Synthesis, microstructure and mechanical properties of ceria stabilized tetragonal zirconia prepared by spray drying technique

Ceria stabilized zirconia powders with ceria concentration varying from 6 to 16 mol% were synthesized using spray drying technique. Powders were characterized for their particle size distribution and specific surface area. The dense sintered ceramics fabricated using these powders were characterized for their microstructure, crystallite size and phase composition. The flexural strength, fracture toughness and microhardness of sintered ceramics were measured. High fracture toughness and flexural strength were obtained for sintered bodies with 12 mol% of CeO₂. Flexural strength and fracture toughness were dependent on CeO₂ concentration, crystallite size and phase composition of sintered bodies. Correlation of data has indicated that the transformable tetragonal phase is the key factor in controlling the fracture toughness and strength of ceramics. It has been demonstrated that the synthesis method is effective to prepare nanocrystalline tetragonal ceria stabilized zirconia powders with improved mechanical properties. Ce-ZrO₂ with 20 wt% alumina was also prepared with flexural strength, 1200 MPa and fracture toughness, 9.2 MPa√m.     

(1 − x)PNZ-xBT ceramics derived from mechanochemically synthesized powders

Nanosized (1−x)Pb(Zn_1/3Nb_2/3)O₃-xBaTiO₃ (PZN-BT, x=0.05, 0.10, 0.15, 0.20, 0.25, and 0.30) powders were synthesized directly from their corresponding oxide mixture via a high-energy ball milling process. Almost single phase was achieved in the composition range of PZN-BT. The grain size estimated from SEM observation was about 50 nm, being in good agreement with that (20 nm) calculated from XRD patterns. PZN-BT ceramics were also obtained by sintering the synthesized powders at 1050°C for 1 h. The grain size of the final ceramics decreases from 4.5 to 1.2 μm as BT content increases from 0.05 to 0.30. The properties, such as microstructure, lattice constant, phase composition, dielectric constant as a function of composition of the PZN-BT ceramics, were investigated and discussed.     

Investigation on crystalline phases and mechanical properties of TZP ceramics prepared from sol-gel powders

Y₂O₃-stabilized tetragonal zirconia polycrystalline (TZP) ceramics containing 1–5 mol% Y₂O₃ were prepared by hot pressing and pressureless sintering of sol-gel-derived powders. Sintered ceramics were evaluated for their density, grain and crystallite size, width of transformation zone, crystalline phases and mechanical properties. Variation in the values of fracture toughness and flexural strength has been explained on the basis of crystallite size and proportion of transformable tetragonal phase, which are influenced by the concentration of Y₂O₃ in TZP ceramics. Correlation of the data has indicated that the transformable tetragonal phase is the key factor in controlling the fracture toughness and strength of ceramics.     

纳米晶Ba_（1－x）Pb_xTiO_3的合成与表征

以醋酸铅、硬脂酸钡和钛酸丁酯为原料，用硬脂酸凝胶法（ＳＡＧ）合成了粒度均匀、粒径１０－２０ｎｍ的Ｂａ（１－ｘ）ＰｂｘＴｉＯ３纳米晶粉末．利用红外光谱（ＩＲ）、热重（ＴＧ）和差热分析（ＤＴＡ）研究了纳米晶粉末的合成过程．用ＴＥＭ、ＸＲＤ观察和研究纳米晶的形貌及晶体结构，并用发射光谱测定样品的纯度．     

Nanosized hydroxyapatite powders derived from coprecipitation process

Nanosized hydoxyapatite (Ca₁₀(PO₄)₆(OH)₂ or HA) powders were prepared by a coprecipitation process using calcium nitrate and phosphoric acid as starting materials. The synthesized powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) specific area measurment techniques. Single phase HA, with an average grain size of about 60 nm and a BET surface area of 62 m²/g, was obtained. No grain coarsening was observed when the HA powders were heated at 600°C for 4 hours. HA ceramics were obtained by sintering the powders at temperatures from 1000°C to 1200°C. Dense HA ceramics with a theoretical density of 98% and grain size of 6.5 m were achieved after sintering the HA powders at 1200°C for 2 hours. HA phase was observed to decompose into tricalcium phosphate when sintered at 1300°C. The microstructure development of the sintered HA ceramics with sintering temperature was also characterized and discussed.     

