Critical Microstructures for Microcracking in Al2O3-ZrO2 Composites

The internal strains asSociated with the martensitic phase transformation of zirconia were used to introduce microcracks into Al₂O₃/ZrO₂ composites. The degree of transformation was found to be dependent on the volume fraction of ZrO₂ and its size, the latter of which could be controlled by suitable heat treatments. The microstructural changes that occurred during the heat treatments were studied using quantitative microscopy and X-ray diffraction. For materials containing more than 7.5 vol% Zr0₂, the ZrO₂ particles were found to pin the Al₂O₃ grain boundaries, thus limiting the Al₂O₃ grain growth. The limiting grain size was found to be dependent on size and volume fraction of ZrO₂. Heat treatments for the higher volume fraction materials (>7.5 vol% ZrO₂) caused micro-structural changes which resulted in increased amounts of monoclinic ZrO₂ at room temperature; elastic modulus measurements indicated that this was occurring concurrently with microcracking. By combining the ZrO₂ grain-size distributions with the X-ray analysis it was possible to calculate the critical ZrO₂ size required for the transformation. The critical size was found to decrease with increasing amounts of ZrO₂. Hardness and indentation fracture toughness were measured on the composites. Grain fragmentation was observed at the edge of the indentations and microcracks were observed directly, using an AgNO₃ decoration technique, near the indentations.     

Nanosilver-Coated Porous SiC–Si3N4 Composite Using Microwave-Assisted Process

Using a novel microwave-assisted process, nano-Ag-coated continuous porous SiC–Si₃N₄ substrate was fabricated from a solution containing AgNO₃ salts and ethylene glycol. The detailed microstructure of the fabricated substrate was investigated depending on the amount of AgNO₃ salts in the starting solution and the microwave irradiation time. From a solution containing 0.4 g of AgNO₃ for 60 s irradiation time, the Ag nanoparticles, ∼25 nm in diameter, were homogeneously coated on the continuous porous SiC–Si₃N₄ matrix as well as on the surface of the Si₃N₄ whiskers. However, the Ag nanoparticles (∼15 nm) deposited from a solution containing 0.6 g of AgNO₃ for 60 s irradiation time showed maximum homogeneity and narrow size distribution. The components of Si, N, and Ag were homogeneously distributed on the deposited layer. The deposited Ag nanoparticles covered with a thin (∼2 nm), amorphous layer had nanocrystallinity and adhered well to the surface of the Si₃N₄ whiskers.     

PbTiO3-PbO-B2O3 Glass-Ceramics by a Sol-Gel Process

PbTiO₃ (PT)-PbO-B₂O₃ glass-ceramics were produced by a sol-gel process. Achievement of high PT content at levels unattainable by conventional glass-ceramics preparation methods was semiquantitatively shown. PT content was similar to the designed PT volume fraction and seemed rather unaffected by the composition of the glassforming component at a calcination temperature of 700°C. A higher ratio of PbO to B₂O₃ in the glassforming component resulted in a low PT crystallization temperature, <500°C. PT crystals 1-2 μm in size were obtained at calcination temperatures >600°C.     

Prominent Nanocrystallization of 25K2O·25Nb2O5·50GeO2 Glass

Some K₂O-Nb₂O₅-GeO₂ glasses are prepared, and their crystallization behaviors are examined. 25K₂O·25Nb₂O₅·50GeO₂ glass with the glass transition temperature T _g= 622°3C and crystallization onset temperature T _x= 668°3C shows a prominent nanocrystallization. The crystalline phase is K_3,8Nb₅Ge₃O_20,4 with an orthorhombic structure. The sizes of crystals in the crystallized glasses heat-treated at 630° and 720°3C for 1 h are °10 and 20–30 nm, respectively, and the crystallized glasses obtained by heat treatments at 620°-850°3C for 1 h maintain good transparency. The density of crystallized glasses increases gradually with increasing heat-treatment temperature, and the volume fraction of crystals in the sample heat-treated at 630°3C for 1 h is estimated to be ∼35%. The usual Vickers hardness and Martens hardness (estimated by nanoindentation) of 25K₂O·25Nb₂O₅·50GeO₂ glass change steeply by heat treatment at T _g, i.e., at around 35% volume fraction of nanocrystals. The present study demonstrates that the composite of nanocrystals and the glassy phase has a strong resistance against deformation during Vickers indenter loading in crystallized glasses.     

