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.     

Nanostructured Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> composite synthesized by sol–gel technique: powder processing and microstructure

Al₂O₃–ZrO₂ composite gel powder was prepared by sol–gel route. The gel precursor compositions were preferred to achieve yield of 5–15 mol% zirconia after calcination of respective powders. The precursor gel was characterized by Differential Thermal Analysis (DTA)/Thermo Gravimetric (TG), IR and X-ray Diffraction study (XRD). The analysis reveal the gel contained pseudoboehmite and amorphous Zr(OH)₄, which was decomposed in three and two stages respectively. The phase transformation of alumina during calcination followed the sequence of pseudoboehmite → bayerite → boehmite → γ-Al₂O₃ → θ-Al₂O₃ → α-Al₂O₃, while that of ZrO₂ follows amorphous ZrO₂ → t-ZrO₂ → (t + m) ZrO₂. Fourier Transform Infrared Spectroscopy (FTIR) studies showed that the number of M–OH and M–O bond increases with zirconia due to a change in the cationic charge of the composite powder. Transmission Electron Microscopy (TEM) photograph of calcined powder exhibited the presence of dispersed as well as agglomerated nano sized spherical particles. SEM and Electron Probe Microscope Analysis (EPMA) confirmed the near uniform distribution of zirconia particles in the alumina matrix.     

Preparation and characterization of alumina–iron cermets by hot-pressing of nanocomposite powders

Alumina composites with 0–36 vol% iron metal dispersed inclusions have been prepared by a new processing route. Nanostructured powders were synthesized by a high energy dry ball-milling process and then consolidated by sintering at 1700 K under a pressure of 30 MPa. The materials consist of micrometre-size Al₂O₃ with metallic Fe in isolated regions from 10 μm down to nanometre size. From low to high metallic contents, the same type of interwoven microstructure is observed. Hardness, elastic and shear moduli, fracture toughness and the size of the inclusions vary regularly with the metal content. Addition of metal increased the fracture toughness from 3.0 to 8 MPa m^1/2. This revised version was published online in November 2006 with corrections to the Cover Date.     

Fracture toughness of alumina/lanthanum titanate laminate composites with a weak interface

Layers of lanthanum titanate (La₂Ti₂O₇) and α-alumina (α-Al₂O₃) were employed to form a layered composite in order to improve the fracture toughness of monolithic alumina. The composites were produced by two different processing methods. In the first, individually presintered pellets of α-Al₂O₃ and La₂Ti₂O₇ were stacked together and hot-forged. In the second, tape cast molten salt La₂Ti₂O₇ and dense α-Al₂O₃ were stacked together and hot-forged. The forged composite samples were investigated by optical microscopy, scanning electron microscopy (SEM), Vickers indentation and three-point bending. During the hot-forging process, an interphase, aluminum titanate (Al₂TiO₅) was found to form as a result of the reaction between α-Al₂O₃ and La₂Ti₂O₇. The flexural strength and the fracture toughness of the resulting laminate composites were found to be 320 MPa and 7.1 MPa m^1 / 2, respectively. Indentation experiments showed that the newly formed Al₂TiO₅ at the interface is sufficiently weak to promote crack deflection and hence increase the fracture energy and mechanical properties of the composite.     

Fracture toughness,strength and Vickers hardness of yttria-ceria-doped tetragonal zirconia/alumina composites fabricated by hot isostatic pressing

Yttria-ceria-doped tetragonal zirconia ((Y, Ce)-TZP)/alumina (Al₂O₃) composites were fabricated by hot isostatic pressing (HIP) at 1400–1600 °C and 147 MPa for 30 min in Ar gas using fine powders prepared by hydrolysis of ZrOCl₂ solution. The mechanical properties of these ceramic composites were evaluated. The fracture toughness and bending strength of the composites consisting of 25 wt% Al₂O₃ and tetragonal zirconia with compositions 4 mol% YO_1.5-4 mol% CeO₂-ZrO₂, 2.5 mol% YO_1.5-4 mol% CeO₂-ZrO₂ and 2.5 mol% YO_1.5-5.5 mol% CeO₂-ZrO₂ fabricated by HIP at 1400 °C were 6–7 MPa m^1/2 and 1700–1800 MPa. Fracture toughness, strength and hardness of (Y, Ce)-TZP/Al₂O₃ composites were strongly dependent on HIP temperature. The fracture strength and hardness were increased, and grain growth of zirconia grains and phase transformation from the tetragonal to the monoclinic structure of (Y, Ce)-TZP during HIP in Ar at high temperature (1600 °C) were suppressed by the dispersion of Al₂O₃ into (Y, Ce)-TZP.     