Synthesis and microstructure characterization of tetragonal Zr1–xTixO2 (x = 0–1) solid solutions

Oxide powders of Zr_1–xTi_xO₂ (x = 0–1) solid solutions with micron-sized particles were synthesized via a solution combustion method. The synthesis process and Zr/Ti molar ratio were optimized to produce powders with the tetragonal crystal structure. X-ray diffraction, Raman spectroscopy and transmission electron spectroscopy results confirm that a full crystallization microstructure with the single tetragonal phase is obtained after calcination at 600 °C while maintaining the crystallite size <30 nm. Zr/Ti oxide mixtures with Zr ≥ 67 mol% exhibit a tetragonal crystal structure and the embedding Ti in ZrO₂ improves the structure stability. The nitrogen sorption results indicate that the powders possess mesoporous morphology with medium specific surface areas (∼10–50 m²/g). Chemical stability tests show that these powders are relatively stable with negligible removal of titanium and zirconium after elution by 0.5 mol/L HCl. Density functional theory was used to calculate the most stable structure with low energy for the selected composition.     

Hrtem study of nanocrystalline zirconia powders

Zirconia powders with grain sizes between 4 and 35 nm were synthesized by the gas condensation technique. Different qualities (grain size, grain size distribution) of powders have been observed and can be attributed to different synthesis conditions (mainly temperature gradients) within the UHV chamber. The existence of necks between single particles has been observed. These necks are due to a first sintering process during the oxidation of the metal/ suboxide clusters condensed on the walls in the synthesis chamber. Several stages of this sintering process are documented by high-resolution micrographs. Furthermore, some particles exhibit a shell-like structure with monoclinic ZrO₂ in the outer region and tetragonal ZrO₂ in the inner region. This is an indication of (i) the martensitic phase transition character of zirconia in general, and (ii) the existence of a critical particle size in n-ZrO₂ responsible for the metastability of a tetragonal polymorph in nanosized zirconia powder. Lattice distortions in some directions can be concluded from image reconstruction of the digitized micrograph of a single nanosized ZrO₂ particle.     

Preparation of crystal-controlled Y-TZP/Al2O3 nanocomposites

ZrO₂-Y₂O₃-Al₂O₃ nanocrystalline powders with different grain sizes have been synthesized using a chemical coprecipitation method. Nano-powders were compacted uniaxially and densified in a vacuum hot-pressing furnace. Density, pore size distribution, grain size and composition of the composites were determined by various techniques, including BET gas absorption, field-emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). It has been shown that the porosity, grain and pore size of the ceramics can be controlled by the initial powder size and sintering temperature. Fully densified ceramics with narrow grain size distribution in the range of 100 ?? 500 nm could be obtained.     

Hydroxyapatite-based ceramic materials prepared using solutions of different concentrations

Hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂, powders with enhanced sinterability have been synthesized through precipitation from calcium nitrate and ammonium hydrogen phosphate solutions at pH 9, t= 60°C, and a Ca/P atomic ratio of 1.67, and their properties have been studied: phase composition, particle size distribution, loose density, and green density. The initial solution concentration is shown to influence the properties of the powders and the ceramics fabricated from them. Comparison of the particle size distributions in disaggregated powders and the grain size distributions in the ceramics indicates that the ceramics inherit the structure of the corresponding powders. Optimizing the synthesis conditions in order to enhance the sinterability of the powders, we obtained green compacts with the highest shrinkage rate in the range 850–950°C and shrinkage onset at 600°C, which is 100–150°C lower in comparison with powders synthesized in earlier studies from calcium nitrate and ammonium hydrogen phosphate.     