Mechanical Properties of Hot-Pressed TiB2-ZrO2 Composites

The use of monoclinic ZrO₂ as an additive improves the mechanical properties of TiB₂-based composites without the use of stabilizers. In particular, TiB₂-30% ZrO₂ compacts exhibited a transverse rupture strength of 800 MN/m², few pores, and a K_{I c} of 5 MPa·m^1/2. The high strength and toughness are thought to result mainly from the presence of partially stabilized tetragonal ZrO₂ and from solid solution of (TiZr)B₂ formed in sintering.     

Crystallization and Properties of Fe2O3—CaO—SiO2 Glasses

Nucleation and crystal growth rates and properties were studied in a two-stage heat treatment process for Fe₂O₃-CaO-SiO₂ glasses. Glass transition (T_g) and crystallization temperatures (T _c ) for the glasses lay between about 612.0° and 710.0°C, and 858.5° and 905.0°C, respectively, and magnetite was the main crystal phase. For a glass of 40Fe₂O₃. 20CaO·40SiO₂ (in wt%) the maximum nucleation rate was (68.6 ± 7) × 10⁶/mm³·s at 700°C, and the maximum crystal growth rate was 9.0 nm/min^1/2 at 1000°C. The mean crystal size of the magnetite increased from 30 to 140 nm with variation of nucleation and crystal growth conditions. The glass showed the maxima in saturation magnetization and coercive force, 212.1 × Wb/m² and 30.8 × 10³ A/m, when heat-treated for 4 h at 1000°C and 1050°C, respectively. The variation of the saturation magnetization could be quantitatively interpreted well in terms of the volume fraction of the magnetite, whereas that of the coercive forces could be explained only qualitatively in terms of the particle size of the magnetite. Hysteresis losses showed the maximum value of 1493 W/m³ when heat-treated at 1000°C for 4 h prenucleated at 700°C for 60 min, and increased linearly with increasing heat treatment time under a magnetic field up to 800 × 10³ A/m.     

Crystallization of MgO-Al2O3-SiO2-ZrO2 Glasses

The crystallization of MgO-Al₂O₃-SiO₂-ZrO₂ glasses at 1000°C was studied. Isothermal heat treatments of a cordierite-based glass (2MgO.2Al₂O₃.5SiO₂= Mg₂Al₄Si₅O₁₈) with 7 wt% ZrO₂ produced surface crystallization of α-cordierite and tetragonal ZrO₂ ( t -ZrO₂). These phases advanced into the glass by cocrystallization of t -ZrO₂ rods in an α-cordierite matrix with a well-defined orientation relation. The t -ZrO₂ rods were unstable with respect to diffusional breakup (a Rayleigh instability) and decomposed into rows of aligned ellipsoidal and spheroidal particles. The t -ZrO₂ was very resistant to transformation to monoclinic symmetry. With a similar glass containing 15 wt% ZrO₂, surface crystallization of α-cordierite and t -ZrO₂ was accompanied by internal crystallization of t -ZrO₂ dendrites. Transformation of the dendrites to mono-clinic symmetry was observed under some conditions.     

