Hydrothermal Crystallization of Zirconia and Zirconia Solid Solutions

Zirconia as well as yttria-zirconia and calcia-zirconia solid-solution powders were crystallized under hydrothermal conditions from (co)precipitated hydroxides. The morphology of the powder particles is strongly dependent on the crystallization conditions. The powders crystallized in a water solution of Na, K, and Li hydroxides show elongated particles of much larger sizes than those which result from the process carried out in pure water or a water solution of Na, K, or Li chlorides. The shapes of the latter particles are isometric. The growth mechanism of the elongated particles is suggested.     

Processing of monodispersed ZrO2 powders

Monodispersed ZrO₂ fine particles were synthesized by the hydrolysis of the metal alkoxide in alcohol solution. Differential thermal analysis-thermogrametric analysis (DTA-TG) revealed that the weith loss of bound water with an endothermic reaction occurred below 320°C, and that the crystallization to the tetragonal phase from an amorphous phase occurred at 430°C.Calcined ZrO₂ powders were crystallized and consisted of spherical monodispersed ZrO₂ fine particles similar to their precursors. The state of dispersed particles in suspension was modified by pH adjustment. In a neutral suspension, particles were agglomerated, but in a basic medium they were well dispersed by a high negative charge in their zeta potential. Ordered compacts were produced by gravitational settling from the basic suspension. Three-dimensional close-packed arrays of particles were also observed in ordered compacts.     

Synthesis,characterization and sintering of Li2TiO3 nanoparticles via low temperature solid-state reaction

Synthesis of fine Li₂TiO₃ powders via low-temperature solid-state reaction (LTSSR) was studied. Solid Li₂CO₃ and H₂TiO₃ were blended by planetary ball mill with deionized water as medium. Calcination of the milled powder at low temperature of 500 °C resulted in the formation of pure Li₂TiO₃ nanoparticles. Another Li₂TiO₃ powder was also prepared by the conventional solid-state reaction (SSR) and a good comparison between different routes was realized. The results show that the particle size of LTSSR powder is significantly decreased to 19.6 nm while the one obtained by SSR is 146.6 nm. Low temperature calcined powders have less agglomeration and higher sinterability, which can be sintered at lower temperature. Pebbles sintered from the LTSSR powders at 750 °C exhibit small grain size (650 nm), high relative density (85.1%) and satisfactory crush load (42.8 N), whereas the SSR pebbles can only be sintered above 950 °C with the relative density close to 80%. Besides, the LTSSR samples also have a higher conductivity at room temperature, indicating the lower tritium diffusion barrier in ceramics. It is confirmed that H₂TiO₃ rather than TiO₂ is more appropriate for the solid-state reaction to produce Li₂TiO₃ powders with nano-size particles and favorable properties.     

Sinterability,microstructures and electrical properties of Ni/Sm-doped ceria cermet processed with nanometer-sized particles

Ni/Sm-doped ceria (SDC) cermet was prepared from two types of NiO/SDC mixed powders: Type A—Mechanical mixing of NiO and SDC powders of micrometer-sized porous secondary particles containing loosely packed nanometer-sized primary particles. The starting powders were synthesized by calcining the oxalate precursor formed by adding the mixed nitrate solution of Ce and Sm or Ni nitrate solution into oxalic acid solution. Type B—Infiltration of Ni(NO₃)₂ solution into the SDC porous secondary particles subsequently freeze-dried. Type B powder gave denser NiO/SDC secondary particles with higher specific surface area than Type A powder. The above two types powders were sintered in air at 1100–1300 °C and annealed in the H₂/Ar or H₂/H₂O atmosphere at 400–700 °C. Increased NiO content reduced the sinterability of Type A powder but the bulk density of Type B powder compact showed a maximum at 34 vol.% NiO (25 vol.% Ni). Type B cermet was superior to Type A cermet in achieving fine-grained microstructure and a homogeneous distribution of Ni and SDC grains. The electrical resistance of the produced cermet decreased drastically at 15 vol.% Ni for Type B and at 20 vol.% Ni for Type A.     

