High-pressure sintered yttria stabilized zirconia ceramics

Fast densification of 8YSZ ceramics under a high pressure of 4.5 GPa was carried out at different temperatures (800, 1000, 1450 °C), by which a high relative density above 92% could be obtained. FT-Raman spectra indicate that the 8YSZ underwent a phase transition from partially tetragonal to partially cubic phase as temperatures increase from 1000 to 1450 °C when sintering under high pressure. The electrical properties of the samples under different high-pressure sintering conditions were measured by complex impedance method. The total conductivity of 0.92 × 10⁻² S cm⁻¹ at 800 °C has been obtained for 8YSZ under high pressure at 1450 °C, which is about 200 °C lower than that of the samples prepared by conventional pressureless sintering.     

Synthesis of nanocrystalline 8 mol% yttria stabilized zirconia powder from sucrose derived organic precursors

An organic precursor synthesis of 8 mol% yttria stabilized zirconia (YSZ) powder from Zr–Y composite nitrate solution and sucrose has been studied. Oxidation of sucrose in Zr–Y composite nitrate solution containing excess nitric acid in situ generates hydroxy carboxylic acids that forms a white sol which showed peaks at 1640 cm⁻¹ and 1363 cm⁻¹ in IR spectrum corresponding to hydroxy carboxylic acid complexes of Zr and Y. Precursor mass obtained by drying the sol on calcinations at 600 °C produced loosely agglomerated particles of cubic YSZ. Deagglomerated YSZ contain submicron particles with D₅₀ value of 0.5 μm and the particles are aggregates of nanocrystallites of nearly 10 nm size. Compacts prepared by pressing the YSZ powder sintered to 96.7% TD at 1450 °C. The sintered YSZ ceramic showed an average grain size of 2.2 μm.     

Effects of TiO2 on microstructural,mechanical properties and in-vitro bioactivity of plasma sprayed yttria stabilised zirconia coatings for dental application

One of the most compatible coatings, known as yttria-stabilised zirconia polycrystal (YZP) is deposited on metallic Ti alloys due to its excellent hardness and aesthetic value as well as its low affinity for plaques. However, poor bioactivities of YZP and the existence of micro crack propagations due to the aging of YZP may result in spontaneous implant failure thus limiting its clinical use. In this work, YZP coating reinforced titania (TiO₂), which is formed via a plasma spray technique was investigated in order to enhance the bioactivity and the mechanical properties of YZP coatings for dental implants. Based on microstructural studies performed on the deposited coating, a distinguished lamellar structure comprising YZP and TiO₂ was observed. It was found that the reinforcement of TiO₂ in YZP coating significantly reduced the crack due to the improved densities and the lamellar structure. The mechanical properties were also found to improve with 90% of hardness, 45% of adhesion strength and 54% of Young's Modulus with TiO₂ addition, which is desirable for dental implants. An in-vitro bioactivity test was then conducted by immersing the coatings in a simulated body fluid (SBF). As a result, an apatite formation was found on the YZP/TiO₂ coating surface after 3 days of immersion. Besides, it was verified in an XRD analysis that the crystalline TiO₂ was found in a rutile phase which was highly effective in generating apatite (natural mineral in human bones) on YZP coatings, proving that the bioactivities of the coating were significantly improved. Further studies were also performed on the SBF treatment, which took up to 14 days also demonstrated that only a small decrease in hardness was noted, indicating that YZP/TiO₂ coatings had reached an excellent mechanical stability.     

Studies on the synthesis and sintering of nanocrystalline yttria

Nanocrystalline yttria powders were synthesized from yttrium nitrate by the citrate gel-combustion technique. The auto-ignition of five different gels with fuel to oxidant (citric acid/nitrate) ratios 0.25, 0.5, 0.75, 1.0 and 1.1 was studied. All these mixtures yielded precursors which upon calcination in air at 1073 K yielded yttria. The bulk densities, specific surface area, X-ray crystallite size, size distribution of particles as well as the residual carbon present in these powders were determined. The influence of the fuel to oxidant ratio on the powder properties was analyzed. Scanning electron microscopy (SEM) showed that these powders were porous while the high resolution transmission electron microscopy (HRTEM) revealed that they consist of randomly oriented cuboidal nanocrystallites with an average crystallite size of 25±7 nm. These powders were compacted at 120 MPa without any lubricant or binder and their sinterability was studied. Pellets with a sintered density as high as 98–99% T.D. (theoretical density) could be obtained at a relatively low sintering temperature of 1673 K. Studies on the dependence of the properties of nanocrystalline yttria powders on the composition of the initial mixture used in the citrate gel-combustion as well as the sintering characteristics of these powders are being reported for the first time. Our investigations revealed that an initial mixture comprising equimolar quantities of the nitrate and citric acid yielded a powder with characteristics most suitable for fabricating yttria crucibles.     