Microstructure and dielectric relaxor behavior of Ba(Zr0.2Ti0.8)O3–(Ba0.7Ca0.3)TiO3–BaBi4Ti4O15 ceramics by tape casting

Plate-like BaBi₄Ti₄O₁₅ powders were used to fabricate 0.952[Ba(Zr_0.2Ti_0.8)O₃–(Ba_0.7Ca_0.3)TiO₃]–0.048BaBi₄Ti₄O₁₅(abbr. BZCT-BBT) ceramics by tape casting. The microstructure and dielectric relaxor behaviors of BZCT-BBT ceramics were investigated. BZCT-BBT ceramics can be sintered well at 1,100?°C and mainly consisted of tetragonal perovskite phase and BaBi₄Ti₄O₁₅ (abbr. BBT) phase. The lattice constants decrease as the sintering temperature increases due to substitution of Bi³⁺ for the A-site atoms of the perovskite structure. There is no obvious difference between the structure in the perpendicular and parallel directions, however, an evident difference of dielectric properties in the two directions is observed. Comparing with Ba(Zr_0.2Ti_0.8)O₃–(Ba_0.7Ca_0.3)TiO₃(abbr. BZCT) ceramics, BZCT-BBT ceramics show obvious relaxor characteristics which are evidenced by the degree of diffuseness γ calculated using the modified Curie–Weiss law. Meanwhile, the addition of BBT decreases T_m, which results from the decrease of grain size. The reduction of ε_m is mainly caused by phase structure deviation from the coexisting rhombohedral and tetragonal structure to single tetragonal.     

Ferroelectric and optical properties of Ba5Li2Ti2Nb8O30 ceramics potential for memory applications

Giant grained (42 μm) translucent Ba₅Li₂Ti₂Nb₈O₃₀ ceramic was fabricated by conventional sintering technique using the powders obtained via solid state reaction route. These samples were confirmed to possess tetragonal tungsten bronze structure (P4bm) at room temperature. The scanning electron microscopy established the average grain size to be close to 20 μm. The photoluminescence studies carried out on these ceramics indicated sharp emission bands around 433 and 578 nm at an excitation wavelength of 350 nm which were attributed to band-edge emission as the band gap was 2.76 eV determined by Kubelka–Munk function. The dielectric properties of these ceramics were studied over wide frequency range (100–1 MHz) at room temperature. The decrease in dielectric constant with frequency could be explained on the basis of Koops theory. The dielectric constant and the loss were found to decrease with increasing frequency. The Curie temperature was confirmed to be ~370 °C based on the dielectric anomaly observed when these measurements were carried out over a temperature range of 30–500 °C. This shows a deviation from Curie–Weiss behaviour and hence an indicator of the occurrence of disordering in the system, the γ = 1.23 which confirms the diffuse ferroelectric transition. These ceramics at room temperature exhibited P–E hysteresis loops, though not well saturated akin to that of their single crystalline counterparts. These are the suitable properties for ferroelectric random access memory applications.     

Rate-controlled synthesis and sintering of nanocrystalline barium titanate powder

The densification and grain size during sintering as well as particle size, of the barium titanate powder during Pechini decomposition-synthesis depends on the heating rate and this dependence originates from the kinetic competition between elementary transformation mechanisms, inherent in the two processes. The given competition is the main reason for development of the optimum mode of the mentioned thermal activated processes. As developed at the NCSU (USA) the Rate-Controlled Sintering (RCS) is known to allow the obtaining of dense and finegrained ceramics with improved properties. As developed at the IPMS (Ukraine) the Rate-Controlled Synthesis is directed to prepare nanocrystalline unagglomerated ceramic powders suitable for RCS. The extreme behavior of the BaTiO₃ particle size as a function of heating rate is established and the optimal temperature-time path is calculated and verified to obtain the best powder of 20–25 nm particles. The change in microstructure and phase composition with heating rate is considered in details. The advantages of the RCS to achieve density of 99.9% and grain size around 100–150 nm are presented in comparison with the linear heating rate regime.     

Dielectric Ba(Ti1?xSnx)O3 (x?=?0.13) ceramics, sintered by spark plasma and conventional methods

A two-step sintering approach composed of spark-plasma-sintering (SPS) technique at 1000 °C for 1 min and under a uniaxial pressure of 63 MPa followed by conventional sintering at 1400 °C for 3 h is proposed for synthesis of dense Ba(Ti_0.87Sn_0.13)O₃ ceramics. Starting powders had grain size of about 90 nm and were obtained by co-precipitation. The SPS pellets consist of submicron (300–500 nm) grains. X-ray diffraction analysis of as-prepared Ba(Ti_0.87Sn_0.13)O₃ ceramic shows the occurrence of cubic and tetragonal phase coexistence for the pellets obtained after SPS processing and the presence of only tetragonal phase in the samples after the second (conventional) sintering. Grain uniformity in the final product is high, with average size of ~2 μm. The apparent densities of the sintered pellets at temperature of 1400 °C were ~92% of the theoretical value of Ba(Ti_0.87Sn_0.13)O₃. The ceramics exhibit a high relative dielectric constant of 6,550 and a dielectric loss (tan δ) = 0.078 at Curie temperature of 63 °C and 10 Hz.     