Synthesis and characterization of nanocrystalline forsterite through citrate–nitrate route

Nanocrystalline forsterite, Mg₂SiO₄, powder was synthesized according to the citrate–nitrate technique using an aqueous solution of magnesium nitrate, colloidal silica, citric acid, and ammonia. The dried precursor and the powders calcined at different temperatures were characterized by X-ray diffraction (XRD), simultaneous thermal analysis (STA), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The initial crystallization temperature of forsterite was around 770 °C while fully crystallized forsterite was obtained at 860 °C with a crystallite size of about 30 nm.     

An investigation on flowability and compressibility of AA 6061100 − x-x wt.% TiO2 micro and nanocomposite powder prepared by blending and mechanical alloying

This work investigates the relationships between the components of powders, namely, the powder surface morphology, the flow characteristics and the compressibility of low-energy (microcomposite) and high-energy (nanocomposite) ball milled powders of Al 6061 alloy reinforced with TiO₂ particles. The morphology of the above powder as the function of reinforcement and the milling time was studied by using the scanning electron microscope (SEM). The changes in powder characteristics such as the apparent density, tap density, true density and flow rate were examined by the percentage of reinforcement and milling time. The cohesive nature of the powder was also investigated in terms of Hausner ratio and Kawakita plot. Further, the particle/agglomerate size of low-energy and high-energy ball milled powders was explained by the laser particle size analyzer. X-ray peak broadening analysis was used to determine structural properties of mechanically alloyed powders. The compressibility behavior was examined by the compaction equation proposed by Panelli and Ambrosio Filho to investigate the deformation capacity of the powder. The compressibility behavior, namely, the densification parameter (A) of the microcomposite powder (irregular morphology) was decreased significantly with increasing TiO₂ content due to the disintegration of TiO₂ particles and the cluster formation followed by its agglomeration. The compressibility behavior, namely, the densification parameter (A) of the nanocomposite powder (equiaxed and almost spherical) was decreased slowly with increasing TiO₂ content due to work hardening on the matrix powder. With increased milling time, the compressibility behavior of AA 6061-10 wt.% TiO₂ composite powders increased up to 30 h of milling due to embedding of TiO₂ particles with matrix and changes in powder morphology and finally decreased after 40 h due to work hardening effect.     

One-step synthesis of fine SrTiO3 particles using SrSO4 ore under alkaline hydrothermal conditions

The employment of mineral SrSO₄ crystals and powders for preparing SrTiO₃ compound was investigated, with coexistence of Ti(OH)₄·4.5H₂O gel under hydrothermal conditions, at various temperatures (150–250 °C) for different reaction intervals (0.08–96 h) in KOH solutions with different concentrations. The complete dissolution of the SrSO₄ crystal occurred at 250 °C for 96 h in a 5 M KOH solution, resulting in the synthesis of SrTiO₃ particles with two different shapes (peanut-like and cubic). In contrast, very fine SrTiO₃ pseudospherical particles were crystallized when SrSO₄ powders were employed as precursor. Variations on the SrTiO₃ particle shape and size were found to be caused by the differences in the dissolution rate of the SrSO₄ phase in the alkaline KOH solution. The crystallization of SrTiO₃ particles was achieved by a bulk dissolution–precipitation mechanism of the raw precursors, and this mechanism was further accelerated by increasing the reaction temperature and concentration of the alkaline media. Kinetic data depicted that the activation energy required for the formation of SrTiO₃ powders from the complete consumption of a SrSO₄ single crystal plate under hydrothermal conditions, is 27.9 kJ mol⁻¹. In contrast, when SrSO₄ powders were employed (28–38 μm), the formation of SrTiO₃ powder proceeded very fast even for a short reaction interval of 3 h at 250 °C in a 5 M KOH solution.     

Aqueous sol–gel synthesis of zirconium titanate (ZrTiO4) nanoparticles using chloride precursors

Zirconium titanate powders were synthesized by a straightforward sol–gel method using zirconium and titanium chlorides as metal precursors, deionized water as solvent and oxygen donor, and a NaOH solution for adjusting pH to 7. According to transmission electron microscopy, amorphous particles of nearly 5 nm in size with a relatively spherical morphology were prepared. Thermogravimetry and differential scanning calorimetery analyses on the xerogel at a heating rate of 10 °C/min indicated a crystallization temperature of 690 °C, which is comparable with previous reports. Furthermore, via differential scanning calorimetery studies using the Kissinger's equation, the activation energy for ZrTiO₄ crystallization was determined to be 850 kJ/mol. Structural evaluations in the isothermal regime, using X-ray diffraction experiments, implied the onset of ZrTiO₄ crystallization at 550 °C.     