Eight mole percent yttria stabilized zirconia powders by organic precursor route

An organic precursor-mixing route has been developed for preparation of 8 mol% yttria stabilized zirconia (8YSZ) ceramics. Polymeric salt of succinic acid with yttrium and zirconium has been prepared separately by treating sodium succinate with yttrium chloride and zirconyl chloride followed by washing with water and drying at 120 °C. Thorough mixing of the two salts in stoichiometric proportions by planetary ball milling followed by calcination at 850 °C resulted in a precursor powder containing nanocrystalline (∼40 nm) monoclinic zirconia, tetragonal YSZ, cubic YSZ and yttria. Compacts prepared after deagglomeration of powder by planetary ball milling produce 8YSZ ceramics having density 99.3% TD on sintering at 1550 °C for 2 h.     

Studies on the synthesis of nanocrystalline yttria powder by oxalate deagglomeration and its sintering behaviour

Nanocrystalline yttria powders were synthesized from deagglomerated yttrium oxalate. The precipitation of this oxalate was carried in two different modes viz., addition of aqueous oxalic acid into yttrium nitrate solution (forward strike) and vice versa (reverse strike) followed by ultrasonication in acetone and water. Nanocrystalline yttria was obtained by calcining the oxalate in air at 1073 K. The bulk densities, specific surface area, X-ray crystallite size, size distribution of particles as well as the quantity of carbon residue in these powders were determined. The influence of the deagglomeration medium on the powder properties was analyzed. Scanning electron microscopy (SEM) showed that these powders comprised irregular agglomerates while the high resolution transmission electron microscopy (HRTEM) revealed that the constituent units of these agglomerates were randomly oriented cuboidal nanocrystallites (20–40 nm). These powders were compacted at 120 MPa without any lubricant or binder and their sinterability was studied. Pellets with sintered density as high as 97.5% T.D. (theoretical density) could be obtained at a relatively low sintering temperature of 1873 K. Synthesis of nanocrystalline yttria powders by oxalate deagglomeration route as well as the systematic studies of their properties and sinterabilities are being reported for the first time. It was further demonstrated in this study that higher sintered densities could be obtained with less number of process steps and at a much lower compaction pressure. Samples prepared by reverse strike yielded a powder with characteristics most suitable for fabricating high density yttria bodies. 1673 K would be the optimum temperature for sintering the compacts made out of this powder.     

机械法制莫来石微粉的性能与烧结

利用环缝磨、搅拌磨制得了Ｄ０．５达μｍ左右的莫来石微粉。该粉体粒度分布窄，机械力化学活性高。用此微粉与细粉进行压坯烧结试验表明，其粒径比和体积比对烧结有很大影响。在粒径比相差不大的情况下，对应每一烧结温度均存在一个微粉最低有效加入量，且烧结温度越高，该加入量越小；当粒径比相差很大时，此加入量值变得不太明显，但少量微粉引入即可显著提高坯体的烧结性能。     

Firing characteristics of size-controlled silver-glass composite powders prepared by spray pyrolysis

Size-controlled spherical silver-glass composite powders were directly prepared by using spray pyrolysis. The mean sizes of the composite powders changed from 0.34 to 0.78 μm when the concentration of the spray solution was changed from 0.05 to 2 M. The firing characteristics of composite powders formed from the spray solutions with a glass content equal to 3 wt.% of the silver component were affected by the mean sizes of the powders. Silver-conducting films formed from large-sized composite powders had a denser structure than those formed from small-sized composite powders. Further, silver-conducting films formed from composite powders with a mean size of 0.78 μm had specific resistances of 3 and 2 μΩ cm at firing temperatures of 450 and 500 °C. However, silver-conducting films formed from composite powders with a mean size of 0.34 μm had specific resistances of 8.2 and 6.9 μΩ cm at firing temperatures of 450 and 500 °C.     

