Microstructure stability of fine-grained silicon carbide ceramics during annealing

Fine-grained silicon carbide ceramics with an average grain size of 140 nm or smaller were prepared by low-temperature hot-pressing of very fine -SiC powders using Al₂O₃-Y₂O₃-CaO (AYC) or Y-Mg-Si-Al-O-N glass (ON) as sintering additives. The microstructure stability of the resulting fine-grained SiC ceramics was investigated by annealing at 1850°C and by evaluating quantitatively the grain growth behavior using image analysis. The phase transformation of SiC in AYC-SiC was responsible for the accelerated abnormal grain growth of platelet-shaped grains. In contrast, the phase transformation in ON-SiC was suppressed, which resulted in a very stable microstructure.     

Preparation of Ultrafine Tetragonal ZrO2–CeO2Solid Solutions

Nanometer-sized tetragonal Zr_{1 – x} Ce _x O_{2 –} powders were prepared by hydroxide precipitation and sol–gel processing. The effects of gel-aging time and solution concentration on the phase composition and particle size of the powders were studied. The ceramics prepared by sintering ultrafine powders at 1500°C had a density of 6.0 g/cm³, open porosity of 4%, and closed porosity below 1%.     

Microstructural development and mechanical properties of pressureless-sintered SiC with plate-like grains using Al2O3-Y2O3 additives

Dense SiC ceramics with plate-like grains were obtained by pressureless sintering using -SiC powder with the addition of 6 wt% Al₂O₃ and 4 wt% Y₂O₃. The relationships between sintering conditions, microstructural development, and mechanical properties for the obtained ceramics were established. During sintering of the -SiC powder compact the equiaxed grain structure gradually changed into the plate-like grain structure that is closely entangled and linked together through the grain growth associated with the phase transformation. With increasing holding time, the fraction of phase transformation, the grain size, and the aspect ratio of grains, increased. Fracture toughness increased from 4.5 MPa m^1/2 to 8.3 MPa m^1/2 with increasing size and aspect ratio of the grains. Crack deflection and crack bridging were considered to be the main operative mechanisms that led to improved fracture toughness.     

Preparation and transport properties of aqueous sol-gel synthesized NaCo2O4−δ

We have successfully prepared thermoelectric materials NaCo₂O_4– at lower temperature (700°C) using aqueous sol-gel methods. We find that the electrical resistivity and thermopower of NaCo₂O_4– depend strongly on the sintering temperature and partial pressure of oxygen. The oxygen content of NaCo₂O_4– is found to decrease with increasing sintering temperature. The sample prepared at the combination of 700°C and pure flowing oxygen exhibits the highest value of power factor.     

Sintering mechanisms and microstructural development of coprecipitated mullite

Coprecipitated mullite precursor powders of the bulk compositions 78 wt% Al₂O₃+22 wt% SiO₂ (high-Al₂O₃ material) and 72 wt% Al₂O₃+28 wt% SiO₂ (low-Al₂O₃ material) have been used as starting materials. The precursor powders were calcined at 600, 950, 1000, 1250, and 1650 C, and test sintering runs were performed at 1550, 1600, 1650, 1700, and 1750 C. Homogeneous and dense ceramics were obtained from cold isostatically pressed (CIPed) powders sintered in air at 1700 C. Therefore, all further sintering experiments were carried out at 1700 C. After pressureless sintering, sample specimens were hot isostatically pressed (HIPed) at 1600 C and 200 bar argon gas pressure. Sintering densifications of low Al₂O₃ materials ranged between 94% and 95.5%. There was no clear dependency between densification and calcination temperature of the starting powders. High-Al₂O₃ compositions displayed sintering densities which increased from 97% at 600 C calcination temperature to 99% at 950 C calcination temperature. Higher calcination temperatures first caused slight lowering of the sintering density to 95.5% (calcination temperature 1250 C) but later the density strongly decreased to a value of 85% (calcination temperature 1650 C). HIPing of pressureless sintered specimens prepared from powders calcined between 600 and 1100 C yielded 100% density. At the given sintering temperature of 1700 C, the microstructure of sample specimens was influenced by Al₂O₃/SiO₂ ratios and by calcination temperatures of the starting powders. Homogeneous and dense microstructures consisting of equiaxed mullite plus some minor amount of -Al₂O₃ were produced from high-Al₂O₃ powders calcined between 600 and 1100 C. Low-Al₂O₃ sample specimens sintered from precursor powders calcined between 600 and 1100 C were less dense than high-Al₂O₃ materials. Their microstructure consisted of relatively large and elongated mullite crystals which were embedded in a fine-grained matrix of mullite plus a coexisting glass phase. The different microstructural developments of high- and low-Al₂O₃ compositions may be explained by solid-state and liquid-phase sintering, respectively. The microstructure of HIPed samples was very similar to that of pressureless sintered materials, but without any pores occurring at grain boundaries.     

