Microstructural and densification study of natural Indian magnesite in presence of zirconia additive

The sintering and microstructural evaluation of Indian magnesite was carried out in presence of zirconia. Zirconia in monoclinic form was added in the range 3–6 wt% with respect to raw magnesite and the sintering temperature selected were 1500–1600°C for 2 h. The main impurities present in the magnesite were Fe₂O₃, CaO, SiO₂. The natural crystalline magnesite could be sintered with bulk density of 3.38 g/cc (A.P. 1.54%) at 1550°C/2 h. But the higher bulk density (3.50 g/cc) and minimum apparent porosity (A.P. 0.25%) was attained at 1550°C/2 h with the 3 wt% zirconia additive. On firing magnesite with zirconia as additive, a crystalline phase, magnesio-zirconate, was identified at the triple point regions of the direct bonded periclase grains. The morphology of the periclase grains were changed from subrounded/rounded to angular shaped in presence of zirconia as additive.     

3D printing of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Cu–O interpenetrating phase composite

Porous alumina preforms were fabricated by indirect 3D printing using a blend of alumina and dextrin as a precursor material. The bimodal granulate powder distribution with a bed density of 0.8 g/cm³ was increased to 1.4 g/cm³ by overprinting. The porosity of the sintered bodies was controlled by adjusting the printing liquid to precursor powder ratio in the range of 33–44 vol%. The green bodies exhibited bending strengths between 4 and 55 MPa. An isotropic linear shrinkage of ~17% was obtained due to dextrin decomposition and Al₂O₃ sintering at 1600 °C. Post-pressureless infiltration of the sintered preforms with a Cu–O alloy at 1300 °C for 1.5 h led to the formation of a dense Al₂O₃/Cu–O interpenetrating phase composite (IPC). X-ray analysis of the fabricated composites showed the presence of α-Al₂O₃, Cu and Cu₂O. CuAl₂O₄ spinel was not observed at the grain boundaries during HRTEM examination. The Al₂O₃/Cu–O interpenetrating phase composite revealed a fracture toughness of 5.5 ± 0.3 MPam^1/2 and a bending strength of 236 ± 32 MPa. In order to demonstrate technological capability of this approach, complex-shaped bodies were fabricated.     

Sintering and technological properties of alumina/zirconia/nano-TiO2 ceramic composites

The present work focuses on studying the effect of nano TiO₂ (0.0–25 mass%) on the sintering behavior and mechanical properties of alumina/zirconia ceramic composites. Al₂O₃–ZrO₂–TiO₂ oxides mixture was sintered at 1600 °C to obtain the desired composites. The sinterability and the technological properties of these ceramic composites, i.e. the sintering parameters and microhardness as well as thermal shock resistance were investigated. Moreover, phase composition and microstructure of the sintered bodies were examined using X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The results revealed that nano TiO₂ is a beneficial component for alumina/zirconia ceramic composites. The batch containing 20 mass% TiO₂ exhibited the highest sintering and mechanical properties as well as resistance to thermal shock. The obtained microstructure exhibited high compacted ceramic matrix composites.     

Phase formation and texture development in mullite/zirconia composites fabricated by templated grain growth

Mullite is a promising candidate for advanced ceramic applications but its low fracture toughness and difficulties in sintering are the main limitations for more widespread industrial applications. Therefore, mullite/zirconia composites were prepared from a reactive mixture of alumina and zircon powders. Additives, TiO₂ and MgO, were used to modify aluminosilicate glass to increase densification and <001> aluminum borate templates were incorporated to texture mullite in [001] by templated grain growth. Mullite/zirconia phase formation was complete at 1450°C in the presence of both templates and additives, as compared to 1500°C for the samples with only additives and to 1600°C for the samples with only templates. Dense mullite/zirconia composites with highly <001>-textured mullite grains (Lotgering factor ∼1) and a retention of ∼13% tetragonal ZrO₂ were fabricated after sintering at 1450°C for 2 h. A high quality of mullite texture with a degree of orientation parameter of 0.22 and a narrow distribution of elongated mullite grains within 8.8° around [001] were successfully obtained in the composites.     

