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.     

Hot Isostatic Pressing of Silicon Nitride with Boron Nitride, Boron Carbide, and Carbon Additions

Si₃ N₄ test bars containing additions of BN, B₄C, and C, were hot isostatically pressed in Ta cladding at 1900° and 2050°C to 98.9% to 99.5% theoretical density. Room-temperature strength data on specimens containing 2 wt% BN and 0.5 wt% C were comparable to data obtained for Si₃ N₄ sintered with Y₂O₃, Y₂O₃ and Al₂O₃, or ZrO₂. The 1370°C strengths were less than those obtained for additions of Y₂O₃ or ZrO₂ but greater than those obtained from a combination of Y₂O₃ and Al₂O₃. Scanning electron microscope fractography indicated that, as with other types of Si₃N₄, roomtemperature strength was controlled by processing flaws. The decrease in strength at 1370°C was typical of Si₃N₄ having an amorphous grainboundary phase. The primary advantage of non-oxide additions appears to be in facilitating specimen removal from the Ta cladding.     

Effect of Oxidation on Mechanical Properties of Fibrous Monolith Si3N4/BN at Elevated Temperatures in Air

The oxidation behavior and its effect on the mechanical properties of fibrous monolith Si₃N₄/BN after exposure to air at temperatures ranging from 1000° to 1400°C for up to 20 h were investigated. After exposure at 1000°C, only the BN cell boundary was oxidized, forming a B₂O₃ liquid phase. With increasing exposure temperature, the Si₃N₄ cells began to oxidize, forming crystalline Y₂Si₂O₇, SiO₂, and silicate glass. However, in this case, a weight loss was observed due to extensive vaporization of the B₂O₃ liquid. After exposure at 1400°C, large Y₂Si₂O₇ crystals with a glassy phase formed near the BN cell boundaries. The oxidation behavior significantly affected the mechanical properties of the fibrous monolith. The flexural strength and work-of-fracture decreased with increasing exposure temperature, while the noncatastrophic failure was maintained.     

BiNbO4-Based Glass–Ceramic Composites for Microwave Applications

The effect of a bespoke glass sintering aid, 0.3Bi₂O₃–0.3Nb₂O₅–0.3B₂O₃–0.1SiO₂ (BN1), developed from the base ceramic composition, BiNbO₄ (BN), on the sinterability, microstructure, and microwave (MW) dielectric properties of BN ceramics has been investigated. Densities >97% theoretical could be achieved at 1020°C for samples with up to 15% BN1 additions. The resulting microstructure was composed of BN laths surrounded by a residual glass phase that contained small fibrous crystals. Some evidence of dissolution of BN crystals was observed. Optimum properties were exhibited for samples with 15 wt% of glass addition sintered for 4 h at 1020°C with a relative permittivity ɛ_r=38, a MW quality factor Q × f ₀=17 353 at 5.6 GHz, and a temperature coefficient of resonant frequency τ_f=−10 ppm/°C. The high Q × f ₀, ɛ_r, and low τ_f, coupled with a relatively low sintering temperature, suggest that the use of bespoke glass sintering aids of this type may have great potential for the fabrication of MW ceramics.     

Direct Synthesis and Hydration of Calcium Aluminosulfate (Ca4Al6O16S)

Calcium aluminosulfate (Ca₄Al₆O₁₆S or C₄A₃̄) was prepared by direct synthesis from calcium and aluminum nitrates, and aluminum sulfate. CaAl₄O₇(CA₂) formed as an intermediate at 900°C, and C₄A₃̄ was the main phase after calcination at 1100°C. The specific surface areas after calcination at 1100° and 1300°C were ∼2.5 and 1 m²/g, respectively. Hydration was investigated using XRD, DSC, SEM, conduction calorimetry, and solid-state ²⁷Al MAS-NMR spectroscopy. Calorimetry showed that the induction period was longer than that of a sample prepared using conventional solid-state sintering, and this was attributed to the formation of amorphous coatings. Crystalline hydration products, principally calcium monoaluminosulfate hydrate and aluminum hydroxide, appeared subsequently. Although the induction period was very long, complete hydration occurred as early as 3 d in the sample calcined at 1100°C and was 91% complete in the sample calcined at 1300°C.     