Effects of TiO2 addition on the sintering of ZrO2·TiO2 compositions and on the retention of the tetragonal phase of zirconia at room temperature

The production of tetragonal zirconia polycrystalline (TZP) ceramics and the identification of factors controlling retention of the tetragonal phase in the ZrO₂·TiO₂ system have been investigated. In this binary system, it was not possible to retain tetragonal zirconia polycrystals at room temperature for a range of compositions sintered above 1200 °C. A decrease in the martensitic transformation temperature of zirconia with titania addition was observed, but the effect was insufficient to retain the tetragonal phase at room temperature. In solid solution, the TiO₂ additions act to suppress ZrO₂ densification, this leading to grain growth when attempts are made to attain higher densities. The use of fine powders, fast firing or sintering in reducing conditions altered densification but was not able to generate a final grain size sufficiently small to avoid spontaneous tetragonalmonoclinic transformation on cooling. Based on the results obtained for ZrO₂·MO_x systems, the main factors involved in the retention of tetragonal zirconia at room temperature are discussed in an attempt to incorporate thermodynamical and the stress field effects.     

Synthesis and characterization of low cost willemite based glass–ceramic for opto-electronic applications

This paper presents a comprehensive study on thermal, structural and optical properties of novel willemite glass–ceramics. The precursor glass in the ZnO–SLS glass system was successfully prepared using conventional melt-quenching technique and willemite (Zn₂SiO₄) glass–ceramics were derived from this precursor glass by a control crystallization process. The effect of heat-treatment temperature on the phase transformation, morphology and size of Zn₂SiO₄ crystal phase was examined using X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) techniques. Furthermore, fourier transform infrared reflection (FTIR) spectroscopy was used to evaluate the Zn₂SiO₄ crystal structural evolution. The average size of Zn₂SiO₄ crystallite obtained from calculation of XRD is found to be in the range 30–60 nm, whereas the grain size observed in FESEM is in range of 200–400 nm. The appearance of SiO₂, ZnO₄ and Zn–O–Si bands detected from FTIR indicate the formation of Zn₂SiO₄ crystal phase. Besides, the study of the optical band gap has found that optical band gap of the glass–ceramics decreased as the heat treatment temperature increased. The photoluminescence spectra of willemite glass–ceramics exhibit two different emissions around 525 nm (green) and 585 nm (yellow); exhibit a characteristic of broad absorption band around 260 nm. These two different spectra reveal that the luminescence performance of the willemite glass–ceramics was enhanced with the progression of heat treatment temperature due to different located energy levels of the β-Zn₂SiO₄ and α-Zn₂SiO₄ crystalline phase. Such luminescent glass–ceramics was expected to find potential applications in phosphors and opto-electronic devices.     

Rapid formation of lead magnesium niobate-based ferroelectric ceramics via a high-energy ball milling process

Pyrochlore-free nano-sized 0.90Pb(Mg_1/3Nb_2/3)O₃(PMN)-0.10PbTiO₃(PT) and 0.65PMN-0.35PT powders were synthesized from oxides via a high-energy ball milling process. Single perovskite phase PMN-PT were readily formed from the oxide mixture after milling for only 2 h. The grain size calculated from X-ray diffraction (XRD) patterns of all samples is about 20 nm, which is in agreement with the observation from scanning electron microscopy (SEM) (20-50 nm). PMN-PT ceramics were obtained by sintering the milled powders at temperature from 1000 to 1100°C for 2 h. The dielectric, ferroelectric properties of the PMN-PT ceramics derived from the synthesized powders were comparable with the reported results in the literature.     

