Phase structure and piezoelectric properties of Ca- and Ba-doped K1/2Na1/2NbO3 lead-free ceramics

Piezoelectric lead-free ceramics, K_1/2Na_1/2NbO₃ (KNN) modified with alkaline-earth (AE) Ca²⁺ and Ba²⁺, have been prepared by the conventional solid-state reaction method. The effect of doping level on sinterability and functional response of KNN was studied. In this way, discs doped with 0 to 2 mol% of Ba²⁺ and Ca²⁺ were sintered at 1125 °C for 2 h. It was observed that AE changed drastically the microstructure and grain size of KNN when it was added in concentrations higher than 0.5 mol%. Addition of 0.5 mol% of Ba²⁺ and Ca²⁺ produced a softening effect in the ferroelectric properties of the material, while samples prepared with higher contents than 0.5 mol% showed poor properties.     

Synthesis and characterization of nanocrystalline mullite powders at low annealing temperature using a new technique

For the first time orthorhombic mullite nanoparticles (12 nm) have been synthesized via the co-precipitation technique using mixture of sodium aluminate and sodium silicate solutions as monophasic salts at low annealing temperature 1000 °C. The AC and DC electrical properties of the sintered mullite ceramics were investigated. The results indicated the precursor directly transformed to 3:2 molar ratio orthorhombic mullite. Meanwhile, the surface area of the produced o-mullite at 1000 °C was 15.1 m²/g which increased to 37.3 m²/g with addition of CTAB as a cationic surfactant. TEM images investigated that the microstructure was changed from rod-like shape to roughly spherical shape with addition of surfactant. The DC electrical resistivity of mullite sample sintered at 1600 °C was 16 times greater than that sintered at 1300 °C. The minimum dielectric loss value of 0.014 was obtained at 1600 °C sintering temperature at 1.5 MHz.     

Low-temperature sintering of (K,Na)NbO3-based lead-free piezoceramics with addition of LiF

Dense Li/Ta-codoped KNN-based piezoceramics with d₃₃^* up to 375 pm/V were successfully fabricated by conventional sintering at a temperature as low as 900 °C by using LiF as a sintering additive. The reduction of densification temperature up to 200 °C was realized by a transient liquid phase sintering mechanism, consequently no grain boundary phase was observed in the sintered samples. It was found that the addition of LiF could further shift down the tetragonal–orthorhombic transition point (T_T-O), indicating that a small amount of Li⁺ could diffuse into the A-site of KNN matrix. The introduction of LiF enhanced the linearity of strain curves of the ceramics, which is unambiguously in favor for the actuator application. The present work reveals that low-temperature sintered LiF-doped KNN-based piezoceramics demonstrates promising potential in multilayer-structured actuator applications.     

Reaction sintering of β-tricalcium phosphates and their mechanical properties

Various kinds of calcium oxides, carbonates and phosphates were used as the raw materials, and β-TCP ceramics was fabricated by reaction sintering at 1100 °C, and the sinterability, the reaction sintering behavior and mechanical properties of reaction-sintered β-TCP were investigated. Reaction-sintered bodies using CaHPO₄ + HAp consisted of single β-TCP phase, and bulk density and bending strength increased with extending sintering time. On the contrary, normal-sintered β-TCP synthesized using CaHPO₄ + HAp did not change in bulk density and bending strength with extending sintering time. Reaction-sintered body using CaHPO₄ + HAp as the raw materials showed higher bulk density and bending strength than normal sintered β-TCP.     

Compaction pressure effect on microstructure and electrochemical performance of GdBaCo2O5+δ cathode for IT-SOFCs

In order to optimize the morphology of starting powder, raw GBCO powder synthesized via solid state reaction was repeatedly compacted by uniaxial die pressing at two apparent compaction pressures of 500 and 1000 MPa. The particle size distribution curves and SEM images indicated that, with increasing compaction pressure and number of compaction times, the larger particles in the powder were gradually broken apart and the particle size became small and uniform. Then the effect of pressing treatment for the starting GBCO particles on the microstructure and performance of sintered cathode was studied. The results demonstrated that, after being sintered under the same conditions, the cathode prepared from the treated GBCO particles showed a finer microstructure compared with that prepared from the raw GBCO particles. In addition, optimizing the morphology of the starting GBCO powder by pressing treatment could improved the cathode performance and made the polarization resistance of final cathode reduce from 1.33 Ω cm² to 0.40 Ω cm² at 600 °C.     