Internal friction,crack length of fracture origin and fracture surface energy in alumina-zirconia composites

Two series of alumina-zirconia composites, i.e. alumina-unstabilized zirconia and alumina-partially stabilized zirconia with 3 mol % Y₂O₃, with different zirconia content were slip casted and fired at 1550°C for 3 h. Elastic constant, bending strength and fracture toughness were measured. Internal friction was determined to follow the formation of cracks, nondestructively, which could be one of the fracture origins. The crack length of the fracture origin and the fracture surface energy were calculated by applying Griffith's fracture theory. Microstructures of the fracture surfaces were observed using a scanning electron microscope. For the unstabilized zirconia system, the increase in the internal friction of the order from 10⁻⁴ to 10⁻³ was a guide to find the formation of cracks which lead to the fracture. The increase in the cracks becoming a fracture origin lead to the increase inK _lc and also to the apparent increase in the fracture surface energy. For the partially stabilized zirconia system, the increase in the fracture surface energy with an increase in zirconia content, keeping low internal frictions of the order of 10⁻⁴, indicates the intrinsic strengthening of the grain boundaries in comparison to the unstabilized zirconia system. Internal friction is the most suitable nondestructive physical quantity to find the microcracks which leads to the fracture.     

Reaction sintering fabrication of (AlN, TiN)-Al2O3 composite

The (AlN, TiN)-Al₂O₃ composites were fabricated by reaction sintering powder mixtures containing 10-30 wt.% (Al, Ti)-Al₂O₃ at 1420-1520°C in nitrogen. It was found that the densification and mechanical properties of the sintered composites depended strongly on the Al, Ti contents of the starting powder and hot pressing parameters. Reaction sintering 20 wt.% (Al, Ti)-Al₂O₃ powder in nitrogen in 1520°C for 30 min yields (AlN, TiN)-Al₂O₃ composites with the best mechanical properties, with a hardness HRA of 94.1, bending strength of 687 MPa, and fracture toughness of 6.5 MPa m^1/2. Microstructure analysis indicated that TiN is present as well dispersed particulates within a matrix of Al₂O₃. The AlN identified by XRD was not directly observed, but probably resides at the Al₂O₃ grain boundary. The fracture mode of these composites was observed to be transgranular.     

Effect of CeO2 on reaction-sintered mullite-ZrO2 ceramics

The effect of ceria on mullite formation and the sintering of zircon and alumina powders was investigated. Quantitative X-ray powder analysis was used to determine the formation of mullite and zirconia of both monoclinic and tetragonal forms. Scanning electron microscopy and electron-probe microanalysis were used for microstructural analysis. It was found that the addition of CeO₂ enhanced the formation of mullite and increased the fraction of tetragonal zirconia. The addition of CeO₂ caused the formation of mullite directly from reaction of zircon with alumina without decomposition of zircon into zirconia and silica. In addition to forming a liquid phase, the ceria essentially formed a solid solution with zirconia. The fracture toughness of the mullite-zirconia composites was about 5.5–6.0 MPa m^1/2.     

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.     

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).     

Thermal stability of transition phases in zirconia-doped alumina

Alumina was prepared from an aqueous salt solution by homogeneous precipitation followed by calcination in air. Dependence of the thermal stability of transition phases on the presence of a zirconia dopant and on autoclave treatment prior to calcination was investigated using X-ray diffraction (XRD), differential thermal analysis coupled with thermogravimetric analysis (DTA–TGA) and transmission electron microscope (TEM) analysis. Homogeneous precipitation produced an amorphous trihydrate precipitate; the autoclave treatment converted this to crystalline boehmite (monohydrate). The zirconia was soluble in the transition alumina but was insoluble in α-Al₂O₃ so that phase transformation to α-Al₂O₃ was accompanied by a phase separation to form an alumina-zirconia nanocomposite. The thermal stability of the transition phases was increased both by the dopant and by the autoclave treatment. A combination of both parameters yielded the most stable transition alumina, which withstood 1 h at 1200°C without transformation to α-Al₂O₃. This revised version was published online in November 2006 with corrections to the Cover Date.     