Densification and dielectric properties of SrO–Al2O3–B2O3 ceramic bodies

The influence of SrO (0·0–5·0 wt%) on partial substitution of alpha alumina (corundum) in ceramic composition (95 Al₂O₃–5B₂O₃) have been studied by co-precipitated process and their phase composition, microstructure, microchemistry and microwave dielectric properties were studied. Phase composition was revealed by XRD, while microstructure and microchemistry were investigated by electron-probe microanalysis (EPMA). The dielectric properties by means of dielectric constant (ε _r ), quality factor (Q × f) and temperature coefficient of resonant frequency (τ _f ) were measured in the microwave frequency region using a network analyser by the resonance method. The addition of B₂O₃ and SrO significantly reduced the sintering temperature of alumina ceramic bodies to 1600 °C with optimum density (∼ 4g/cm³) as compared with pure alumina powders recycled from Al dross (3·55g/cm³ sintered at 1700 °C).     

MgAl2O4-γ-Al2O3 solid solution interaction: mathematical framework and phase separation of α-Al2O3 at high temperature

Although existence of MgAl₂O₄-γ-Al₂O₃ solid solution has been reported in the past, the detailed interactions have not been explored completely. For the first time, we report here a mathematical framework for the detailed solid solution interactions of γ-Al₂O₃ in MgAl₂O₄ (spinel). To investigate the solid solubility of γ-Al₂O₃ in MgAl₂O₄, Mg-Al spinel (MgO-nAl₂O₃; n = 1, 1.5, 3, 4.5 and an arbitrary high value 30) precursors have been heat treated at 1000°C. Presence of only non-stoichiometric MgAl₂O₄ phase up to n = 4.5 at 1000°C indicates that alumina (as γ-Al₂O₃) present beyond stoichiometry gets completely accommodated in MgAl₂O₄ in the form of solid solution. γ → α alumina phase transformation and its subsequent separation from MgAl₂O₄ has been observed in the Mg-Al spinel powders (n > 1) when the 1000°C heat treated materials are calcined at 1200°C. In the mathematical framework, unit cell of MgAl₂O₄ (Mg₈Al₁₆O₃₂) has been considered for the solid solution interactions (substitution of Mg²⁺ ions by Al³⁺ ions) with γ-Al₂O₃. It is suggested that combination of unit cells of MgAl₂O₄ takes part in the interactions when n > 5 (MgO-nAl₂O₃).     

The preparation and characterization of SiC-AlN-Fe2Si composites with high porosity from allophane

The reaction products of an allophane heated with carbon at 850–1600 °C in the stream of nitrogen for a given time were characterized by X-ray diffractometry. As a result, it was found that cristobalite and mullite were stable phases at 850–1300 °C, β-Si₃N₄ and α-Al₂O₃ at 1300–1500 °C, and SiC-AlN-Fe₂Si at temperatures higher than 1500 °C. SiC-AlN-Fe₂Si composites with high porosity of about 50% were easily prepared by a heat treatment at a temperature higher than 1500 °C with carbon in a stream of nitrogen. The formation mechanism of the composites is kinetically discussed from a viewpoint of small-pore shrinkage and large-pore expansion by volume diffusion during heating. The resultant microstructure of the composites obtained is also discussed.     

Effect of powder treatment on the crystallization behaviour and phase evolution of Al2O3–High ZrO2 nanocomposites

Al₂O₃–ZrO₂ composites containing nominally equal volume fraction of Al₂O₃ and ZrO₂ have been synthesized through combined gel-precipitation technique. Subsequently the gels were subjected to three different post gel processing treatments like ultrasonication, ultrasonication followed by water washing and ultrasonication followed by alcohol washing. It was observed that while in unwashed samples crystallization took place at low temperature, crystallization was delayed in the washed gels. The phase transition of ZrO₂ in the calcined gels followed the sequence; amorphous → cubic ZrO₂ → tetragonal ZrO₂ → monoclinic ZrO₂. On the other hand, phase transition in alumina followed the sequence amorphous to γ-Al₂O₃, the transition taking place at 650 °C. No α-Al₂O₃ could be detected even after calcination at 950 °C. However, all the sintered samples had α-Al₂O₃. In spite of high linear shrinkage (19–21%) during sintering, the sintered sample had density of only above 70% for all the four varieties of the powders. However, in spite of the low sintered density of the pellets, 31% tetragonal zirconia could be retained after sintering at 1400 °C and it reduced to about 16% at 1600 °C.     