Synthesis of NaA zeolite from kaolin source

In this work, zeolite NaA was successfully synthesized by a hydrothermal method using kaolin as a combined source for silica and alumina. Zeolite NaA with high static water adsorption was synthesized from the low-cost raw material, kaolin, and the reaction parameters were optimized. Metakaolin was obtained by calcining kaolin at temperatures ranged from 953 K to 1173 K. The synthesis mixture was pre-crystallized at 343 K and crystallized at 373 K successively. Zeolite NaA was obtained, which was confirmed by SEM, XRD and the water adsorption analysis. The optimized metakaolinization temperature was found at 973 K. The influence of Na₂O/SiO₂ molar ratio, pre-crystallization time and seed on the crystallization of NaA zeolite was investigated. A thorough mixing of metakaolin and NaOH solution was favourable for the nucleation/crystallization rate. The obtained NaA zeolite under the optimized conditions shows excellent crystallinity and static water adsorption of 28.0 wt-%, which was higher than 25.9 wt-% of the commercial NaA zeolite. Kaolin was suggested to be a feasible and economical raw material for the practical industrial applications for NaA zeolite.     

Physicochemical Properties of Encapsulated Red Raspberry (Rubus idaeus) Powder: Influence of High-Pressure Homogenization

Encapsulated red raspberry (Rubus idaeus) powders with gum arabic were produced using a spray-drying method. The raspberry puree samples were treated with and without high-pressure homogenizers prior to spray drying. The physicochemical properties of spray-dried raspberry powders were analyzed. The median particle size (X ₅₀) of raspberry powder produced with high-pressure homogenized puree (14.6 µm) was smaller than raspberry powder produced without high-pressure homogenization applied to puree (18.3 µm). Glass transition temperatures and water contents of encapsulated raspberry powders were not significantly different (p > 0.05) at equivalent water activities. High-pressure homogenization of puree resulted in greater apparent density and porosity for encapsulated raspberry powder. Greater particle size resulted in higher hygroscopicity and water solubility index (WSI) for encapsulated raspberry powder produced without high-pressure homogenization of puree. Anthocyanins concentration was greater in raspberry powder pretreated with high-pressure homogenization although powder exhibited lower brightness, redness, and yellowness.     

Improved microstructure of alumina ceramics prepared from DBD plasma activated powders

Submicron Al₂O₃ powders were activated by Diffuse Coplanar Surface Barrier Discharge (DCSBD) plasma. The influence of the plasma treatment on the powder properties and their impact on the microstructure of dry and wet shaped ceramics were investigated. Raman and FTIR analyses of treated powders showed a substantial increase of the powder’s surface hydroxylation, surface cleaning, and the presence of adsorbed NO_x originating from the DCSBD. Sintering of the dry shaped plasma treated powders did not influence sintering behavior. On the other hand, the plasma treated powder was able to form stable water suspension without any chemical stabilization aid. Slip cast samples exhibited finer pore size distribution, a higher sinterability, and a finer final microstructure. The grain size of slip casted plasma treated powder was reduced by a factor of 1.7, which facilitated a grain size of 0.68 μm at the relative density of 99.54% t.d. obtained by pressure-less sintering.     