Hydrazine method of synthesis of γ-Fe2O3 useful in ferrites preparation. Part IV – preparation and characterization of magnesium ferrite, MgFe2O4 from γ-Fe2O3 obtained from hydrazinated iron oxyhydroxides and iron (II) carboxylato-hydrazinates

Electro-magnetic properties and microstructural characterization of MgFe₂O₄ synthesized by a ceramic technique at 1000°C from iron oxides, consisting of mainly -Fe₂O₃ and traces of alpha-Fe₂O₃, prepared from iron ore rejects, are compared with the ferrite obtained from commercial alpha-Fe₂O₃. The sources of -Fe₂O₃ are hydrazinated iron (II) carboxylates and iron oxyhydroxides which autocatalytically decompose giving mainly -Fe₂O₃ of uniform particles of 10–30 nm (by scanning electron microscopy (SEM) studies) having high surface area. The ferrite synthesized from such nanoparticle size -Fe₂O₃ gave a porosity of 25% with grains ranging from 0–3 m. On the other hand, MgFe₂O₄ obtained from commercial alpha-Fe₂O₃ grains (of 1–2 m size) gave particles of 0–6 m with a porosity 42%. Saturation magnetization values 922–1168 G are found for MgFe₂O₄ from -Fe₂O₃ source while the alpha-Fe₂O₃ source gave the lowest value, 609. The Curie temperature, T_c, from magnetic susceptibility, initial permeability and resistivity measurements indicated a highest T_c of 737 K for MgFe₂O₄ from alpha-Fe₂O₃, while lower values are found for the ferrite prepared from -Fe₂O₃.     

Pressureless sintering of Y2O3-CeO2-doped sialons

Various sialon materials have been prepared by pressureless sintering at 1775 and 1825 °C using Y₂O₃ and/or Ce0₂ as sintering aids. Constant molar amounts of the oxide mixtures were added in the ratios Y₂O₃/CeO₂: 100/0, 75/25, 50/50, 25/75, 0/100 corresponding to 6.0 and 9.25 wt% for the pure Y₂O₃ and pure CeO₂, respectively. Only one of the compositional series reached full density at 1775 °C with cerium replacing yttrium, whereas at 1825 °C all compositional series except one became dense. The samples sintered showed that yttrium but not cerium stabilizes the sialon phase in these ceramics. The dense cerium-sialon ceramics sintered at 1825 °C have as good hardness and indentation fracture toughness as the corresponding yttrium-sialon ceramics, or even higher for the sialon type of materials. For the mixed - sialon materials the hardness decreased as the amount of a sialon phase decreased by increasing cerium-doping.     

o′-β′ sialon ceramics

Powders of Si₃N₄, Al₂O₃ and SiO₂ were mixed with Y₂O₃ as sintering aid and hot-pressed to form o- sialon. During sintering, the o phase preferentially precipitated in the temperature region of 1550 to 1600 °C, and the phase precipitated at temperatures of 1700 °C and above. The resultant microstructure consisted of dual phases of o and . The mechanical properties of o- sialon were improved with increasing amount of the phase. When SiO₂ required for the formation of the o phase was all included in the grain boundary phase, o- sialon exhibited a three-point bending strength as much as 1400 MPa. The oxidation resistance of o- sialon is expected to improve due to the presence of the o phase, but actually was not so good due to the presence of the grain-boundary glassy phase and impurities.     

Pressureless sintering of β-SiC with Al2O3 additions

-SiC was pressureless sintered to 98% theoretical density using Al₂O₃ as a liquid-phase forming additive. The reaction between SiC and Al₂O₃ which results in gaseous products, was inhibited by using a pressurized CO gas or, alternatively, a sealed crucible. The densification behaviour and microstructural development of this material are described. The microstructure consists of fine elongated -SiC grains (maximum length 10 m and width 2–3 m) in a matrix of fine equi-axed grains (2–3 m) and plate-like grains (2–5m). The densification behaviour, composition and phases in the sintered product were studied as a function of the sintering parameters and the initial composition. Typically, 50% of the -phase was transformed to the -phase.     