Crystallization of BeO, Be2SiO4, and SiO2 from Li2MoO4-MoO3

Single crystals of phenacite (Be₂SiO₄), bromellite (BeO), and tridymite (SiO₂) were grown from an Li₂MoO₄-MoO₃ flux. Phenacite, with rhombohedral symmetry, grew in three distinct shapes with aspect ratios (length/width) as follows: needles (>3), rods (>1.1 to 1.5), and rhombohedral-faced crystals (=1). The latter grew as single crystals; the others were twinned on the     . For most experiments the temperature was held constant at 1165°C and the Li₂MoO₄/MoO₃ ratio at 1/16. The growth mechanism for crystallization was the evaporation of MoO₃. The system produced one to three phases, depending on the BeO/SiO₂ ratio. Bromellite grew until a BeO/SiO₂ ratio of 0.8 was attained. It grew as a hemipyramidal crystal having a short prism with a curved     top or as a hexagonal plate. The pyramid- and prism-shaped crystals were twinned, although a few hexagonal plates were single. Tridymite grew in small hexagonal plates when the BeO/SiO₂ ratio was less than 1.5. The effect of temperature, nucleation, and flux composition on crystal shape, twinning, and occurrence is discussed.     

Nucleation and Crystallization of NaNbO3 from Glasses in the Na2O-Nb2O5-SiO2 System

Transparent glass-ceramics, in which the major phase was NaNbO₃, were obtained by heat treatment of glasses in the Na₂O-Nb₂O₅-SiO₂ system. The structure of the glass and the changes occurring during crystallization as a function of temperature and heating rate were examined by X-ray diffraction, transmission and replication electron microscopy, density, and other measurements. On heating, a rather abrupt formation of uniformly dispersed particles was observed. In the early stages of crystallization, these particles contained NaNbO₃ as loose, radially grown dendrites of identical crystal orientation which became dense during later stages of crystallization. The particle sizes ranged from 200 to 10,000 A, depending on the SiO₂ content of the glass. Transparency of the crystallized material was dependent on the particle size rather than on the amount of NaNbO₃ formed. The temperature at which crystallization occurred increased with the heating rate whereas the viscosity at crystallization decreased. For a given value of the rate of crystal formation per °C of temperature increase, the product (viscosity)ⁿ× (heating rate) was constant. The nucleation and growth phenomena which occurred in these glasses was attributed to microheterogeneities of higher Nb₂O₅ content which formed part of the glass structure.     

Thermochemistry and Aqueous Durability of Ternary Glass Forming Ba-Titanosilicates: Fresnoite (Ba2TiSi2O8) and Ba-Titanite (BaTiSiO5)

Barium titanosilicates are possible oxide forms for the immobilization of short-lived fission products in radioactive waste. Ba₂TiSi₂O₈ (fresnoite) and BaTiSiO₅ (Ba-titanite) samples were prepared by a solid-state synthesis. The enthalpies of formation of Ba₂TiSi₂O₈ crystal and glass at 25°C and of BaTiSiO₅ glass were obtained from drop solution calorimetry in a molten lead borate (2PbO–B₂O₃) solvent at 701°C. The enthalpy of formation for fresnoite composition samples from constituent oxides was exothermic and became more exothermic with increasing crystallinity. Differential scanning calorimetry revealed that the crystallization rate of the fresnoite glasses increased with increasing devitrification. A modified Product Consistency Test-Procedure B (PCT-B) was used to collect solubility data on the fresnoite and titanate phases. The tests suggest that both glassy and crystalline fresnoite exhibit favorable aqueous stability and should be explored further as radioactive waste forms for long-term storage.     

Sintering of a Crystallizable CaO-B2O3-SiO2 Glass with Silver

Effects of Ag addition on sintering of a crystallizable CaO-B₂O₃-SiO₂ glass have been investigated at 700°–900°C in different atmospheres. With Ag content increasing in the range of 1–10 vol%, the softening point, the densification, the onset crystallization temperature, and the total amount of crystalline phase formed of the crystallizable glass are reduced when fired in air. A bloating phenomenon is observed when the crystallizable CaO-B₂O₃-SiO₂ glass doped with 1–10 vol% Ag is fired at 700°–900°C for 1–4 h. Fired in N₂ or N₂+ 1% H₂, however, the above phenomena disappear completely. It is thus believed that the diffusion of Ag into the crystallizable glass, which is caused by the oxidation of Ag in air, is the root cause for the above results observed.     