Influence of the precursor pyrolysis temperature on the microstructure and conductivity of Gd-doped ceria materials

Gd-doped ceria nanopowders have been synthesized via a modified sol–gel technique using different pyrolysis temperatures to produce a range of particle sizes. Such nanocrystalline oxides have been sintered at 1400 °C for 24 h to produce fully dense disks. The microstructural characterization reveals that the pyrolysis temperature notably affects the grain size distribution in the sintered ceramics, e.g. powders treated at 700 °C render the narrowest grain size distribution. The electrochemical characterisation performed by electrochemical impedance spectroscopy shows that the distribution of grain sizes in the dense electrolytes rules the electrical conductivity of CGOs rather than the average grain size. Narrower grain size distributions render electrolytes exhibiting higher overall conductivity, independent of the average grain size.     

Low temperature fabrication of lead-free KNN-LS-BS ceramics via the combustion method

Lead-free piezoelectric 0.992(0.95K_0.5Na_0.5NbO₃–0.05LiSbO₃)–0.008BiScO₃; KNN-LS-BS ceramics were successfully prepared using the combustion method. The highest % perovskite phase was found in the sample calcined at 700 °C for 1 h. The structural phase of orthorhombic structure was also detected in this sample. For the sintered ceramics, a pure tetragonal perovskite phase was observed in the samples sintered between 1025 and 1100 °C. The microstructure of ceramics showed a square or rectangular shape and the average grain size increased with increasing of sintering temperature. The density of the ceramics increased with increasing of sintered temperature up to 1075 °C, were it reached 97.5% of theoretical density and then dropped in value when the sintered temperature further increased. The excellent electrical properties of ε_r at T_c=6600, tanδ at T_c=0.04, P_r (at 40 kV/cm)=19.4 μC/cm² and E_c (at 40 kV/cm)=24.1 kV/cm were obtained in the most dense ceramic. The results indicate that the KNN-LS-BS ceramics are promising lead-free piezoelectric materials.     

Effect of sintering temperature on the microstructure and transparency of Nd,Y:CaF2 ceramics

1 at% Nd, 3 at% Y doped CaF₂ transparent ceramics were obtained by hot pressing at the sintering temperature varing from 500 to 800 °C under vacuum environment with co-precipitated CaF₂ nanopowders. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis showed that the obtained nanoparticles were single fluorite phase with grain size around 26 nm. Scanning electron microscopy (SEM) observations of the Nd, Y: CaF₂ ceramics indicated that the mean grain size of the ceramic sintered at 800 °C was about 748 nm. The influence of the temperature on the grain size, microstructure and optical transmittance was investigated. For the ceramic sintered at 800 °C, the transmittance was 85.49% at the wavelength of 1200 nm. The room temperature emission spectra of Nd: CaF₂ and Nd, Y: CaF₂ ceramics were measured and discussed.     

Microwave sintering of fine grained HAP and HAP/TCP bioceramics

The effect of microwave sintering conditions on the microstructure, phase composition and mechanical properties of materials based on hydroxyapatite (HAP) and tricalcium phosphate (TCP) was investigated. Fine grained monophase HAP and biphasic HAP/TCP biomaterials were processed starting from stoichiometric and calcium deficient nanosized HAP powders. The HAP samples microwave (MW) sintered for 15 min at 900 °C, with average grain size of 130 nm, showed better densification, higher density and certainly higher hardness and fracture toughness than samples conventionally sintered for 2 h at the same temperature. By comparing MW sintered HAP and HAP/TCP samples, it was concluded that pure HAP ceramics have superior mechanical properties. For monophase MW sintered HAP samples, the decrease in the grain size from 1.59 μm to 130 nm led to an increase in the fracture toughness from 0.85 MPa m^1/2 to 1.3 MPa m^1/2.     

