Yb2O3 and Y2O3 co-doped zirconia ceramics

A suspension stabilizer-coating technique was employed to prepare x mol% Yb₂O₃ (x = 1.0, 2.0, 3.0 and 4.0) and 1.0 mol% Y₂O₃ co-doped ZrO₂ powder. A systematic study was conducted on the sintering behaviour, phase assemblage, microstructural development and mechanical properties of Yb₂O₃ and Y₂O₃ co-doped zirconia ceramics. Fully dense ZrO₂ ceramics were obtained by means of pressureless sintering in air for 1 h at 1450 °C. The phase composition of the ceramics could be controlled by tuning the Yb₂O₃ content and the sintering parameters. Polycrystalline tetragonal ZrO₂ (TZP) and fully stabilised cubic ZrO₂ (FSZ) were achieved in the 1.0 mol% Y₂O₃ stabilised ceramic, co-doped with 1.0 mol% Yb₂O₃ and 4.0 mol% Yb₂O₃, respectively. The amount of stabilizer needed to form cubic ZrO₂ phase in the Yb₂O₃ and Y₂O₃ co-doped ZrO₂ ceramics was lower than that of single phase Y₂O₃-doped materials. The indentation fracture toughness could be tailored up to 8.5 MPa m^1/2 in combination with a hardness of 12 GPa by sintering a 1.0 mol% Yb₂O₃ and 1.0 mol% Y₂O₃ ceramic at 1450 °C for 1 h.     

Processing and mechanical properties of ZrO2–TiB2 composites

In this paper, a strategy is described to develop high toughness yttria-stabilised tetragonal zirconia polycrystalline (Y-TZP) composites reinforced with hard TiB₂ particles. The experimental results revealed that fully dense Y-TZP composites with 30 vol.% TiB₂ can be obtained with a moderate hardness of 13 GPa, a high strength up to 1280 MPa and an excellent indentation toughness up to 10 MPa m^1/2 by hot pressing in vacuum at 1450 °C. The toughness of the composites can be tailored between 4 and 10 MPa m^1/2 by varying the yttria stabiliser content of the ZrO₂ matrix between 3 and 2 mol%. An optimum composite toughness was achieved for a ZrO₂ matrix with an overall yttria content of 2.5 mol%, obtained by mixing pure monoclinic and 3 mol% Y₂O₃ co-precipitated ZrO₂ starting powders. An important observation is that the thermal residual tensile stress in the ZrO₂ matrix due to the TiB₂ addition, needs to be taken into account when optimising the transformability of the ZrO₂ matrix in order to develop high toughness Y-TZP composites.     

Mechanical properties of Al2O3/ZrO2 composites

In the present study, both t-phase zirconia and m-phase zirconia particles are incorporated into an alumina matrix. Dense Al₂O₃/(t-ZrO₂+m-ZrO₂) composites were prepared by sintering pressurelessly at 1600 °C. The microstructure of the composites are characterized, the elastic modulus, strength and toughness determined. Because the ZrO₂ inclusions are close to each other in the Al₂O₃ matrix, the yttrium ion originally in t-ZrO₂ particles can diffuse to nearby m-ZrO₂ particles during sintering, and the m-phase zirconia is thus stabilized after sintering. The strength of the Al₂O₃/(t-ZrO₂+m-ZrO₂) composites after surface grinding can reach values as high as 940 MPa, which is roughly three times that of Al₂O₃ alone. The strengthening effect is contributed by microstructural refinement together with the surface compressive stresses induced by grinding. The toughness of alumina is also enhanced by adding both t-phase and m-phase zirconia, which can reach values as high as two times that of Al₂O₃ alone. The toughening effect is attributed mainly to the zirconia t–m phase transformation.     

Aging effects on the characteristics and sintering behavior of coprecipitated Al2O3---ZrO2 powders

Effect of gel aging on the characteristics of zirconia-toughened alumina (ZTA) composites were investigated. The composite powders were prepared by coprecipitation processes using a mixed solution of aluminum nitrate and zirconium oxynitrate. The coprecipitates were aged in an aqueous solution of pH 9 at room temperature. The occurrence of either intra- or intergranular ZrO₂ particles in the Al₂O₃ matrix depended on the aging condition, which also affected the content of tetragonal ZrO₂ (t-ZrO₂). Aging treatment decreased the amount of intragranular ZrO₂, as well as the agglomerate strength of calcined powders, both of which seemed to improve the sintered densities of ZTA ceramic bodies. Through suitable aging processes, sintered ZTA specimens with relative density >99% and intergranular ZrO₂ particles were fabricated.     