Phase Equilibration in ZrO2-Y2O3 Alloys by Liquid-Film Migration

The tetragonal ( t ) and cubic ( c ) ZrO₂ solid solutions in two-phase ZrO₂-8 wt% Y₂O₃ ceramics have low and high solute content, respectively. Annealing samples sintered at 1600°C between 700° and 1400°C requires a change in the volume fraction of the coexisting phases, as well as their equilibrium Y₂O₃ content. The enrichment in Y₂O₃ content of the c -ZrO₂ grains is accomplished by liquid-film migration involving the ubiquitous silicate grain-boundary phase, while the volume fraction of t -ZrO₂ increases by the nucleation and growth of cap-shaped t -ZrO₂ lenses. The interfaces between the c -ZrO₂ matrix and the growing t -ZrO₂ lenses are semicoherent.     

Effect of B2O3 and hBN Crystallinity on cBN Synthesis

Four kinds of BN powders—amorphous BN with B₂O₃, partially crystallized BN without B₂O₃, well-crystallized hBN with B₂O₃, and well-crystallized hBN without B₂O₃—were prepared to determine the effect of B₂O₃ on the crystallization of amorphous BN and the effect of BN crystallinity on the formation of cBN under high pressure (4–5 GPa) and at high temperature (1350–1450°C). The amorphous BN with B₂O₃ easily crystallized and transformed to cBN in the presence of A1N catalyst, while the partially crystallized BN without B₂O₃ did not. The well-crystallized hBN transformed very slowly to cBN without B₂O₃, in contrast to fast transformation with B₂O₃. It is thus found that the transformation from hBN to cBN in the presence of AIN catalyst is determined by the degree of BN crystallinity as well as the presence of B₂O₃. Cubic BN can be synthesized only from crystallized hBN under the experimental conditions used. The formation of cBN from amorphous BN is possible through its prior crystallization, which can occur in the presence of B₂O₃.     

Microstructure and Kinetics of Crystallization of MgO-Al2O3−Si02 Glass-Ceramics

Quantitative X-ray diffraction and microscopy were used to study the morphology development and overall crystallization rate between 900° and 990°C of MgO-Al₂O₃−SiO₂ glasses with added ZrO, TiO₂, CaF₂, or CeO₂. Three basic stages of micro-structural development were distinguishable: I, an induction period, II, a spherulitic crystallization stage, and III, a final crystallization stage. The duration of the induction period, the crystallization rate of the high-quartz solid solution, and the microstructures varied markedly with prior nucleation treatment and the type of modifier present in a glass of nearly equal silica content. The roles of major (high-quartz ss , high cordierite) and of minor crystalline and liquid phases in textural development are discussed, and it is postulated that nucleants (ZrO₂, TiO₂) act also as growth-modifying "impurities" in crystal growth.     

Thermopower of YBa2Cu3O7-δ–Ag Composites

The percolation behavior of normal-state thermopower, resistivity, and superconductivity have been studied in YBa₂Cu₃O_7-δ─Ag (YBCO─Ag) composite systems. The normal-state resistivity and thermopower show a percolation threshold at a Ag volume fraction ( V _Ag) of 20% to 30%, whereas the superconducting network shows a threshold at a V _Ag of ≅70% to 80%. The results obtained from this study show that the YBCO─Ag composite obtained from Ag₂O and YBCO powders is uniformly distributed with Ag and YBCO remaining as separate phases without changing their characteristics. The measurements of thermopower indicate that the normal-state thermopower and phonon-drag thermopower are affected by the Ag addition. The stability of YBCO is increased when it is in composite form.     

Indentation Fracture Response and Damage Resistance of Al2O3-ZrO2 Composites Strengthened by Transformation-Induced Residual Stresses

Indentation fracture behavior of three-layer Al₂O₃-ZrO₂ composites with substantial compressive residual stresses was compared with the behaviors of monolithic Al₂O₃ and Al₂O₃-ZrO₂ ceramics without intentionally introduced residual stresses. The indentation cracks were smaller in the three-layer specimens relative to the monolithic specimens in agreement with the predictions of indentation fracture mechanics theory. Indentation and strength testing were used to show that a residual compressive stress of approximately 500 MPa exists in the outer layers of the three-layer composites. The three-layer specimens showed excellent damage resistance in that the strength differential between the three-layer and monolithic indented specimens was maintained at indentation loads up to 1000 N, the maximum indentation load used in the experiments.     