DeNO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> activity of Ag/γ–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposites prepared via the solvothermal route

Ag/γ–Al₂O₃ with silver loading of 3 wt.% were prepared by the solvothermal-calcination reaction of AgNO₃ in mixed water-alcohol solutions at 50–250 °C for 0–120 min, followed by calcinations at 550 °C for 2 h using γ-Al₂O₃ (SSA: 120–409 m² g⁻¹), γ-AlOOH (SSA: 270 m² g⁻¹), Al(OH)₃ (SSA 10 m² g⁻¹), Al(OCH(CH₃)₂)₃ and Al(NO₃)₃ as an aluminum source. The resultant product produced by the solvothermal reaction was Ag/γ–AlOOH even though a different aluminum source was used and Ag/γ–AlOOH was converted to Ag/γ–Al₂O₃ by the following calcinations. However, the characteristics of them changed greatly depending on the alumina source. The deNO _x catalytic performance of Ag/γ–Al₂O₃ also greatly changed depending on the aluminum precursor and solvothermal solvent in the order γ-AlOOH = γ-Al₂O₃ >> Al(OCH(CH₃)₂)₃ >> Al(NO₃)₃ > Al(OH)₃ and methanol = ethanol > 1-propanol > butanol >> hexanol, since the amount and size of silver particle impregnated and specific surface area of the product changed markedly. Ag/γ–Al₂O₃ prepared by solvothermal-calcination method consisted of homogeneously dispersed fine particles of silver and showed better performance for NO _x decomposition than that by conventional impregnation-calcination method.     

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.     

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.     

Fabrication and mechanical behaviour of Al2O3/Mo nanocomposites

Two types of Al₂O₃/Mo composites were fabricated by hot-pressing a mixture of - or -Al₂O₃ powder and a fine molybdenum powder. For Al₂O₃/5 vol% Mo composite using -Al₂O₃ as a starting powder, the elongated molybdenum layers were observed to surround a part of the Al₂O₃ grains, which resulted in an apparent high value of fracture toughness (7.1 Mpa m^1/2). In the system using -Al₂O₃ as a starting powder, nanometre sized molybdenum particles were dispersed within the Al₂O₃ grains and at the grain boundaries. Thus, it was confirmed that ceramic/metal nanocomposite was successfully fabricated in the Al₂O₃/Mo composite system. With increasing molybdenum content, the elongated molybdenum particles were formed at Al₂O₃ grain boundaries. Considerable improvements of mechanical properties were observed, such as hardness of 19.2 GPa, fracture strength of 884 MPa and toughness of 7.6 MPa m^1/2 in the composites containing 5, 7.5, 20 vol% Mo, respectively; however, they were not enhanced simultaneously. The relationships between microstructure and mechanical properties are also discussed.     

Preparation of zirconia-toughened bioactive glass-ceramics

Bioactive glass-ceramics toughened by tetragonal zirconia polycrystal (TZP) were prepared by hot-pressing mixed powders of the MgO-CaO-P₂O₅-SiO₂ glass and TZP containing 20 to 80% alumina. The bending strength and the fracture toughness of the composite materials were improved compared with those of the material without TZP. These composites showed high bending strengths (400 to 500MPa) and high fracture toughness ( 2.8MPa m^1/2). The existence of a crack deflection mechanism was observed by scanning electron microscopy. After soaking in simulated physiological solution at 100 °C, no phase transformation from tetragonal to monoclinic of TZP in the composites and no degradation in bending strength occurred.     

Mechanical properties of (Y-TZP) — alumina-silicon carbide nanocomposites and the phase stability of Y-TZP particles in it

Al₂O₃-SiC-ZrO₂ composites were investigated to obtain a better understanding of the effect of SiC particles and the stress-induced transformation of Y-TZP on its mechanical properties. The Al₂O₃-SiC-ZrO₂ composites were fabricated by hot pressing using -Al₂O₃, SiC and ZrO₂ mixtures. Fracture toughness and strength of Al₂O₃ were greatly improved by incorporating SiC and ZrO₂ particles which were located mainly inside and between Al₂O₃ grains, respectively. The toughening and strengthening mechanism of these composites and the phase stability of the tetragonal ZrO₂ in the composites before and after high-temperature annealing were investigated by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. It was observed that there is a critical volume fraction of zirconia, above which the phase stability of the tetragonal zirconia increases, despite the grain growth of the zirconia. It is considered that another phenomenon, the residual stresses, affect the phase stability of the tetragonal zirconia. To remove the residual stresses the composites were annealed at 1100 °C. After slow cooling, the tetragonal zirconia became very unstable, especially in samples with the highest fabrication temperature and increasing zirconia content. Even quenching from 1100 °C caused an increase in the monoclinic phase of these samples.     