Processing characteristics of PTCR ceramics with low sintering temperature

The processing behavior of PTCR ceramics of (Ba,Sr,Ca,Pb)TiO₃ solid solution composition with additives of lanthanum oxide (La₂O₃) and boron nitride (BN) was studied. The ceramics can be sintered at temperatures as low as 1100 °C and possess rather low room-temperature resistivity with good PTCR effect. The sample ball milled with de-ionized water exhibits a more uniform microstructure compared to the sample ball-milled with alcohol. Particle size of less than 1 m was found to be adequate for preparing the ceramics and the finer particles (0.45 m) do not significantly improve the PTCR behavior. The performance of the PTCR sample is not sensitive to the sintering parameters such as the sintering time and cooling rate. This may be ascribed to the presence of excess BaO in the sample and the low sintering temperature, thereby eliminating the effect of Ba ion vacancies on the properties of the PTCR sample.     

Microstructures and microwave dielectric characteristics of ceramics with the composition BaO·Nd2O3·5TiO2

The microstructures and the microwave dielectric characteristics of BaO·Nd₂O₃·5TiO₂ ceramics were determined as a function of the sintering conditions. The ceramics were confirmed to have a ternary orthorhombic major phase with minor amounts of Nd₂Ti₂O₇ and TiO₂, and nearly equiaxed fine structures and homogeneous columnar structures were obtained at sintering temperatures of 1340 C and 1370 C, respectively, while discontinuous and excess grain growth were observed at sintering temperatures 1350–1360 C and 1380 C, due to the formation of a liquid phase. The desired value of Qf was achieved in ceramics with fine-grained and/or homogeneous microstructures, and the discontinuous and excess grain growth was found to be seriously harmful to the dielectric properties.     

Y xBayCuzO7− δ solid solutions

Y_xBa_yCu_zO_7– ceramics forming at isobaric conditions were studied by x-ray diffraction analysis, dynamic magnetic measurements and potentiometric titration. It was established that compositions: 0.8 x 1.2 y=2, z=3; x-1, 1.8 y 2.2, z=3; x=1, y=2, 2.7 z 3.4: are in the homogeneity range of 123. It was found that compositions with nonstoichiometric cations rations have minimum T_c.     

R-curve behavior of layered silicon carbide ceramics with surface fine microstructure

By adjusting the : SiC phase ratios in the individual starting powders, a layered SiC consisting of surface and inner layers with distinctively different microstructures are produced by hot-pressing and subsequent annealing. The surface layer consisted of relatively fine, equiaxed -SiC grains, designed for high strength, while the inner layer consisted of elongated -SiC grains, designed for high toughness. By virtue of the common SiC phase and the same sintering aids (Al₂O₃-Y₂O₃), the interlayer interfaces are chemically compatible and strongly bonded. R-curve behavior of the layered SiC was measured and compared with the related monolithic materials. The layered SiC showed better damage tolerance than monolithic materials and stronger R-curve behavior than surface layer. This superior performance of layered SiC ceramics was attributed to the contribution of both high strength of the surface layer for small flaws and high toughness of the inner layer for larger flaws.     

Effects of aluminium on the electrical and mechanical properties of PTCR BaTiO3 ceramics as a function of the sintering temperature

The effect of AI additions on the electrical behaviour of positive temperature coefficient of resistance (PTCR) BaTiO₃ ceramic sintered in air at temperatures ranging between 1220 and 1400° C have been investigated. Two batches of material, both showing a PTCR effect, were prepared identically except that additions of AI₂O₃ (0.55 mol %) were made to one of them. It has been confirmed that the presence of aluminium results in an increase in the temperature at which the maximum resistivity, _max, occurs as well as reducing the sintering temperature, in the presence of silicon, to 1240° C. Additionally, direct comparisons between the two materials have demonstrated that such additions result in an increase of 100% in the minimum resistivity, _min, at sintering temperatures beyond 1280° C. A similar increase in _max for sintering temperatures below 1360° C and a five-fold reduction in the ratio of _max/_min in samples sintered above 1320° C have also been attributed to the presence of aluminium. It was further found that aluminium increases the average grain size by 30% and promotes the formation of a liquid phase.     

Sintering of strontium titanate in the presence of lithium salts in a reducing atmosphere

The possibility of preparing Type III ceramics for multilayer applications has been investigated in the strontium-titanium-oxygen system, using La₂O₃, Nd₂O₃and La_2/3TiO_3– as dopants and lithium salts as sintering agents. The introduction of bismuth was also explored. The sintering process is carried out by adding the lithium salts to mixtures of strontium titanate and dopants which are previously calcined in a reducing atmosphere. The dielectric properties and the microstructure of the ceramics have been studied. The best characteristics have been observed for the particular nominal composition SrTiO₃+0.75 mol% La_2/3Ti_3–+3 mol% Bi₂O₃+10 mol % LiNO₃leading to =20000, tan < 2%,R _i= 10¹¹ cm. These results are interpreted in terms of the formation of anionic vacancies and defects in the A sites of the perovskite ABO₃and of extended defects SrO and Bi₂O ₂ ²⁺ which are coherent with the perovskite matrix.     