Low-Temperature Synthesis of Calcium Hexa-Aluminate

Calcium hexa-aluminate (CaO·6Al₂O₃) has been prepared from calcium nitrate and aluminum sulfate solutions in the temperature range of 1000°–1400°C. A 0.3 mol/L solution of aluminum sulfate was prepared, and calcium nitrate was dissolved in it in a ratio that produced 6 mol of Al₂(SO₄)₃·16H₂O for each mole of Ca(NO₃)₂·4H₂O. It was dried over a hot magnetic stirrer at ∼70°C and fired at 1000°–1400°C for 30–360 min. The phases formed were determined by XRD. It was observed that CaO·Al₂O₃ and CaO·2Al₂O₃ were also formed as reaction intermediates in the reaction mix of CaO·6Al₂O₃. The kinetics of the formation of CaO·6Al₂O₃ have been studied using the phase-boundary-controlled equation 1 − (1 − x )^1/3= K log t and the Arrhenius plot. The activation energy for the low-temperature synthesis of CaO·6Al₂O₃ was 40 kJ/mol.     

Crystallization Kinetics of a Complex Lithium Silicate Glass-Ceramic

Volume crystallization of this glass is nucleated by Li₃PO₄. On heating from room temperature, Li₂SiO₃ appears around 650°C and then converts to Li₂Si₂O₅ around 850°C by reaction with SiO₂ from the melt. Preheating the glass at 1000°C forms larger Li₃PO₄ nuclei that promote additional crystallization of cristobalite in the 650° to 850°C range. Crystallization activation energies calculated from scan-rate dependence of DTA peaks are 270 kJ/mol for Li₂SiO₃ and 360 to 570 kJ/mol for Li₂Si₂O₅.     

Conversion of Tetranary Borate Glasses to Phosphate Compounds in Aqueous Phosphate Solution

In our earlier work, it was found that particles of a ternary alkali-borate glass, containing either CaO or BaO, converted completely to a crystalline phosphate of calcium or barium when reacted in an aqueous phosphate solution at 37°C. The present work is an extension of our earlier work to investigate the conversion of tetranary borate glass with the composition 10Li₂O·10CaO·10(AeO or T₂O₃)·60B₂O₃ (weight percent), where Ae is the alkai-earth metal Mg or Ba, and T is the transition metal La, Sm, or Dy. In the experiments, particles of each glass (150–300 μm) were reacted in 0.25 M K₂HPO₄ solution with a starting pH of ∼9.0 at 37°C. Weight loss and pH measurements indicated that the reaction was complete after 30–50 h, yielding an amorphous product. X-ray fluorescence showed that the as-formed product consisted of a calcium phosphate phase that contained the alkali-earth metal or transition metal present in the starting glass. Heating the as-formed material for 8 h at 600°–700°C produced a mixture of two crystalline phosphates: calcium phosphate and an alkali-earth or transition metal phosphate. The kinetics and mechanism of converting tetranary borate glass to phosphate materials are discussed and compared with data from earlier work for the conversion of ternary borate glass.     

Characterization and Crystallization of Y-Si-Al-O-N Glass

Glasses were prepared from sintered powders ofSi₃N₄, Al₂O₃, Y₂O₃ AlN, andSiO₂ to study their crystallization on subsequent heat treatment. Appreciable crystallization was efected only after the glasses were doped with up to 5 wt% ZrO₂. Electron microscopy and microanalysis showed that the crystalline phase was Y₂O₃·2SiO₂ without detectable Zr. The sofening temperature is in the range 850° to 1020°C. In-situ heating in a high-voltage electron microscope at ∼12OO°C produced renucleation and growth of the crystalline phase; at higher temperatures, however, the glass phase volatilized.     

Effect of Nucleating Agents on the Crystallization of Calcium Phosphate Glasses

Phase evolution in calcium phosphate-based glass ceramics has been examined. Pure CaO:P₂O₅ readily formed a glass which surface nucleated upon annealing, but volume nucleation at 680°C was observed only after the addition of the nucleating agents, TiO₂ and A1₂O₃. Phase separation of Ti and Al occurred along with the nucleation and growth of a calcium phosphate phase, similar to β-Ca₂P₂O₇. Heat treatments at higher temperatures and/or for longer times resulted in crystallization of A1- and Ti-rich, phase-separated regions. A glass with a higher CaO:P₂O₅ ratio (approximately 2:1) could be prepared only when a total of 25-35 mol% of TiO₂, A1₂O₃, and SiO₂ were present in the batch. The glass phase-separated into respective SiO₂- and CaO/P₂O₅-rich regions on cooling. The SiO₂-rich regions did not influence crystallization and remained amorphous throughout the heat treatments. In the CaO/P₂O₅-rich regions, homogeneous volume nucleation of a Ti-rich phase readily occurred followed by the heterogeneous nucleation and growth on these nuclei of a calcium phosphate phase. Although this phase was macroscopically composed of spherulites, TEM revealed that they consisted of intertwined nanodendrites whose individual arms were approximately 20 nm wide and 50 nm long.     