Enhancement of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel formation from coprecipitated precursor by powder processing

Although low temperature fast coprecipitation technique has been used to synthesize stoichiometric (MgO-nAl₂O₃, n = 1) MgAl₂O₄ spinel forming precursor, delayed spinellization has always been the concern in this process. In this article, the precursor of this ‘fast technique’ has been used for bulk production by further processing by high speed mixing with solvents and mechanical activation by attrition milling in terms of superior spinellization. At 1000°C, MgAl₂O₄ — γ-Al₂O₃ solid solution and MgO phases are formed (spinel formed by 1000°C is regarded as primary spinel). At higher temperatures, due to large agglomerate size, MgO can not properly interact with the exsolved α-Al₂O₃ from spinel solid solution to form secondary spinel; and consequently spinellization gets affected. Solvent treatment and attrition milling of the coprecipitated precursor disintegrate the larger agglomerates into smaller size (effect is more in attrition). Then MgO comes in proper contact with exsolved alumina, and therefore total spinel formation (primary + secondary) is enhanced. Extent of spinellization, for processed calcined samples where some alumina exists as solid solution with spinel, can be determined from the percentage conversion of MgO. Analysis of the processed powders suggests that the 4 h attrited precursor is most effective in terms of nano size (< 25 nm) stoichiometric spinel crystallite formation at ≤ 1100°C.     

Sol-gel synthesis of alumina,titania and mixed alumina/titania in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulphonyl) amide

In this paper we report on the synthesis of alumina, titania and mixed alumina–titania in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulphonyl) amide [Py_1,4]TFSA via sol-gel methods using aluminium isopropoxide and titanium isopropoxide as precursors. Our results show that the as-synthesized alumina is mainly mesoporous boehmite with an average pore diameter of 3.8 nm. The obtained boehmite is subject to a phase transformation into γ-Al₂O₃ and δ-Al₂O₃ after calcinations at 800 and 1,000 °C, respectively. The as-synthesized TiO₂ shows amorphous behaviour and calcination at 400 °C yields anatase which undergoes a further transformation to rutile at 800 °C. The as-prepared alumina–titania powders are amorphous and transformed to rutile and α-Al₂O₃ after calcination at 1,000 °C TiO₂. The obtained alumina–titania has a higher surface area than those of alumina or titania. The surface area of the as-synthesized alumina–titania was found to exceed 486 m² g⁻¹, whereas the surface areas of the as-synthesized boehmite and titania were around 100 m² g⁻¹, respectively.     

Templated grain growth of textured mullite/zirconia composites

Mullite is an attractive material for advanced ceramic applications, but its low fracture toughness prevents it from widespread industrial applications. Therefore, mullite/zirconia composites were prepared from a reactive mixture of alumina and zircon with additives of TiO₂ and MgO to increase mechanical properties and densification. <001> aluminum borate templates were used to nucleate, and texture mullite in [001]. Mullite/zirconia formation started at 1350 °C and was complete at 1450 °C. Dense mullite/zirconia composites with highly textured mullite were produced after sintering at 1450 °C. A relatively constant tetragonal ZrO₂ content of 11±2 wt.% was retained at room temperature after sintering between 1350 and 1550 °C. A high quality of texture with an orientation parameter of 0.22 and a very narrow distribution of elongated mullite grains within 8.8° around [001] were successfully produced.     

TEM analysis of the growth of oxide scales at different temperatures in FeAl grade 3 intermetallic alloy

Abstract

Upon the isothermal oxidation of an ODS FeAl Grade 3 intermetallic alloy, a structured oxide scale is developed between 800 and 950°C. TEM studies have revealed a three-layered structure with a top nanoequiaxed alumina, a central alumina and a bottom Fe-Al spinel. At these temperatures, aluminium outward diffusion does not seem to be suppressed neither by the spinel sub-layer nor by the yttria present in the superalloy. However, the formation of metastable θ-Al₂O₃ seems to be significantly hindered. On the contrary, at 1000°C, the spinel phase no longer forms but a columnar alumina layer topped up with a nanoequiaxed structure. Yttria seems then to segregate at the scale/alloy interface and to randomly coarsen to produce an Y-Al oxide phase.     