Grain growth inhibition and mechanical property enhancement by adding ZrO2 to Al2O3 matrix

The critical amount and critical size of ZrO₂ for effective dragging of grain boundary migration occurred at 8 vol% addition for Al₂O₃ ceramic composite, pressureless-sintered at 1600°C for 2h. The fracture toughness was increased from 4·1 to 5·4 MPa m^1/2, and the flexural strength from 290 to 410 MPa at optimal conditions. The enhancement of mechanical properties is attributed to the stress-induced phase transformation toughening when ZrO₂ particles were located intergranularly. Al₂O₃ grain growth is inhibited by ZrO₂ particles pinning at the grain boundaries.     

ZrO2/SiO2- and La2O3/Al2O3-supported platinum catalysts for CH4/CO2 reforming

Surface-phase ZrO₂ on SiO₂ (SZrOs) and surface-phase La₂O₃ on Al₂O₃ (SLaOs) were prepared with various loadings of ZrO₂ and La₂O₃, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH₄/CO₂ reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al₂O₃ and Pt/SiO₂ catalysts. CO₂ or CH₄ pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO₂ to form a stable surface-phase oxide. The lanthana cannot be spread well on Al₂O₃, but it forms a stable amorphous oxide with Al₂O₃. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO₂ and Pt/Al₂O₃ by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO₂ and Pt/Al₂O₃ catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO₂ adsorbed on the basic sites of SZrOs and SLaOs.     

Microstructure and flexure creep behaviour of SiC-particle reinforced Al2O3 matrix composites

The flexure creep behaviour of monolithic Al₂O₃ and 10 vol% SiC-particle reinforced Al₂O₃ matrix composites was investigated in air atmosphere at 1160 to 1400 °C and under a stress of 40 to 125 MPa. Two kinds of SiC particles with different particle sizes and oxygen contents were used in the composites, one having an average size of 0.6 μm with 1.7 vol% SiO₂ impurities and the other of average size 2.7 μm with 3.4 vol% SiO₂ impurities. Compared with the creep behaviour of monolithic Al₂O₃ the strain rate of the composites with 0.6 μm SiC particles did not decrease; however, the composites with 2.7 μm SiC particles exhibited excellent creep resistance. Microstructure analysis showed that the Al₂O₃ grains in the composites with 0.6 μm SiC particles were mainly equiaxed with most of the SiC particles lying at the grain boundaries or triplegrain junctions, whereas the grain features of the composites with 2.7 μm SiC particles were irregular and elongated and most of the SiC particles were entrapped into Al₂O₃ matrix grains. It was revealed that the entrapment of 2.7 μm SiC particles into Al₂O₃ matrix grains was related to the high SiO₂ impurity content on SiC particle surfaces, and the change of grain morphology and the good high-temperature oxidation resistance were responsible for the creep resistance increase of the composites with 2.7 μm SiC particles.     

Ethylene dimerization over NiSO4 supported on Fe2O3-promoted ZrO2 catalyst

The NiSO₄ supported on Fe₂O₃-promoted ZrO₂ catalysts were prepared by the impregnation method. Fe₂O₃-promoted ZrO₂ was prepared by the coprecipitation method using a mixed aqueous solution of zirconium oxychloride and iron nitrate solution followed by adding an aqueous ammonia solution. No diffraction line of nickel sulfate was observed up to 20 wt.%, indicating good dispersion of nickel sulfate on the surface of Fe₂O₃–ZrO₂. The addition of nickel sulfate (or Fe₂O₃) to ZrO₂ shifted the phase transition of ZrO₂ (from amorphous to tetragonal) to higher temperatures because of the interaction between nickel sulfate (or Fe₂O₃) and ZrO₂. 15-NiSO₄/5-Fe₂O₃–ZrO₂ containing 15 wt.% NiSO₄ and 5 mol% Fe₂O₃, and calcined at 500 °C exhibited a maximum catalytic activity for ethylene dimerization. NiSO₄/Fe₂O₃–ZrO₂ catalysts was very effective for ethylene dimerization even at room temperature, but Fe₂O₃–ZrO₂ without NiSO₄ did not exhibit any catalytic activity at all. The catalytic activities were correlated with the acidity of catalysts measured by the ammonia chemisorption method. The addition of Fe₂O₃ up to 5 mol% enhanced the acidity, surface area, thermal property, and catalytic activities of catalysts gradually, due to the interaction between Fe₂O₃ and ZrO₂ and due to consequent formation of Fe–O–Zr bond.     