Morphological and electrochemical properties of LiV3O8 cathode powders prepared by spray pyrolysis

Lithium trivanadate (LiV₃O₈) powders are prepared by spray pyrolysis. The precursor powders of LiV₃O₈ obtained by spray pyrolysis have spherical and rod-like morphologies. The LiV₃O₈ powders post-treated at 300 °C and 400 °C also have spherical and rod-like morphologies. However, the LiV₃O₈ cathode powders post-treated at 500 °C consist of only rod-like crystals. The crystalline structure of the precursor powders that were directly prepared by spray pyrolysis comprised of LiV₃O₈ layers along with a small amount of β-Li_0.33V₂O₅ impurity. The peak due to β-Li_0.33V₂O₅ persisted in the XRD spectrum even after post-treatment at 300 °C. On the other hand, crystalline structures of the powders post-treated at 400 °C and 500 °C comprised pure LiV₃O₈ layers. The initial discharge capacities of the LiV₃O₈ cathode powders decrease from 344 mAh g⁻¹ to 261 mAh g⁻¹ when the post-treatment temperatures increase from 300 °C to 500 °C. The discharge capacities of the LiV₃O₈ cathode powders obtained after post-treatment at 400 °C and 500 °C are approximately 255 mAh g⁻¹ and 236 mAh g⁻¹, respectively, after 40 cycles.     

Synthesis of nanocrystalline 8 mol% yttria stabilized zirconia by the oleate complex route

Nanocrystalline 8 mol% yttria stabilized zirconia (YSZ) powder has been synthesized by the oleate complex route. Oleate complexes of zirconium and yttrium were formed in the hexane rich layer by the reaction of sodium oleate with zirconyl chloride and yttrium chloride at the interface of the two ternary solutions in water–ethanol–hexane system. The zirconyl oletae and yttrium oleate complexes on heating decomposed to oxide through the formation of carbonate intermediates. The powder obtained by calcination at 600 °C for 2 h was cubic YSZ with surface area of 42 m²/g. The YSZ powder contained primary particles of ∼300 nm size and the primary particles were aggregate of crystallites of 5–10 nm. The compacts prepared from the YSZ powder were sintered to ∼99% TD (theoretical density) at 1400 °C. The sintered YSZ had a low average grain size of 0.73 μm.     

Nitrate fusion synthesis and two-step sintering of nanocrystalline yttria stabilized hafnia powders

Bulk quantities of nanocrystalline yttria stabilized hafnia (YSH) powders with crystallite size ranging from 8 to 15 nm were successfully prepared for the first time through nitrate fusion synthesis at a temperature as low as 673 K. The yttrium content was varied from 6 to 30 mol%. The dependence of the properties of the final product on the quantity of the dopant was investigated. Microstructural investigations were carried out with scanning electron microscopy and transmission electron microscopy. A maximum relative sintered density of 98.2 ± 0.3% T.D (theoretical density) was obtained for YSH containing 10 mol% yttrium by using “two-step sintering” at a final temperature of 1773 K. Anisotropic shrinkage factor (0.70–0.95) was found to vary linearly with the compaction pressure. SEM investigations reaffirmed that the sintered pellets comprised uniform distribution of faceted grains and elemental mapping revealed that yttrium is distributed uniformly in these sintered YSH monoliths.     

Nickel particles prepared from nickel nitrate with and without urea by spray pyrolysis

Nickel particles were prepared by spray pyrolysis of 0.5 M Ni(NO₃)₂·6H₂O solution with hydrogen at a residence time of 19 s. All the product particles were composed of nickel oxide and nickel with no trace of nickel nitrate under the condition. The particles were completely reduced to nickel at a furnace set temperature of 410 °C. However, it was not until 850 °C that the spherical particles fully densified and crystallized appeared. Use of urea enhanced the solidness and surface smoothness of the particles, while slightly reducing the rate of metallization. The urea enabled to prepare the nickel particles even without hydrogen though under stricter conditions. The rates of metallization and sintering/crystallization were slightly affected by the residence time and initial salt concentration. Higher crystallized nickel particles had higher resistance to oxidation in air environment.     