并流共沉淀法合成Dy_(2)O_(3)-ZrO_(2)纳米粉体EI北大核心CSCD

采用并流化学共沉淀法合成了Dy_(2)O_(3)掺杂ZrO_(2)(DySZ)纳米粉体材料,系统研究稳定剂掺杂量、阳离子浓度、反应系统pH值和煅烧温度对粉体材料物相组成、晶体结构和微观形貌的影响。结果表明:不同合成工艺条件下,DySZ粉体材料均具有纳米尺度特征,球形颗粒尺寸为10~30 nm,Dy_(2)O_(3)的掺杂可以起到稳定晶型的作用;稳定剂掺杂量对DySZ粉体的物相组成具有明显影响,掺杂量为10%(质量分数)时可合成单一四方相结构的DySZ粉体;DySZ粉体材料的四方度和微观形貌对稳定剂掺杂量、阳离子浓度、反应体系pH值和煅烧温度均不敏感,但其平均晶粒尺寸随稳定剂掺杂量、阳离子浓度和反应体系pH值的升高略有降低,随煅烧温度的提高而显著增加。     

Superplasticity and machinability in a four-phase ceramic

Fine grained four-phase ceramic materials were fabricated to have a combination of high temperature superplasticity and room temperature machinability. The composite ceramics were made of 25 vol.% 3Y-TZP/8YSZ–25 vol.% Al₂O₃–25 vol.% MgAl₂O₄–25 vol.% LaPO₄, using LaPO₄ powders fabricated in-house. X-ray diffraction and scanning electron microscopy revealed that the grain size for the best mixed samples was in the range of 600 nm, tetragonal ZrO₂ transformed into monoclinic, and reactions in the sintered samples produced a new phase, magnetoplumbite (LaMgAl₁₁O₁₉) with lath-like grains. The formation of magnetoplumbite was facilitated by the presence of yttria and by a liquid phase generated at elevated temperatures. These four-phase ceramics had a maximum hardness of 12 GPa and fracture toughness was no more than 3 MPa√m. Deformation rates at 1400 °C under 40 MPa stress were in the superplastic range of 10^?3 s^?1 for most compositions. These four-phase ceramics were machinable as demonstrated using conventional tungsten drill bits.     

Synthesis and characterization of (Na0.85K0.15)0.5Bi0.5TiO3 ceramics by different methods

The (Na_0.85K_0.15)_0.5Bi_0.5TiO₃ (BNKT) powders were synthesized by solid-state method, sol-gel method and stearic acid method. Microstructure, piezoelectric and dielectric properties of the ceramics were investigated. Attempts had been made to understand the reaction processes by using thermo gravimetric (TG) and differential scanning calorimetry (DSC). The BNKT powders have a perovskite structure with average crystallite sizes of 168 nm, 85 nm and 79 nm, corresponding to the solid-state method, the sol-gel method and the stearic acid method, respectively. The ceramics derived from the powder synthesized by sol-gel method presents the most homogeneous microstructure and largest grain size (5-7 μm). The effects of average crystallite size on microstructures and electric properties of the BNKT ceramics were investigated. Both the piezoelectric properties and dielectric properties were enhanced with the increase of grain size.     

Effect of Grain Size on Phase Transformation and Photoluminescence Property of the Nanocrystalline ZrO_2 Powders Prepared by Sol-Gel Method

Nanocrystalline zirconia （ZrO2） powders were prepared by a sol-gel process followed by annealing treatments from 500 to 1200 ℃. Phase transformation, microstructural features and photoluminescence properties were characterized by X-ray diffraction, transmission election microscopy and photoluminescence spectra, respectively. The results show that both monoclinic phase and tetragonal phase exist in the nanocrystalline ZrO2 powders at annealing temperature in the range of 500-900 ℃, and the concentration of monoclinic phase increases with increasing the annealing temperature. Tetragonal phase is totally transformed to monoclinic phase when annealing temperature is up to 900 ℃. The average grain size of the powders also increases when annealing temperature increases. Two emission peaks centered at 390 nm （named as /390） and 470 nm （named as /470） exist in the photoluminescence spectra, and the intensity ratio of /390 to /470 decreases with increasing annealing temperature. The grain size is proposed to be responsible for the phase transformation in the nanocrystalline ZrO2 powders.