New Methods for Preparing Submicrometer Powders of The Tungstate‐Ion Conductor Sc2(WO4)3 and its Al and In Analogs

Two new methods for preparing submicrometer powders of M₂(WO₄)₃, M = Sc, In, and Al via combustion synthesis are reported. Stoichiometric combinations of trivalent metal nitrates, ammonium metatungstate, and either urea or carbohydrazide as the fuel were reacted at 550°C, producing amorphous or poorly crystallized powders with an average particle size ranging from 164 to 350 nm. Calcining the powders at 800°C for 1 h produced well‐crystallized, phase‐pure powders with an average particle size ranging from 210 to 711 nm. Powders sintered at 1000°C for 14 h resulted in pellets that were 87%–95% of the theoretical density, which is notably higher than typically obtained from powders prepared by solid‐state reaction. Whereas there was little difference in the microstructure of Al₂(WO₄)₃ pellets prepared with the two different powders, the carbohydrazide‐derived powders resulted in In₂(WO₄)₃ and Sc₂(WO₄)₃ pellets with a larger grain size than those prepared with urea‐derived powders. The electrical conductivity of the sintered pellets, while comparable to that reported for polycrystalline M₂(WO₄)₃ prepared by solid‐state reaction, was strongly influenced by grain‐boundary effects.     

Influence of mechanical activation on sphene based ceramic material synthesis

Sphene (CaTiSiO₅), a calcium titanosilicate ceramic has been prepared from a powder mixture of CaCO₃, TiO₂ and SiO₂ using vibro-milling for homogenization and activation of precursors. The mechanochemical process initially yielded amorphous powders, which on further calcination, crystallized to yield sphene ceramic. The evolution of the phase composition with thermal treatment was investigated by X-ray powder diffraction (XRPD). Powder morphology and particle size distribution were analyzed by scanning electron microscopy (SEM) and laser diffraction, respectively. Rietveld refinement was employed to get the structural information of the synthesized powder. Densification and microstructure evolution was determined by means of density and scanning electron microscopy (SEM). The most favorable conditions for mechanical activation and synthesis of sphene based ceramic material are reported.     

Polyacrylamide gel synthesis and sintering of Mg2SiO4:Eunanopowder

A Mg₂SiO₄:Eu³⁺ nanopowder was synthesized by a polyacrylamide gel method. In this route, the gelation of the solution is achieved by the formation of a polymer network which provides a structural framework for the growth of particles. The densification of the powders was also studied. An amorphous nanopowder was synthesized and crystallized to Mg₂SiO₄ after heat-treatment via a solid-state reaction at a relatively low temperature of about 700 °C. The powders prepared by the polyacrylamide gel method showed better sinterability than the powders synthesized by the conventional sol–gel method. The relative density of the sample was 97% at 1500 °C.     

Natural and synthetic hydroxyapatite/zirconia composites: A comparative study

Zirconia precursor was precipitated in a HAp particles suspension using two HAp powders of natural origin and a synthetic powder. The first natural HAp was extracted from animal bones by treatment with hot NaOH solution and the second one by treatment under hydrothermal conditions with water.Hydrous zirconia was precipitated in the HAp suspension. Pressureless sintering was performed at 1000–1300 °C and hot pressing at 1050–1300 °C.It was found that zirconia additive promotes decomposition of both HAp of natural origin as well as the synthetic one. The most stable HAp was the one extracted from bovine bones by treatment with water in an autoclave. This reaction leads to the formation of β–TCP and the CaO–ZrO₂ solid solution.The hot pressed composites show essentially higher strength and fracture toughness as compared to the pure hydroxyapatite polycrystals.     

Bioactivity and biodegradability of high temperature sintered 58S ceramics

Bioactive glasses are often considered in bone tissue engineering applications where mechanical strength is essential. As such, bioactive glass scaffolds are often sintered to improve mechanical strength. However, sintering can lead to crystallization, which reduces bioactivity and biodegradability. It has generally been considered that amorphous biomaterials exhibit better bioactivity. However, the in-vitro bioactivity and biodegradability of the sintered 58S made from initial amorphous powder and partially crystalline powder with the same chemical compositions (60SiO₂-36CaO-4P₂O₅ (mol%)) have not been compared before.In this study, 58S bioactive glass (fully amorphous) and glass-ceramic (partially crystallized) powders were synthesized using the sol-gel process, followed by heat-treating at 600 °C for 3 h (calcination). The powders were mixed with carboxymethyl cellulose solution as a binder, shaped in a cylindrical mold, dried, and then sintered at 1100 °C for 5 h. The in-vitro bioactivity and biodegradability of the sintered samples were assessed in simulated body fluid (SBF) for times up to 28 days. The specimens were investigated before and after immersion in SBF using X-ray powder diffraction (XRD), Scanning Electron Microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR). The In-vitro bioactivity and biodegradability rate of the sintered 58S produced from the glass ceramic powder were higher than that from fully amorphous powder. This study shows that the initial structure after calcination is important and affects the subsequent crystallization during sintering. Therefore, crystallinity and formation of hydroxyapatite after calcination are important controlling mechanisms that can increase the bioactivity and biodegradability rate of sintered 58S.     