Sol–Gel Synthesis of Strontium Pyroniobate and Calcium Pyroniobate

Strontium and calcium pyroniobates were prepared by a sol–gel process, using strontium/calcium metal and niobium ethoxide as precursors. The formation of Sr₂Nb₂O₇ occurred at 750°C via an intermediate perovskite phase of composition close to Sr_0.82NbO₃. The crystallization of Ca₂Nb₂O₇ occurred at 600°C directly without any intermediate phases. Sintered Sr₂Nb₂O₇ and Ca₂Nb₂O₇ pellets showed a preferred grain orientation. Microstructural studies revealed an increase in grain growth and associated orientation with sintering temperature.     

Nucleation and Crystallization of a Lead Halide Phosphate Glass by Differential Thermal Analysis

The nucleation and crystallization mechanisms of a lead halide phosphate glass [40P₂O₅·30PbBr₂·30PbF₂ (mol%)] were investigated by differential thermal analysis (DTA) and X-ray diffraction analysis. There were two crystalline phases in the crystallized samples: the major phase was PbP₂O₄, and the minor phase was PbP₂O₆. The average activation energy for crystallization, E , for two different particle sizes of this glass was determined to be 119 ± 4 kJ/mol by the Kissinger method and 124 ± 4 kJ/mol by the Augis–Bennett method. The Avrami constants were determined to be 1.6 and 2.5 for particle sizes of 203 and 1040 μm, respectively, by the Ozawa equation, and 1.7 and 2.4 for particle sizes of 203 and 1040 μm, respectively, by the Augis–Bennett equation. The decrease in the crystallization peak height in the DTA curve with increasing particle size suggested that the particles crystallize primarily by surface crystallization. A nucleation-rate type curve was determined by plotting either the reciprocal of the temperature corresponding to the crystallization peak maximum, 1/ T _p, or the height of the crystallization peak, (δ T )_p, as a function of nucleation temperature, T _n. The temperature where nucleation can occur for this glass ranges from 360°–450°C and the maximum nucleation rate is at 420°± 10°C.     

High Quality and Yield in Potassium Titanate Whiskers Synthesized by Calcination from Hydrous Titania

Hydrous titanium dioxide (TiO₂· n H₂O) was used to prepare K₂Ti₂O₅ single crystals, K₂Ti₄O₉ whiskers and K₂Ti₆O₁₃ whiskers at 820°, 940°, and 1110°C, respectively, by calcination. At T < 820°C, dehydration of hydrous titania, decomposition of potassium carbonate, and reaction between titanate and potassium oxide occurred simultaneously, ending with a crystallization reaction of K₂Ti₂O₅ single crystals at 820°C. Subsequently, K₂Ti₂O₅ single crystals convert into K₂Ti₄O₉ whiskers at 940°C, and K₂Ti₄O₉ whiskers further convert into K₂Ti₆O₁₃ whiskers at 1110°C. The reaction temperatures for the generations of these types of potassium titanates were all 10°–40°C lower than the corresponding temperatures when anatase was used as the reactant. The whiskers synthesized in the present study exhibited uniform size, good morphology, and a high yield.     

The System Al2O3-Cr2O3-Sio2

Liquidus phase equilibrium data are presented for the system Al₂O₃-Cr₂O₃-SiO₂. The liquidus diagram is dominated by a large, high-temperature, two-liquid region overlying the primary phase field of corundum solid solution. Other important features are a narrow field for mullite solid solution, a very small cristobalite field, and a ternary eutectic at 1580°C. The eutectic liquid (6Al₂O₃-ICr₂O₃-93SiO₂) coexists with a mullite solid solution (61Al₂O₃-10Cr₂O₃-29SiO₂), a corundum solid solution (19Al₂O₃-81Cr₂O₃), and cristobalite (SO₂). Diagrams are presented to show courses of fractional crystallization, courses of equilibrium crystallization, and phase relations on isothermal planes at 1800°, 1700°, and 1575°C. Tie lines were sketched to indicate the composition of coexisting mullite and corundum solid solution phases.     

