toughening approach. A simple grain-pullout model was used to estimate the toughening increment due to bridging by the platelet grains; the value obtained was in good agreement with toughness curves derived from indentation-strength measurements. Finally, fabrication of trilayer specimens, whereby outer layers of equiaxed A1₂O₃:CA₆ composite were strongly bonded to the platelet A1₂O₃:CA₆ composite, demonstrated high strength over the range of tested flaw sizes.     

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.     

Microcontact Printed BaTiO3 and LaNiO3 Thin Films for Capacitors

There is an ongoing need to develop new technologies to enable further down-scaling of layer thicknesses in multilayer ceramic devices, for example, in multilayer capacitors (MLC). Microcontact printing of chemical solutions of both the dielectric and electrode layers was explored as an economical means of preparing patterned thin films for MLC without requiring photolithography. For this purpose, methanol/acetic acid-based BaTiO₃ solutions were spun onto polydimethylsiloxane stamps, printed onto substrates, pyrolyzed, and crystallized. LaNiO₃ was used as a prototype electrode that could also be microcontact printed. The line edge roughness produced this way was on the order of a tenth of a micrometer, which should enable very small margins. The printed layer thickness was also very uniform. Microcontact printed capacitors with a single dielectric layer were fabricated and found to have dielectric constants >800 with loss tangents <2%. Alignment between subsequent layers is readily achieved. Multilayer dielectric/electrode stacks could be fabricated without cracking or delaminations. Consequently, microcontact printing appears to be a viable potential means of preparing MLC with layer thicknesses in the range of ≤0.2 μm.     

Synthesis and Characterization of a Remarkable Ceramic: Ti3SiC2

Polycrystalline bulk samples of Ti₃SiC₂ were fabricated by reactively hot-pressing Ti, graphite, and SiC powders at 40 MPa and 1600°C for 4 h. This compound has remarkable properties. Its compressive strength, measured at room temperature, was 600 MPa, and dropped to 260 MPa at 1300°C in air. Although the room-temperature failure was brittle, the high-temperature load-displacement curve shows significant plastic behavior. The oxidation is parabolic and at 1000° and 1400°C the parabolic rate constants were, respectively, 2 × 10⁻⁸ and 2 × 10⁻⁵ kg²-m⁻⁴.s⁻¹. The activation energy for oxidation is thus =300 kJ/mol. The room-temperature electrical conductivity is 4.5 × 10⁶Ω⁻¹.m⁻¹, roughly twice that of pure Ti. The thermal expansion coefficient in the temperature range 25° to 1000°C, the room-temperature thermal conductivity, and the heat capacity are respectively, 10 × 10⁻⁶°C⁻¹, 43 W/(m.K), and 588 J/(kgK). With a hardness of 4 GPa and a Young's modulus of 320 GPa, it is relatively soft, but reasonably stiff. Furthermore, Ti₃SiC₂ does not appear to be susceptible to thermal shock; quenching from 1400°C into water does not affect the postquench bend strength. As significantly, this compound is as readily machinable as graphite. Scanning electron microscopy of polished and fractured surfaces leaves little doubt as to its layered nature.     

Dielectric Properties of Electrophoretically Deposited and Isothermally Pressed BaTiO3 Thick Films

Thick BaTiO₃ films were prepared on platinum metallic foils by the electrophoretic deposition (EPD) technique using BaTiO₃ nanoparticles. In order to increase the density of the thick film, the green film was pressed under an isostatic pressure of 200 MPa before high-temperature sintering. The microstructures of deposited films were examined using X-ray diffraction and scanning electron microscopy techniques. Dielectric properties of the thick films were investigated. As the films grow thicker, the dielectric constant increases gradually and the dielectric loss decreases slightly. The experimental results indicate that isostatic pressing is an effective method to process thick films with dense microstructure and better dielectric properties.     

Surface Chemical Characterization of Ceramic Materials: Adsorption and Degradation of 3,6,9-Trioxadecanoic Acid on Nano-ZrO2

This paper deals with the specific interaction of the dispersant 3,6,9-trioxadecanoic acid (TODA) with nano-ZrO₂ surfaces. Special interest was directed towards degradation behavior of the adsorbates and its influence on dispersant capabilities of TODA regarding stabilization of ethanolic nano-ZrO₂ suspensions. ZrO₂ adsorption sites and the adsorbates formed are examined by diffuse reflectance infrared Fourier transform spectroscopy, thermal analysis, ¹H-, and ¹³C-cross polarization magic angle spinning solid-state nuclear magnetic resonance spectroscopy. ¹H as well as ¹³C-chemical shifts and the configurations of the corresponding adsorbed TODA species on zirconia sites are predicted by means of density functional theory quantum chemical calculations for supporting the interpretation of the experimental spectral data obtained. This work shows that combination of analytical and theoretical methods is an effective approach characterizing surface chemical properties of ceramic materials, determining sorption properties of organic process additives, investigating correspondent elementary and degradation reactions as well as clarifying cause-effect relationships in ceramic processes.     

Synthesis of ZrO2 and Y2O3-Doped ZrO2 Thin Films Using Self-Assembled Monolayers

Undoped or Y₂O₃-doped ZrO₂ thin films were deposited on self-assembled monolayers (SAMs) with either sulfonate or methyl terminal functionalities on single-crystal silicon substrates. The undoped films were formed by enhanced hydrolysis of zirconium sulfate (Zr(SO₄)·4H₄O) solutions in the presence of HCl at 70°C. Typically, these films were a mixture of two phases: nanocrystalline tetragonal- ( t -) ZrO₂ and an amorphous basic zirconium sulfate. However, films with little or no amorphous material could be produced. The mechanism of film formation and the growth kinetics have been explained through a coagulation model involving homogeneous nucleation, particle adhesion, and aggregation onto the substrate. Annealing of these films at 500°C led to complete crystallization to t -ZrO₂. Amorphous Y₂O₃-containing ZrO₂ films were prepared from a precursor solution containing zirconium sulfate, yttrium sulfate (Y₂(SO₄)₃8·H₂O), and urea (NH₂CONH₂) at pH 2.2–3.0 at 80°C. These films also were fully crystalline after annealing at 500°C.     

Microstructure, Conductivity, and NO2 Sensing Characteristics of α-Al2O3-Doped (8 mol% Sc2O3)ZrO2 Composite Solid Electrolyte

α-Al₂O₃-doped (8 mol % Sc₂O₃)ZrO₂ composite solid electrolyte has been investigated in the fabrication of solid-state ceramic gas sensors. The microstructure and electrical conductivity of the composite solid electrolyte have been measured over a range of temperature from 240°C to 596°C. The composite solid electrolyte has been found to exhibit a higher conductivity compared with the commonly used (8 mol% Y₂O₃)ZrO₂ at temperatures above ∼448°C. The sensing characteristics for NO₂ detection have been studied in the temperature range of 500–650°C at the low concentration from 10 to 30 ppm and at high concentration from 100 to 500 ppm of NO₂. The NO₂ sensor was found to respond reproducibly and rapidly to the variations of NO₂, concentration, indicating that the composite solid electrolyte has promising application as a solid electrolyte for on-board exhaust gas monitoring.