Microstructural design and high temperature tensile deformation behaviour of 8 mol% yttria stabilized cubic zirconia (8YCSZ) with SiO2 additions

In the present study, the microstructural evolution and high temperature deformation behaviours of 8 mol% Y₂O₃ stabilized cubic zirconia (8YCSZ) containing up to 10 wt% SiO₂ is investigated. The experimental results show that the SiO₂ doped specimens sintered at 1400 °C contain only the cubic crystalline phase and SiO₂ has the very limited solubility of 0.3 wt% in cubic zirconia. This suggests that only small part of the SiO₂ dissolves in the cubic zirconia and the rest of SiO₂ segregates at grain boundaries and multiple junctions as amorphous (glassy) phase. This glassy phase prevents the grain growth by minimizing grain boundary energy and mobility, which results from solute segregation at the grain boundary and its drag. The deformation of the undoped 8YCSZ is characterized by large strain hardening with limited elongation. This is mainly due to severe grain growth during high temperature deformation. The addition of the SiO₂ results in a decrease in strain hardening and enhanced tensile elongation. These effects have been further improved with the increase of the SiO₂ addition reaching the elongation to failure of 152% for 10 wt% SiO₂ doped specimen in tension at a temperature of 1400 °C and strain rate of 1.3 × 10⁻⁴ s⁻¹. The decreased strain hardening and increased ductility in the SiO₂ doped specimens are due to the segregation of amorphous glassy phase to the grain boundaries, thus hindering grain growth and facilitating grain boundary sliding, which is the primary mechanism of deformation in fine grained materials at high temperatures.     

Effect of precursor characteristics on zirconia and ceria particle morphology in spray pyrolysis

Ultrasonic spray pyrolysis of acetate-based precursors with precisely measured precursor drop size was employed to produce ZrO₂ and CeO₂ particles. A bimodal size distribution of the product particles indicates a significant influence of the gas-to-particle conversion mechanism in addition to the conventionally accepted one-particle-per-drop mechanism. Due to the differences in solubility of the precursors, ZrO₂ particles are spherical in shape and smooth on their surfaces while the CeO₂ particles are bowl-like in shape with uneven surfaces. Spherical and monodispersed particles with a peak diameter <100 nm can be obtained by reducing the precursor concentrations to 0.01 wt.% in both the different precursor system.     

Microstructure and high-temperature sintering properties of APS coatings prepared from spherical thin-walled hollow-shell powders

High-performance thermal barrier coatings (TBCs) made of 4 mol.% Y₂O₃–stabilized ZrO₂ (4YSZ) powder with a spherical thin-walled hollow-shell (STHS) structure exhibited a special microstructure different from the conventional lamellar structure of air plasma-sprayed (APS) coatings. The as-sprayed STHS APS coatings had a completely tetragonal prime (t′) structure and non-lamellated closed-cell structure with high porosity, which resulted in relatively low thermal conductivity (～1.0 W m^?1 K^?1) and high Vicker's hardness (～6 GPa). The influences of high-temperature aging on the microstructure stability, phase stability, and sintering capability were investigated after long-time heat treatment at different temperatures. The characterization results indicated that the pore content was basically constant, and it was less than 0.5% for sintered linear shrinkage of the STHS coatings after heat treatment at 1500 °C for 100 h. Furthermore, no spalling appeared in the STHS APS coating with the t′ phase structure after 101 thermal cycles of the water-quenching method at 1050 °C, and no monoclinic ZrO₂ (m-ZrO₂) phase was present in all of the STHS coatings after aging at 1200 °C for 1–1100 h. The excellent anti-sintering properties and phase stability of the STHS coatings are attributed to the closed-pore microstructure and the highly pure t′ phase composition with uniform distribution of ions, respectively. The results suggested that the non-lamellated closed-cell microstructure is beneficial for improving the coating properties, and the results also provide guidelines for microstructure design of TBCs using a feedstock powder.     

Microstructure and mechanical properties of yttria stabilized zirconia coatings prepared by plasma spray physical vapor deposition

Plasma spray physical vapor deposition (PS-PVD) was used to deposit yttria stabilized zirconia (YSZ) coatings with different columnar morphologies by varying the spray distance. Although similar quasi-columnar structures were formed at the spray distances of 600 mm and 1400 mm, the formation mechanisms of particles in the coatings were different. Besides, an electron beam physical vapor deposition (EB-PVD) like columnar coating out of pure vapor was deposited at a spray distance of 1000 mm and the columnar consisted of elongated nano-sized secondary columns. The hardness and Young׳s modulus of the coatings were investigated. Compared to the other two quasi-columnar structures, the EB-PVD like columnar coating exhibited higher hardness (~9.0 GPa ) and Young׳s modulus (~110.9 GPa), mainly due to its low porosity and defect.     