Microstructure and mechanical properties of chromium and chromium/nickel particulate reinforced alumina ceramics

A range of Al₂O₃-Cr and Al₂O₃-Cr/Ni composites have been made using either pressureless sintering in the presence of a graphite bed or hot pressing. Examination of the microstructures shows that they are fully dense (typically 98–99% of the theoretical density) and that the micrometre-scale metallic particles remain discrete and homogeneously dispersed in all composites. All of the hot pressed specimens had higher flexural strengths than the sintered materials. Within each processing route, the composites had slightly lower strength values than the equivalent monolithic alumina specimens. This was attributed to weak interfacial bonding. Fracture toughness behaviour was investigated using indentation and double cantilever beam methods. All of the composites were found to be tougher than the parent alumina and to show resistance-curve behaviour. For the composites, maximum fracture toughness values were 5–6 MPa m^1/2 (about double the value for alumina) for process zone sizes of a few millimetres, although steady state was not reached in the limited number of specimens tested. Examination of fracture surfaces and indentation cracks showed that the toughening potential of the metal particles was not exploited to any significant extent. This was mainly due to weak metal-Al₂O₃ interfaces, but also because of carbon embrittlement of the metallic particles in which chromium was the major constituent.     

Advanced ceramics: Combustion synthesis and properties

Fine-particle ceramic powders such as chromites, manganites, ferrites, cobaltites, aluminas (α-Al₂O₃, Cr³⁺/Al₂O₃, zirconia-toughened alumina, mullite and cordierite), ceria, titania, zirconia (t, m, c and PSZ), dielectric oxides (MTiO₃, PZT and PLZT) as well as highT _c cuprates have been prepared by the combustion of redox compounds or mixtures. The combustion-derived oxide materials are of submicron size with a large surface area and are sinteractive.     

Catalytic activity of CuO-loaded TiO<Subscript>2</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> for NO Reduction by CO

The activities in NO + CO reaction of CuO-loaded TiO₂/γ-Al₂O₃ catalysts prepared by precipitation (P), co-precipitation (C-P), or sol-gel (S-G) were examined using a micro-reactor-gas chromatography (GC) system. The study showed higher catalytic activity of 12%CuO/15%TiO₂/γ-Al₂O₃ (P) than that of 12%CuO/15%TiO₂/γ-Al₂O₃ (S-G) or 12%CuO/15%TiO₂/γ-Al₂O₃ (C-P) in air condition, compared with higher activity of 12%CuO/15%TiO₂/γ-Al₂O₃ (P) or 12%CuO/15%TiO₂/γ-Al₂O₃ (S-G) than that of 12%CuO/15%TiO₂/γ-Al₂O₃ (C-P) in H₂ condition. The specific surface area and crystallite formation had little effect on catalytic activities. H₂-temperature programmed reduction (TPR) revealed four reduction peaks of 12%CuO/15%TiO₂/γ-Al₂O₃ (P), three reduction peaks of 12%CuO/15%TiO₂/γ-Al₂O₃ (S-G), but only one reduction peak of 12%CuO/15%TiO₂/γ-Al₂O₃ (C-P). CuO diffraction peaks were detected only in 12%CuO/15%TiO₂/γ-Al₂O₃ (P), indicating that CuO was highly dispersed on the other two TiO₂/γ-Al₂O₃ catalysts. As a result, 12%CuO/15%TiO₂/γ-Al₂O₃ (P) had the highest activity of reducing NO. During NO + CO reaction, the absorption peaks of intermediate product N₂O were shown at 150 °C by 12%CuO/15%TiO₂/γ-Al₂O₃ (P), at 200 °C by 12%CuO/15%TiO₂/γ-Al₂O₃ (S-G), and at 100 °C by 12%CuO/15%TiO₂/γ-Al₂O₃ (C-P) after H₂ pretreatment at 400 °C for 1 h.