The formation of NaMg2Al15O25 in an α-Al2O3 matrix and its effect on the mechanical properties of alumina

An in-situ sintering reaction was designed to produce lath-like \-alumina in an -alumina matrix in order to make alumina ceramics stronger and tougher. The reaction sequence to produce \-alumina (NaMg₂Al₁₅O₂₅) requires the formation of \-alumina (NaAl₁₁O₁₇) and spinel (MgAl₂O₄) at around 1100 dgC followed by a solid-state reaction of these two phases to give \-alumina at elevated temperatures; this reaction is complete at around 1600 °C. The in-situ sintering reaction produces near-theoretically dense alumina ceramics in which lath-like \-aluminas are homogeneously distributed. The bending strength and fracture toughness increase to 620 MPa and 5 MPam^1/2, respectively; these increases are thought to be due to the suppression of grain growth as well as the crack deflection and bridging associated with lath-like \-alumina.     

Synthesis, crystal structure and X-ray powder diffraction data of the phosphor matrix 4SrO·7Al2O3

The white phosphor matrix 4SrO·7Al₂O₃ has been synthesized by firing the appropriate mixture of SrCO₃, Al(OH)₃ and H₃BO₃ in the molar ratios 1:3.5:0.135 at 1300°C for 4–7 h. The crystal structure of 4SrO·7Al₂O₃ has been determined as a orthorhombic Pmma space group with a=24.7451(2)Å, b=8.4735(6)Å, c=4.8808(1)Å, V=1023.41(3)ų, Z=2, and D=3.66 g cm^–3 by the Rietveld analysis. The refinement figures of merit are R_p=8.26, R_wp=11.60, R_bragg=4.44 and s=2.61 for 844 reflections with 2<119.94°. And the corresponding X-ray powder diffraction data are presented for search/match analysis.     

Study on the dielectric properties of oxide-doped Ba(Ti,Sn)O3 ceramics prepared from ultrafine powder

Ultrafine BaTiO₃ and BaSnO₃ powders were prepared by thermal decomposition of oxalates through synthesis by the method of co-precipitation; Dy₂O₃, Nb₂O₅ and ZnO, used as dopants, were added to the main constituents, known as the tailor-made Ba(Ti, Sn)O₃, according to the indicated compositions, then the batches were mixed until they became homogeneous. Careful treatment was necessary in later stages of the process of ceramic making. The dielectric properties of the ceramics were measured. It was found that high , low tan and low d/dt were characteristics of these ceramics. The results could be explained by the effects of peak shifting, broadening and grain-size inhibition. The relationship between composition, structure and properties is discussed.     

Phase transformation and microstructural changes of Si3N4 during sintering

Changes of density, the - phase transformation, and composition of grains and grain boundaries during sintering of Si₃N₄ with various sintering conditions using additives of Y₂O₃ and Al₂O₃ were investigated. The phase determination of individual Si₃N₄ grains was performed by convergent beam electron diffraction. The relations between densification and transformation were divided into two groups, depending on the additive compositions. Aluminium dissolution into Si₃N₄ grains occurred mostly during - transformation process. The concentrations of aluminium and oxygen in the grain boundaries decreased as the - transformation progressed.     

Preparation of superconducting Bi-Sr-Ca-Cu-O ceramics by the sol-gel method

Superconducting Bi-(Pb)-Sr-Ca-Cu-O ceramics were prepared through the sol-gel method using an aqueous solution of metal acetates containing acetic acid and tartaric acid. The conditions of gelation and conversion of gel to Bi₂Sr₂CaCu₂O_x phase were studied by thermal analysis, infrared absorption spectroscopy and X-ray diffraction technique. It was found that transparent gels were obtained from the solutions containing tartaric acid, with a molar ratio of C₄H₆O₆/Cu of about 0.4. The gel matrix was assumed to be composed of carboxylate anions and metal cations. A gel of molar composition BiSrCaCu = 2223 was decomposed to CaCO₃, CaO, CuO and Bi_1-x Sr_xO_y (x = 0.2 to 0.3) at low temperatures of 270 to 600 ° C and produced Bi₂Sr₂CaCu₂O_x phase at 800 ° C via complex intermediate states. A rapid cooling of the heated product increasedT _c (end) in the gel of molar composition BiSrCaCu = 2223, while a slow cooling increasedT _c (end) in the lead-containing gel of molar composition BiPbSrCaCu = 1.850.351.92.03.1. The latter showedT _c (onset) at 115 K andT _c (end) at 105K.