Mechanical properties and toughening mechanism of WC-doped ZrB2–ZrSi2 ceramic composites by hot pressing

WC-doped ZrB₂–ZrSi₂ ceramic composites were fabricated by hot pressing at temperatures ranging from 1450 °C to 1550 °C. The influence of ZrSi₂ content on the mechanical properties of the composites was investigated by means of three point bending test and single edge notched-beam test, respectively. The microstructure and phase composition were characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD) analysis. The results revealed that: (i) the highest relative density was 99.5% for the composite fabricated at 1550 °C; (ii) the doping of WC refined the grain size and led to an anisotropic grain growth which was evidenced by the occurrence of elongated grains; (iii) the highest strength and fracture toughness were 585 MPa and 6.87 MPa m^1/2, respectively; (iv) the main toughening mechanism was considered as the pull out of elongated grains and the deflection of cracks.     

Sol–gel derived CaO–B2O3–SiO2 glass/CaSiO3 ceramic composites: processing and electrical properties

The CaO–B₂O₃–SiO₂ glass/CaSiO₃ ceramic (CBS/CS) composites were fabricated via sol–gel processing routes. Their densification behavior, structures and dielectric properties were investigated. The precursors of CBS glass and CS ceramic filler were firstly obtained via individual soft chemical route and then mixed together in various proportions. The results indicated that the structures of CBS/CS composites are characteristic of CS and CaB₂O₄ (CB) ceramic phases distributed in the matrix of glass phase at 800–950 °C. The CS ceramic phase not only acts as fillers, but nuclei for the crystallization of CBS glass as well such that the CS content exhibits an effect on the densification and dielectric properties of the composites. The CBS/CS composites with 10% CS sintered at 850 °C own dielectric properties of ε_r < 5 and tanδ = 6.4 × 10⁻⁴ at 1 MHz.     

A study of phase stability and mechanical properties of hydroxylapatite–nanosize α-alumina composites

Hydroxylapatite (HA)–nanosize alumina composites were synthesized to study their phase stability and mechanical properties. To make these composites, nanosize α-Al₂O₃ powder was used because of its better sinterability and densification as compared to nanosize γ-Al₂O₃. The composites were air sintered without pressure and hot pressed in vacuum at 1100 °C and 1200 °C. In the composites, HA decomposed to tri-calcium phosphate faster after the air sintering than hot pressing. Moreover, hexagonal unit cell volume of HA left in the composites showed that there was more decomposition of HA after the air sintering than hot pressing. It also showed that HA in the composites was OH⁻ and Ca²⁺ deficient. As the amount of alumina increased, sinterability considerably decreased. Hot pressing at 1200 °C resulted in better mechanical properties (μ-hardness and fracture toughness) than the hot pressing at 1100 °C.     

Phase stability,microstructure and high-temperature properties of NbSi<Subscript>2</Subscript>- and TaSi<Subscript>2</Subscript>-oxide conducting ceramic composites

NbSi₂- and TaSi₂-based electroconductive ceramic composites with the addition of 40–70 vol% Al₂O₃ and ZrO₂ particles were fabricated by high-temperature sintering (1400–1600 °C) under argon. Their phase stability, microstructural evolution, oxidation kinetics and electrical properties were studied at high temperatures. The densification of the composites was improved by increasing the oxide phase content and sintering temperature. The interaction of the starting metal disilicides with residual oxygen sources resulted in the formation of the hexagonal-structured 5–3 metal silicide (Nb₅Si₃ and Ta₅Si₃) phases. The increasing sintering temperature and volume percentage of the oxide phase reduced the pest oxidation, particularly for the silicide–alumina composites, which exhibited lower oxidation-induced mass changes than their dense monolithic metal silicides. Depending on the silicide–oxide volume percentage, their electrical conductivities ranged from 5.3 to 111.3 S/cm at 900 °C. Their phase stability, reduced oxidation rates and high electrical conductivities at high temperatures show promise for future high-temperature applications in advanced sensing.     