Fabrication and properties of transparent Tb:YAG fluorescent ceramics with different doping concentrations

Terbium doped yttrium aluminum garnet (Tb:YAG) transparent ceramics with different doping concentrations were fabricated by the solid-state reaction method using commercial Y₂O₃, α-Al₂O₃ and Tb₄O₇ powders as raw materials. Samples sintered at 1750 °C for 20 h were utilized to observe the optical transmittance, microstructure and fluorescence characteristics. It is found that all the Tb: YAG ceramics with different doping concentrations exhibit homogeneous structures with grain size distributions around 22–29 µm. For the 5 at% Tb:YAG transparent ceramics, the grain boundaries are clean with no secondary phases. The photoluminescence spectra show that Tb:YAG ceramics emit predominantly at 544 nm originated from the energy levels transition of ⁵D₄→⁷F₅ of Tb³⁺ ions, and the intensity of the emission peak reaches a maximum value when the Tb³⁺ concentration is 5 at%. The in-line transmittance of the 5 at% Tb:YAG ceramics is 73.4% at the wavelength of 544 nm, which needs to be further enhanced by optimizing the fabrication process. We think that Tb:YAG transparent ceramics may have potential applications in the high-power white LEDs.     

Two-Step Sintering of oxide ceramics with various crystal structures

The influence of Two-Step Sintering (TSS) process on the final microstructure of oxide ceramic materials with three different crystal structures was studied. Two kinds of alumina (particle size 100 nm resp. 240 nm) as well as tetragonal zirconia (stabilized with 3 mol% Y₂O₃, particle size 60 nm) and cubic zirconia (8 mol% Y₂O₃, 140 nm) powders were cold isostatically pressed and pressurelessly sintered with different heating schedules. The microstructures achieved with TSS method were compared with microstructures achieved with conventional Single-Step Sintering (SSS) schedule. The results showed that the efficiency of the TSS of these oxide ceramics was more dependent on their crystal structure than on their particle size and green body microstructure. The method of TSS brought only negligible improvement of the microstructure of tetragonal zirconia and hexagonal alumina ceramics. On the other hand, TSS was successful in the sintering of cubic zirconia ceramics; it led to a decrease in grain size by a factor of 2.     

Microstructural features and electrical properties of copper oxide added potassium sodium niobate ceramics

In this study, effects of 0.5, 1.0 and 1.5 mole% CuO addition on the properties of potassium sodium niobate (K_0.5Na_0.5)NbO₃-KNN ceramics were investigated. Pure KNN and CuO-added KNN pellet samples were sintered at 1100 and 1090 °C for 4 h, respectively. Phase analysis showed that all samples crystallized in pure orthorhombic perovskite phase. Addition of 1.0 and 1.5 mole% CuO caused grain growth, densification and formation of a liquid phase at the grain boundaries. Curie temperature has shifted from 480 to 435 °C with increasing CuO ratio. The most remarkable characteristic of the hysteresis loops were the constricted nature of the 0.5 mole% CuO-added KNN's curve and the antiferroelectric-like appearance of the 1.5 mole% CuO-added KNN's curve. Piezeoelectric properties of d₃₃ = 120 pC/N, k_p = 0.27 and Q_m = 772 were obtained from the 1.5 mole% CuO-added KNN.     

Foam-gelcasting preparation,microstructure and thermal insulation performance of porous diatomite ceramics with hierarchical pore structures

Hierarchically pore-structured porous diatomite ceramics containing 82.9∼84.5% porosity were successfully prepared for the first time via foam-gelcasting using diatomite powder as the main raw material. Sizes of mesopores derived from the raw material and macropores formed mainly from foaming were 0.02∼0.1 μm and 109.7∼130.5 μm, respectively. The effect of sintering temperature, additive content and solid loading of slurry on pore size and distribution, and mechanical and thermal properties of as-prepared porous ceramics were investigated. Compressive strength of as-prepared porous ceramics increased with sintering temperature, and the one containing 82.9% porosity showed the highest compressive strength of 2.1 ± 0.14 MPa. In addition, the one containing 84.5% porosity and having compressive strength of 1.1 ± 0.07 MPa showed the lowest thermal conductivity of 0.097 ± 0.001 W/(m·K) at a test temperature of 200 ̊C, suggesting that as-prepared porous ceramics could be potentially used as good thermal insulation materials.     