Transient studies of carbon dioxide reforming of methane over Pt/ZrO2 and Pt/Al2O3

The mechanism of the CO₂ reforming of methane reaction over the Pt/ZrO₂ catalyst was investigated using a temporal analysis of products (TAP) reactor system. For comparative purposes, the reaction pathway using a Pt/Al₂O₃ catalyst was also examined. A reaction sequence is suggested for both catalysts. Over both catalysts, methane decomposition takes place over platinum. The main difference between the two catalysts concerns the carbon dioxide dissociation. Over Pt/Al₂O₃ this step is assisted by hydrogen. Over Pt/ZrO₂ this step takes place over the zirconia support and involves surface vacancies. Moreover, large pools of formate and carbonate species are present on the zirconia. Transient studies conducted to determine the origin of carbon species accumulated during CO₂ reforming revealed that more than 99% of the carbon was derived from the methane molecule over both catalysts. Over the Pt/ZrO₂ catalyst, only a single very reactive carbon species was detected, while over the Pt/Al₂O₃ a second less active species was also formed.     

Polysilazane derived micro/nano Si3N4/SiC composites

The pyrolised polysilazanes poly(hydridomethyl)silazane NCP 200 and poly(urea)silazane CERASET derived Si–C–N amorphous powders were used for preparation of micro/nano Si₃N₄/SiC composites by hot pressing. Y₂O₃–Al₂O₃ and Y₂O₃–Yb₂O₃ were used, as sintering aids. The resulting ceramic composites of all compositions were dense and polycrystalline with fine microstructure of average grain size <1 μm of both Si₃N₄ and SiC phases. The fine SiC nano-inclusions were identified within the Si₃N₄ micrograins. Phase composition of both composites consist of , β modifications of Si₃N₄ and SiC. High weight loss was observed during the hot pressing cycle, 12 and 19 wt.% for NCP 200 and CERASET precursors, respectively. The fracture toughness of both nanocomposites (NCP 2000 and CERASET derived) was not different. Indentation method measured values are from 5 to 6 MPa m^1/2, with respect to the sintering additive system. Fracture toughness is slightly sensitive to the SiC content of the nanocomposite. Hardness increases with the content of SiC in the nanocomposite. The highest hardness was achieved for pyrolysed CERASET precursor with 2 wt.% Y₂O₃ and 6 wt.% Yb₂O₃, HV 23 GPa. This is a consequence of the highest SiC content as well as the chemical composition of additives.     

Effects of ZrO2/Al2O3 properties on the catalytic activity of Pd catalysts for methane combustion and CO oxidation

Zirconia supported on alumina was prepared and characterized by BET surface area, X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), temperature programmed desorption (TPD), and pulse reaction. 0.2% Pd/ZrO₂/Al₂O₃ catalyst were prepared by incipient wetness impregnation of supports with aqueous solution of Pd(NO₃)₂. The effects of support properties on catalytic activity for methane combustion and CO oxidation were investigated. The results show that ZrO₂ is highly dispersed on the surface of Al₂O₃ up to 10 wt.% ZrO₂, beyond this value tetragonal ZrO₂ is formed. The presence of a small amount of ZrO₂ can increase the surface area, pore volume and acidity of support. CO–TPD results show that the increase of CO adsorption capacity and the activation of CO bond after the presence of ZrO₂ lead to the increase of catalytic activity of Pd catalyst for CO oxidation. CO pulse reaction results indicate that the lattice oxygen of support can be activated at lower temperature following the presence of ZrO₂, but it does not accelerate the activity of 0.2% Pd/ZrO₂/Al₂O₃ for methane combustion. 0.2% Pd/ZrO₂/Al₂O₃ dried at 120 °C shows highest activity for CH₄ combustion, and the activity can be further enhanced following the repeat run. The increase of treatment temperature and pre-reduction can decrease the activity of catalyst for CH₄ combustion.     

Formation of Y3Al5O12–Al2O3 eutectic microstructure with off-eutectic composition

Homogeneous-eutectic microstructure of Y₃Al₅O₁₂–Al₂O₃ system without coarse primary crystals was formed at an off-eutectic composition. This method utilizes a low migration rate in an amorphous phase. A mixture of Y₂O₃ and Al₂O₃ having the off-eutectic composition was melted and quenched rapidly to form an amorphous phase. A heat-treatment of the amorphous phase at 1000 °C and 1300 °C for 30 min formed Y₃Al₅O₁₂ and Al₂O₃ phases. SEM observation of this material, which was formed from the amorphous phase at 1300 °C for 30 min, showed homogeneous eutectic-like microstructure. The formation of the primary crystals (coarse Al₂O₃), which are always observed in the off-eutectic compositions by ordinary method, was completely suppressed.     