Influence of sintering parameters on tribological properties of ceria stabilized zirconia bio-ceramics

Nano-structured ceria stabilized zirconia powder was synthesized from their respective nitrate salts using a wet chemical co-precipitation method. Dried powder was calcined at different temperatures. Particle size of calcined powders was measured by X-ray diffraction (Scherrer equation) and high resolution transmission electron microscopy. Relative quantities of phases (e.g. monoclinic, tetragonal and cubic) were estimated using rigorous Rietveld analysis. The powder was compacted and sintered conventionally following different time and temperature schedules in order to optimize the sintering schedule for fabrication of dense material. The microstructures of the sintered samples were observed by field emission scanning electron microscopy. Vickers hardness (∼945 VHN) showed appreciable increase (>35%) in the hardness value compared to earlier reported ones. Fretting wear of some of the selected samples was carried out in un-lubricated condition. Wear volume and specific wear rate were estimated and correlated with the microstructure. Fatigue microcrack formation, plastic deformation, grain pull-out and abrasion were found to be the main wear mechanisms.     

Stability of rare‐earth‐doped spherical yttria‐stabilized zirconia synthesized by ultrasonic spray pyrolysis

Phase stability is one of the crucial requirements for any material that can be used at elevated temperature applications such as thermal barrier coating (TBC). The most traditional TBC material, partially stabilized zirconia, limits the operating temperature due to its phase transformation. Conversely, the low thermal conductivity of fully stabilized zirconia (YSZ) may enable effective reduction in the surface temperature on the coated component, while avoiding deleterious phase transitions, although still being subjected to sintering and grain growth. It has been reported that addition of rare‐earths as dopants to YSZ can significantly increase resistance to grain growth at high temperature. Keeping this under consideration, this work investigates the role of rare‐earths (lanthanum and gadolinium) in increasing thermal stability of YSZ microspheres, the building blocks for high‐temperature photonics for reflective TBC. The spheres were produced by ultrasonic spray pyrolysis, and the doping led to significant improvement of stability by significant inhibition of grain growth. While the individual dopants showed significant growth and sintering inhibition up to 900°C, co‐doping with 4% (in mol) of each (Gd and La) led to coarsening resistance up to 1000°C for 3 hours, when particles retained reasonable spherical features with nanometric crystallite sizes.     

Physical properties of 8 mol% Ceria doped yttria stabilised zirconia powder and ceramic and their behaviour during annealing and sintering

The thermal behaviour of 8 mol% Ceria doped 16 mol% yttria stabilised zirconia (Ce-YSZ) powder, synthesised by the wet co-precipitation method, has been investigated in details. The lattice parameter, mean crystallite size and lattice distortions have been determined as a function of calcination temperature. After grinding by attrition followed by fractionating in acetone, the powders were compacted and sintered at 1600 °C in air for 5 h. The sintering behaviour of pellets was studied by dilatometry, revealing different sintering behaviour depending on the calcination temperature of the powders and the type of agglomerates. The influence of these latter parameters on the microstructure of pellets has been investigated. The pellets produced from powders calcined at low-temperature, from 110 to 600 °C, present the highest densities and the best morphological structure.     

Flash sintering of yttria-stabilized zirconia powders coated with nanoscale films of alumina by atomic layer deposition

The addition of small quantities of aluminum oxide (Al₂O₃) to 8 mol% yttria-stabilized zirconia (8YSZ) benefits conventional sintering by acting as a sintering aid and altering grain growth behavior. However, it is uncertain if these benefits observed during conventional sintering extend to flash sintering. In this work, nanoscale films of Al₂O₃ are deposited on 8YSZ powders by particle atomic layer deposition (ALD). The ALD-coated powders were flash sintered using voltage-to-current control and current rate experiments. The sintering behavior, microstructural evolution, and ionic conductivities were characterized. The addition of Al₂O₃ films changed the conductivity of the starting powder, effectively moving the flash onset temperature. The grain size of the samples flashed with current rate experiments was ~65% smaller than that of conventionally sintered samples. Measurement of grain size and estimates of sample density as a function of temperature during flash sintering showed that small quantities of Al₂O₃ can enhance grain growth and sintering of 8YSZ. This suggests that Al₂O₃ dissolves into the 8YSZ grain boundaries during flash sintering to form complexions that enhance the diffusion of species controlling these processes.