Enhanced dielectric and piezoelectric properties in Li/Sb-modified (Na,K)NbO3 ceramics by optimizing sintering temperature

In this paper, lead-free (Na_0.474K_0.474Li_0.052)(Nb_0.948Sb_0.052)O₃ ceramics were synthesized by a conventional solid-state reaction route. The effects of sintering temperature on the crystal structure, microstructure, densification, dielectric properties, and ferroelectric properties of the KNNLS ceramics were addressed. X-ray diffraction patterns and Raman spectrum indicated a transition from orthorhombic to tetragonal phase during the sintering temperature region. This transition is attributed to the migration of Li between the matrix grain and grain boundary. Scanning electron microscopy study revealed increased grain size and enhanced densification with increasing sintering temperature. The density of the ceramics sintered at 1080 °C reached a maximum value of 4.22 g/cm³. KNNLS ceramics sintered at an optimum temperature of 1080 °C exhibited high piezoelectric properties, that is 242 pC/N for d₃₃, 0.42 for k_p and 18.2 μC/cm² for P_r.     

Densification and mechanical properties of hot-pressed ZrN ceramics doped with Zr or Ti

The densification of hot-pressed ZrN ceramics doped with Zr or Ti have been investigated at 1500–1700 °C. It is shown that either Zr or Ti additive can facilitate the densification process. ZrN with 20 mol% Zr or Ti (named ZNZ and ZNT) sintered at 1700 °C can achieve above 98% relative densities whereas densification temperature up to 2000 °C is necessary for pure ZrN. The densification improvements are attributed to solid solution of Zr or Ti into ZrN to form non-stoichiometric ZrN_1?x or (Zr, Ti)N_1?x. The microstructures and mechanical properties of ZNZ and ZNT samples have been examined. Large grain size and flat fracture surface existed in ZNT sample sintered at 1700 °C, which lead to poor toughness as low as 2.3 MPa m^1/2. On the contrary, the fracture toughness of ZNZ sample sintered at 1700 °C was up to 5.9 MPa m^1/2, attributed to fine and uniform grain size distribution.     

Improvement of the piezoelectric and ferroelectric properties of (K,Na)0.5NbO3 ceramics via two-step calcination–milling route

A second calcination–milling step was introduced in the conventional processing of (K, Na)_0.5NbO₃ (KNN) ceramics (sintered in air) to further homogenenize the particle size distribution of the pre-sintered powders. The ceramic derived from the powders prepared by the two-step route possesses grains with better uniformity and is more compact. The relative density of the bulk ceramic reached 96.9%. Excellent properties are obtained in as-prepared KNN ceramics with k_p=44%, d₃₃=111 pC/N, tanδ=0.85%, ε₃₃^T/ε_o=311, Q_m=193, P_r=25.4 μC/cm², d₃₃^⁎=251 pm/V, which are superior to those of the ceramics derived from the powders calcined once as used in the traditional processing. These results indicate that twice-calcination–milling route is shown to be a facile and effective way to simultaneously improve the piezoelectric and ferroelectric properties of KNN ceramics without sintering aids.     

Effect of high energy milling process on microstructure and piezoelectric/dielectric properties of K0.475Na0.475Li0.05NbO3 solid solution

K_0.475Na_0.475Li_0.05NbO₃ (abbreviated as NKLN) ceramic of near the morphotropic phase boundary (MPB) composition was synthesized by two different processes. The first one is the high energy milling [sometimes abbreviated as HEM hereafter] process, which involves mixing the starting materials and milling the calcined powder using a high energy nano-mill, in order to obtain nano-sized particles. The second one is a conventional mixed oxide method. The HEM process of the starting materials lowered the calcination temperature to the extent of 200 °C as compared with conventionally fabricated NKLN. The particle size of the powder, exposed to the HEM process, reduced to 40 nm, whereas the conventionally ball-milled powder had a larger size of 420 nm after the mixing process. Furthermore, the HEM process improved the reaction activity and homogeneity of the materials used throughout the process, accompanying the enhancement of the sintering density, grain uniformity, and the decrease of grain size. In order to investigate the effects of the HEM process on the electric properties of NKLN ceramics, the dielectric and piezoelectric properties of sintered specimens fabricated by two different processes were evaluated. It was found that the properties of the nano-sized NKLN ceramic near the MPB composition were increased by the modified method, showing the maximum values of d₃₃=179 pC/N, k_p=34% and K₃₃^T=440 compared with 132 pC/N, 29%, and 400, respectively in the conventional process. Further evidence for the grain size effect was investigated by the polarization–electric field curve at room temperature. The remnant polarization for the nano-sized NKLN specimen had a higher value of 24.3 μC/cm² compared with that of 13.7 μC/cm² for conventional NKLN, whereas the coercive field had a similar value. The modified mixing and milling method was considered to be a new and promising process for lead-free piezoelectric ceramics owing to their excellent piezoelectric/dielectric properties.     