Calcia–alumina fibre-reinforced Al 7075 alloy composites produced by melt-infiltration: Interfacial wetting and reaction

Inviscid melt-spun calcia–alumina (CA) fibre-reinforced aluminium 7075 alloy matrix composites were produced at 700 and 927°C by using a melt-infiltration method. Interfacial wetting and chemical reaction of the composites were investigated by using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD). The composites processed at 700°C showed interfacial wetting and magnesium accumulation at the interfacial region. The composites processed at 927°C showed the formation of a 15 μm thick interphase region as well as excellent interfacial wetting. EDS analysis gave averaged compositions of this interface region at 63.5 at% Al and 31.5 at% Mg, which corresponds to the composition of spinel, MgAl2O4. The formation of spinel at the interface was confirmed by XRD analysis on the CA fibres separated from the composites. This revised version was published online in November 2006 with corrections to the Cover Date.     

Mechanical properties and oxidation behaviors of carbon/carbon composites with C–TaC–C multi-interlayer

To improve the mechanical properties and oxidation-resistance properties, a C–TaC–C multi-interlayer structure was introduced in carbon/carbon (C/C) composites by chemical vapor infiltration. Compared with conventional C/C composites, a higher fracture toughness and strength have been achieved by using the C–TaC–C multi-interlayer. In addition, the composites also exhibit a higher preliminary oxidation temperature and a lower mass loss at high temperatures. The oxidation rate of the composites increases with temperature increasing in the range of 700–1300 °C, reaching a maximum value at 1300 °C, then decreases in 1300–1400 °C. A hexagonal structure of Ta₂O₅ phase is obtained when being oxidized at 700–800 °C, and it transforms to an orthorhombic phase at temperatures above 900 °C. The structures of C–TaC–C multi-interlayer are intact without cracks or porosities after being oxidized at 700–800 °C. In 900–1300 °C, the composites are oxidized uniformly with the formation of pores. At temperatures above 1300 °C, there are oxidation and non-oxidation regions with the oxidation process being controlled by diffusion.     

Porous alumina ceramics prepared by slurry infiltration of expanded polystyrene beads

To produce highly porous MgO-doped alumina (Al₂O₃) ceramics, expanded polystyrene (EPS) beads were packed as a pore former and well-dispersed alumina slurry was used to infiltrate the pore space in the EPS bead compacts. The alumina particle-EPS bead green compacts were then heated to 1550°C in air to burn out the pore former and subsequently densify the MgO-doped alumina struts. The porous Al₂O₃ ceramics were featured with uniformly distributed open pore structures with porosities ranging from 72 to 78% and a pore interconnectivity of about 96%. The macropore size and the pore window size could be controlled by adjusting the size of the EPS beads and the contacting area between the EPS beads. The compressive strengths of the porous Al₂O₃ ceramics were in the range of 5.5–7.5 MPa, similar to those of cancellous bones (2–12 MPa). The porous alumina ceramics were further made bioactive after the dip coating of a sol-gel derived 58 S bioglass powder, followed by sintering at 1200°C.     

Si-incorporated alumina phases formed out of diphasic mullite gels

The diphasic mullite gel forms o-mullite on heating via intermediate spinel phase. Characterization of the latter phase with various physico-chemical techniques is concisely reviewed. It is noticeable that XRD intensity of both the amorphous scattering band and the diffraction peak of Al–Si spinel phase changes during each step of transformation processes of diphasic gel. Accordingly, the integrated area of the intensity peak of amorphous band and that of Al–Si spinel phase generated during heating diphasic gels were measured by XRD technique with the help of X’Pert Graphics and Profit softwares. The amount of free SiO₂ (A) content present at various stages of heating diphasic gels was estimated by classical alkali leaching study standardized earlier. The results show that diphasic gel which forms an aluminosilicate (A) phase initially by dehydration and dehydroxylation, subsequently crystallizes to Al–Si spinel phase. In consequence, the ratio of XRD peak of spinal phase to that of amorphous band increases in the temperature range of 600–1000 °C. This study confirms the earlier view of incorporation of silica into the alumina structure with formation of Al–Si spinal phase. Complementary alkali leaching study indicates the existence of non-crystalline silica-rich aluminous phase other than free non-crystalline silica during heating diphasic gel at ~1000 °C.

---