Effect of fuel type on morphology and reactivity of combustion synthesised MgAl2O4 powders

Abstract

Two types of stoichiometric MgAl₂O₄ spinel powders were prepared by combustion synthesis routes, using sucrose (SCS) or urea (UCS) as fuel. For comparative purposes a stoichiometric MgAl₂O₄ powder was also prepared by solid state reaction synthesis (SS powder). Pressed compacts of the three powder types were sintered at various temperatures ranging from 1575 to 1625°C for 2 h. After grinding, SCS and SS powders had very narrow particle size distributions, with average particle sizes of 3·17 and 4·13 μm respectively, whereas UCS powder showed a wide particle size distribution with an average particle size of 37·76 μm. Their corresponding surface areas were found to be 65·8, 8·67, and 8·06 m² g^-1. The SCS MgAl₂O₄ powder sintered at 1625°C for 2 h had a bulk density of 3·44 g cm^-3 (96% of theoretical), an apparent porosity of 1·76%, and water absorption of 0·519%. The superior properties of SCS powders compared with other spinel powders are attributed to the higher surface area induced by the larger size of the sucrose molecule and the greater amount of gas evolved during sucrose combustion.     

Effects of calcination atmosphere on monodispersed spherical particles for highly optical transparent yttria ceramics

Highly sinterable powders are required for the fabrication of transparent ceramics. Here, we studied the effects of calcination atmosphere on the characteristics of monodispersed spherical Y₂O₃ powders, such as crystallite size and particle density, for high optical transparent ceramics. It was found that vacuum calcination around the crystallization temperature is the crucial step to eliminate intragranular pores in the spherical particle. The fast decomposition rate in a vacuum creates smaller crystallites, and the following higher calcination temperature results in the enhancement of pore elimination. The in‐line transmittance of the transparent Y₂O₃ ceramics, vacuum sintered at 1750°C, was improved by increasing the particle density of the as‐calcined powders. This result indicates that the high‐density starting particles effectively enhance the pore elimination during the fabrication of transparent Y₂O₃ ceramics.     

Rate enhancement of hydrogen generation through the reaction of magnesium hydride with water by MgO addition and ball milling

The variations of the amount of hydrogen generated with the kind of powders and the condition of the magnesium and magnesium hydride powders were investigated. By the reaction of Al, TiH₂ and unmilled and milled Mg powders with water, the H₂ generation rates were very low and the quantities of H₂ generated were extremely small. The quantity of H₂ generated by the reaction of unmilled MgH₂ powder with water was greater than those generated by the reactions of Al, TiH₂, and unmilled and milled Mg powders with water. The MgH₂ powder milled for 2 h, with finer particles, generated much more H₂ by its reaction with water than unmilled MgH₂ powder. The MgH₂ + 5%MgO powder milled for 2 h generated much more H₂ by its reaction with water than the Al, TiH₂, unmilled Mg, milled Mg, unmilled MgH₂, and milled MgH₂ powders.     

Reactive alumina production for the refractory industry

In this study, fine reactive alumina powder production was investigated using Bayer gibbsite as a starting material. Experimental studies consist of three steps; in the first step, the soda content was reduced by means of boric acid and distilled water. In the second step, the effect of heating rate and calcinations temperature on crystal size, phase transformation and surface area were investigated and characterization of the powders was performed by means of XRD and SEM analyses. In the third step, the powders obtained optimum conditions were ground in an attritor mill and then particle size distribution and surface area were measured. The soda content of the gibbsite was reduced from 0.325 to 0.05% by H₃BO₃ treatment, calcination at 1200 °C and then washing in distilled water. The higher the heating rate, the smaller the crystal size is. Alumina ceramics with a density higher than 94.70% of theoretical density were obtained.