Ceramic tiles derived from coal fly ash: Preparation and mechanical characterization

Coal fly ash (CFA) accounts for a large fraction of the solid waste produced in China. Hence, there is an urgent need for the effective utilization of CFA, for example, as a raw material for ceramics production. In this study, clay- and feldspar-like materials fabricated by alkali activation pre-treatment of CFA were mixed with untreated CFA (regarded as a quartz-like material) and sintered to prepare fully ash-based ceramic tiles. The obtained tiles exhibited excellent sintering properties, e.g., low firing temperature and a wide sintering range; further, they showed better green strength (due to hydrogen bonding) and post-sintering performance (due to fluxing and mullite skeleton effects) than ceramic tiles produced exclusively from untreated CFA. The fully ash-based ceramic tiles sintered at 1100 °C exhibited optimal post-sintering properties (bulk density, 2.5 g/cm³; rupture modulus, 50.1 MPa; and water absorption, 0%). Thus, the proposed method is well suited for preparing a novel kind of ceramic tiles completely derived from CFA, highlighting its importance in the field of fly ash ceramics.     

Effects of TiO2 starting materials on the synthesis of Li2ZnTi3O8 for lithium ion battery anode

Lithium zinc titanate (Li₂ZnTi₃O₈) anode materials have been successfully synthesized using rutile-TiO₂ with different particle sizes as titanium sources via a molten-salt method. Various physical and electrochemical methods are applied to characterize the effects of TiO₂ particle sizes on the structures and physicochemical properties of the Li₂ZnTi₃O₈ materials. When the particle size of TiO₂ is too small (10 nm), it is difficult to homogeneously mix TiO₂ with the other raw materials. Thus, the final product Li₂ZnTi₃O₈ has poor crystallinity, large particle size, small specific surface area, pore volume and average pore diameter, which are disadvantageous to its electrochemical performance. Using TiO₂ with the proper particle size of 100 nm as the titanium source, the Li₂ZnTi₃O₈ (R-100-LZTO) with excellent electrochemical performance can be obtained. At 1 A g⁻¹, 175.8 and 163.6 mA h g⁻¹ are delivered at the 1st and the 200th cycles, respectively. The largest capacities of 163, 133.3 and 122.5 mA h g⁻¹ are delivered at 2.5, 5 and 6 A g⁻¹, respectively. The good high-rate performance of the R-100-LZTO originates from the good crystallinity, small particle size, large specific surface area and average pore diameter, low charge-transfer resistance and high Li⁺ diffusion coefficient.     

Ni4Nb2O9 ceramics prepared by the reaction-sintering process

Fabrication of Ni₄Nb₂O₉ ceramics via a reaction-sintering process was investigated. A mixture of raw materials was sintered into ceramics by bypassing calcination and subsequent pulverization stages. Ni₄Nb₂O₉ phase appeared at 1300 °C and increased with increasing soak time. Ni₄Nb₂O₉ content was found >96% in 1350 °C/2 h sintering pellets. A density of 5.71 g/cm³ was obtained for pellets sintered at 1350 °C for 2 h. This reaches 96.5% of the theoretical density. As the sintering temperature increased to 1350 °C, an abnormal grain growth occurred and grains >100 μm could be found. ?_r of 15.4–16.9 are found in pellets sintered at 1200–1300 °C. Q × f increased from 9380 GHz in pellets sintered at 1200 °C to 14,650 GHz in pellets sintered at 1250 °C.