Rapid Crystallization of SiO2-Al2O3 Glasses

The crystallization of Al₂O₃-rich glasses in the system SiO₂-Al₂O₃ which were prepared by flame-spraying and/or splat-cooling was studied by DTA, electron microscopy, and X-ray diffraction. Over a wide range of compositions, the crystallization temperature ( T_x ) remained near 1000°C, changing smoothly with composition. In all cases crystallization of mullite was detected by X-ray diffraction. In the low-Al₂O₃ region, coarsening of the microstructure during crystallization was observed by electron microscopy. In the high-Al₂O₃ region mullite and γ-Al₂O₃ cocrystallized; this behavior may be interpreted as evidence of a cooperative process of crystallization at the respective T_x 's. The crystallite size of the mullite immediately after rapid crystallization increased continuously with increasing Al₂O₃ content. In light of the T_x data, the adequacy of the evidence for the proposed metastable miscibility gap in the SiO₂-Al₂O₃ system is questioned.     

Crystallization of MgO-CaO-SiO2-P2O5 Glass

The crystallization behavior of a glass with a composition of 40 wt% 3CaO · P₂O₅−60 wt% CaO · MgO · 2SiO₂ was investigated. The primary crystalline phase was apatite with a dendritic form and ellipsoidal shape. β-(3CaO · P₂O₅) and CaO · MgO · 2SiO₂ were crystallized as samples heated to 990°C, and a three-layer structure was obtained. The development and morphology of this construction were explained by both the surface crystallization of the apatite and CaO · MgO · 2SiO₂ and the bulk crystallization of apatite and the CaO · MgO · 2SiO₂-β-(3CaO · P₂O₅) composite.     

Sol-Gel Route to Ferroelectric Layer-Structured Perovskite SrBi2Ta2O9 and SrBi2Nb2O9 Thin Films

Precursors for layer-structured perovskite thin films of SrBi₂Ta₂O₉ (SBT) and SrBi₂Nb₂O₉ (SBN) were prepared by the reactions of a strontium-bismuth double methoxyethoxide and tantalum or niobium methoxyethoxide in methoxyethanol, followed by partial hydrolysis. Several spectroscopic techniques, such as ¹H-, ¹³C-, and ⁹³Nb-NMR (nuclear magnetic resonance), and Fourier-transform infrared spectroscopy were used to analyze the arrangement of the metals and oxygen in the precursor molecules. The precursors contained Sr-O-M (where M is Ta or Nb) bonds (i.e., a strontium is connected to two MO₆ octahedra) and Sr-O-Bi bonds with a bismuth atom bonded to the oxygens of the MO₆ octahedron. The arrangement of metals and oxygens was considered to be similar to the layer-structured perovskite crystal sublattice. As a result, the sol-gel-derived SBT thin films crystallized, by rapid thermal annealing in an oxygen atmosphere below 550°C, and they exhibited preferred (115) orientation. The crystallinity improved and the crystallite size increased with temperature up to 700°C. In the case of SBN thin films, a low heating rate (2°C/min) was necessary for the control of the crystallographic (115) orientation, whereas a rate of 200°C/s (rapid thermal annealing) produced films that exhibited c -axis orientation. The (115) SBT thin film, heated to 700°C, exhibited improved ferroelectric properties.     

Comparison of KIc Values for Al2O3-ZrO2 Composites Obtained from Notched-Beam and Indentation Strength Techniques

Values of K_Icfor hot-pressed AL₂O₃-ZrO₂ composites were measured using notched-beam and indentation strength techniques. The results are compared with K factors at the mirror/mist boundary and at crack branching. It was found that the indentation strength technique provides a more consistent estimation of K_Ic, than the notched-beam technique.