Effect of Silicon Carbide Additions on the Crystallization Behavior of a Magnesia-Lithia-Alumina-Silica Glass

Glass in the MgO-Li₂O-A1₂O₃-SiO₂ system was observed to crystallize readily at temperatures from 700° to 900°C. The primary crystalline phase evolved was Li₂Si₂O₅, and the secondary phase evolved was Li₂SiO₃. The glass was amorphous after heating in air at 1050°C for 30 min. The addition of 0.5 wt% SiC powder resulted in the crystallization of Li₂SiO₃ during heating in air at 1050°C for 30 min. It was suggested that the difference in crystallization behavior with Sic addition was due to dissolution of Sic into the oxide glass.     

Calcium Phosphate Cements Prepared by Acid–Base Reaction

We investigated the characteristics of calcium phosphate cements (CPC) prepared by an exothermic acid–base reaction between NH₄H₂PO₄-based fertilizer (Poly-N) and calcium aluminate compounds (CAC), such as 3CaO · Al₂O₃ (C₃A), CaO · Al₂O₃ (CA), and CaO · 2Al₂O₃ (CA₂), in a series of integrated studies of reaction kinetics, interfacial reactions, in-situ phase transformations, and microstructure development. Two groups were compared: untreated and hydrothermally treated CPC specimens. The extent of reactivity of CAC with Poly-N at 25°C was in the following order: CA > C₃A ≫ CA₂. The formation of a NH₄CaPO₄· x H₂O salt during this reaction was responsible for the development of strength in the CPC specimens. The in-situ phase transformation of amorphous NH₄CaPO₄· x H₂O into crystalline Ca₅(PO₄)₃(OH) and the conversion of hydrous Al₂O₃ gel →γ-AIOOH occur in cement bodies during exposure in an autoclave to temperatures up to 300°C. This phase transformation significantly improved mechanical strength.     

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.     

Effect of Sintering Aid Composition on the Processing of Si3N4/BN Fibrous Monolithic Ceramics

Si₃N₄/BN fibrous monoliths were prepared with 4 wt% Y₂O₃ added as a sintering aid to the Si₃N₄. Residual carbon, present in the billet before hot-pressing, was shown to influence the final microstructure. The sintering aid glass, known to migrate into the BN cell boundaries during hot-pressing, was not sufficient in quantity to prevent premature shear failure when samples were tested in flexure. Increasing the hot-pressing temperature alleviated this problem. For flexure samples tested at 1400°C, fibrous monoliths fabricated with 4 wt% Y₂O₃ demonstrated linear-elastic loading behavior at a greater stress than fibrous monoliths fabricated with 6-wt%-Y₂O₃/2-wt%-Al₂O₃ sintering aids.     

Synthesis of Strontium Dialuminate Via an Ethylenediaminetetraacetic Acid Precursor

Strontium dialuminate (SrAl₄O₇) can be synthesized by crystallization of amorphous spray-dried precursors or solidification from the liquid. In this paper, SrAl₄O₇ was prepared via the ethylenediaminetetraacetic acid precursor route. Differential thermal analysis, thermogravimetric, fourier transform infrared spectroscopy, and X-ray diffraction (XRD) were used to characterize the precursors and the oxide powders derived. XRD analysis showed that single-phase SrAl₄O₇ was obtained from pulverized resin at a temperature of 1050°C for 2 h and SrAl₄O₇ can be stable at least up to 1200°C. Single-phase SrAl₄O₇ was not obtained from the citrate acid route.     

Effect of P2O5 on the Crystallization of Lead Silicate Glasses

The effect of P₂O_S on the devitrification of binary lead silicate glasses containing 64 and 59 mol% PbO was studied. Glasses underwent isothermal crystallization treatments at 400°, 450°, 500°, and 550°C. A polymorph of 3PbO₂SiO₂ was the major product of crystallization for all compositions of glasses. Secondary products of crystallization were found to be a polymorph of PbOSiO₂ in the 59 mol% and a low-temperature polymorph of 2PbOSiO₂ in the 64 mol% PbO glasses. Dominant mode of crystallization in both binary glasses was surface devitrification at all temperatures studied. Addition of P₂O₅ promoted internal crystallization in the form of spherulites. 400°C was found to be the most effective temperature for nucleating spherulitic growth. Crystallization at 400°C led to high concentrations of spherulites in all glasses containing at least 0.5 mol% P₂O₅. Concentrations of 0.5 mol% P₂O₅ were needed to produce detectable levels of spherulitic nucleation at r<400°C.