Phase diagram of the system: Al2O3–ZrO2

The system Al₂O₃–ZrO₂ was studied by differential thermal analysis in inert atmosphere and in vacuum. The eutectic was located at 1866°C and 40% mass of ZrO₂. Zirconia solid solution at the eutectic temperature is up to 1.1±0.3% mass of Al₂O₃. Enthalpy of melting of this eutectic is 1080±90 J/g. Pure ZrO₂ transforms from monoclinic to tetragonal at 1162±7°C, but the saturated solid solution of ZrO₂, with 0.7±0.2% mass Al₂O₃ at this temperature, transforms at 1085±5°C. Inverse transitions occur with hysteresis correspondingly at 1055±5 and 995±5°C. Enthalpy of transformation of pure ZrO₂ from monoclinic to tetragonal phase is 42±5 J/g (5.2±0.6 J/mol) but only 30±5 J/g for a ZrO₂ saturated solid solution.     

Fracture toughness of (Ce) stabilized ZrO2/Al2O3 composites

Three techniques for the determination of K_Ic in Ce-stabilized ZrO₂/Al₂O₃ composites have been evaluated: the single-edge-notched beam (SENB); the indentation strength in bending (ISB) and the indentation fracture (IF). Comparative measurements, performed on samples prepared by sintering uniaxially pressed powders obtained by a chemical route, showed that whatever the technique used, K_Ic increased as the Al₂O₃ grain size decreased.

The three methods give similar results if some procedural improvements are introduced, namely: (i) the polished samples are annealed prior to testing: (ii) a more reproducible notching technique would be developed for the SENB method; and (iii) the crack shape and length are known exactly in the IF technique.

In the IF test, the crack shape profile is of Palmquist type at low indentation loads while a transition to a half-penny-shaped crack occurs at higher loads.     

Microstructure and mechanical properties of ZrO2-2 mol% Y2O3 ceramics

The microstructure and mechanical properties of ZrO₂-2 mol% Y₂O₃ ceramics were studied on samples prepared by cold isostatic pressing and pressureless sintering. It was shown that the density of the alloy increases with increasing sintering temperature. The Vickers hardness decreases with the appearance of the monoclinic phase and increasing its content. Compared with the single tetragonal phase, the (t + m) dual-phase structure with microcracks has a much higher fracture toughness (16·5 MPa√m) because of a complex mechanism of toughening (transformation, microcracks and residual stresses).     

Fabrication of pore-gradient Al2O3–ZrO2 sintered bodies by fibrous monolithic process

Functionally pore-gradient Al₂O₃–ZrO₂ composites where the porosity is dependent on the extrusion ratio and number of shell layer were fabricated by a fibrous monolithic process. The size and volume fraction of the pores were controlled by different numbers of shell layers, which contained various sizes and a different volume percentage of the pore-forming agent. In the pore-gradient, Al₂O₃–ZrO₂ bodies having a dense core part, some defects such as cracks, swelling and delamination occurred during the sintering process due to the low extrusion ratio. However, these defects were completely removed as the extrusion ratio increased, and the shell layers as well as the core part had a continuously porous structure. In the shell part, various sizes of pores from 70 to 250 μm in diameter were observed.     

Synthesis and thermal expansion of ZrO2/ZrW2O8 composites

In this work, a ceramic composite of ZrW₂O₈ and ZrO₂ was synthesized, in order to investigate the possibility of compensating the positive thermal expansion of ZrO₂ with the negative thermal expansion (NTE) compound ZrW₂O₈, tailoring the thermal expansion of these composites. The NTE material was mixed with varying amounts of ZrO₂. The thermal expansion coefficients of this series of composites decrease with increasing amounts of ZrW₂O₈. Nevertheless, a negative deviation from the values expected by the rule of mixtures was found to be most pronounced in the middle of the compositional region.     

Low-temperature reaction-sintering of mullite ceramics with an Y2O3 addition

Mullite ceramics were fabricated at relatively low temperatures from powder mixtures of -Al₂O₃ and quartz, with an Y₂O₃ addition. The mullitization process was analyzed by X-ray diffraction. The densification behavior was investigated as a function of the Y₂O₃ content, sintering temperature and holding time as well as mullite seeds. It has been shown that mullitization occurs via a nucleation and growth mechanism within an yttrious aluminosilicate glass, but lattice and grain-boundary diffusion becomes important during the densification process. Moreover, the incorporation of mullite seeds was observed to enhance both mullitization and densification. At 1400°C for 5 h or 1450°C for 2 h, 15 mol% Y₂O₃-doped and 5 mol% mullite-seeded specimens can be sintered to almost full density.     

High temperature neutron diffraction study of the Al2O3–Y2O3 system

The phase diagram of the Al₂O₃–Y₂O₃ system has been investigated with five different compositions by XRD and in situ high temperature neutron diffractometry. High purity YAG, YAP and YAM compounds have been produced successfully through a melt extraction technique. High temperature neutron diffraction has made it possible to follow, in real time, the reactions involved in this system, especially to determine the temperature range of each reaction, which would have been impossible to determine by other means. A good agreement between the experimental results and the phase diagram of the Al₂O₃–Y₂O₃ system has been observed.