Preparation of Li2TiO3 ceramic with nano-sized pores by ultrasonic-assisted solution combustion

Li₂TiO₃ is a candidate material for tritium breeding in the future nuclear fusion reactor. In this study, Li₂TiO₃ powder was synthesized by ultrasonic-assisted solution combustion synthesis (USCS) in a single step. The ultrasonic transducer with the power of 1000 W was introduced in the synthesis process. The crystallite size of Li₂TiO₃ powder prepared by utilization of ultrasonic power is significantly decreased to ∼5.0 nm, while the one obtained without ultrasonic power is 20.0 nm. Li₂TiO₃ ceramic sintered from USCS powder at 800 °C exhibits the small grain size of 330 nm and the open pores size of 140 nm. The crush load of the ceramic reaches 37.2 N although the structure is porous. Compared with the ceramic prepared by solid-state reaction and conventional solution combustion synthesis, USCS sample has a higher conductivity of 2.0 × 10⁻⁶ S m⁻¹ at room temperature, indicating the lower tritium diffusion barrier in the ceramic.     

Temperature stability and high-Qf of low temperature firing Mg2SiO4–Li2TiO3 microwave dielectric ceramics

In this work, a series of low-temperature-firing (1−x)Mg₂SiO₄–xLi₂TiO₃–8 wt% LiF (x = 35–85 wt%) microwave dielectric ceramics was prepared through conventional solid state reaction. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses showed that the Li₂TiO₃ phase was transformed into cubic phase LiTiO₂ phase and secondary phase Li₂TiSiO₅. Partial substitution of Mg²⁺ ions for Ti³⁺ ions or Li⁺Ti³⁺ ions increased the cell volume of the LiTiO₂ phase. The dense microstructures were obtained in low Li₂TiO₃ content (x ≤ 65 wt%) samples sintered at 900 °C, whereas the small quantity of pores presented in high Li₂TiO₃ content (x ≥ 75 wt%) samples sintered at 900 °C and low Li₂TiO₃ content (x = 45 wt%) sintered at 850 and 950 °C. Samples at x = 45 wt% under sintering at 900 °C for 4 h showed excellent microwave dielectric properties of ε_r = 10.7, high Q × f = 237,400 GHz and near-zero τ_f = − 3.0 ppm/°C. The ceramic also exhibited excellent chemical compatibility with Ag. Thus, the fabricated material could be a possible candidate for low temperature co-fired ceramic (LTCC) applications.     

A novel low-firing microwave dielectric ceramic Li2ZnGe3O8 with cubic spinel structure

A Li₂ZnGe₃O₈ ceramic was investigated as a promising microwave dielectric material for low-temperature co-fired ceramics applications. Li₂ZnGe₃O₈ ceramic was prepared via the conventional solid-state method. X-ray diffraction data shows that Li₂ZnGe₃O₈ ceramic crystallized into a cubic spinel structure with a space group of P4₁32. Dense ceramic with a relative densities of 96.3% were obtained when sintered at 945 °C for 4 h and exhibited the optimum microwave properties with a relative permittivity (ε_r) of 10.3, a quality factor (Q × f) of 47,400 GHz (at 13.3 GHz), and a temperature coefficient of resonance frequency (τ_f) of −63.9 ppm/°C. The large negative τ_f of Li₂ZnGe₃O₈ ceramic could be compensated by rutile TiO₂, and 0.9Li₂ZnGe₃O₈–0.1TiO₂0·1TiO₂ ceramic sintered at 950 °C for 4 h exhibited improved microwave dielectric properties with a near-zero τ_f of −1.6 ppm/°C along with ε_r of 11.3 and a Q × f of 35,800 GHz (11.6 GHz). Moreover, Li₂ZnGe₃O₈ was found to be chemically compatible with silver electrode when sintered at 945 °C.     

Comparison of the microwave and conventional sintering of Li2TiO3 ceramic pebbles

Microwave sintering was employed in the fabrication of Li₂TiO₃ ceramic pebbles using the powders synthesized via hydrothermal method. The as-prepared Li₂TiO₃ powders exhibited high reactivity with an average particle size as small as 40?nm. A comparative study between the microwave and conventional sintering behavior of Li₂TiO₃ pebbles was systematically investigated. The microstructure and density analyses showed that the presence of microwaves accelerated the densification and grain growth, thus decreasing the sintering temperature. Besides, an accelerated phase transformation from α-Li₂TiO₃ to β-Li₂TiO₃ was observed in microwave processing. The Li₂TiO₃ ceramic pebbles obtained by microwave sintering exhibited high density, good mechanical property and uniform microstructure, which might hold good potential as tritium breeding materials for blankets. The results showed that the microwave sintering was a promising process for the fabrication of Li₂TiO₃ pebbles.     

Parallel preparation and properties investigation on Li2O-Nb2O5-TiO2 microwave dielectric ceramics

A parallel preparation method was developed using dry powders as starting materials to synthesize multi-compositional microwave dielectric ceramics. The Li₂O-Nb₂O₅-TiO₂ ternary system was investigated as a model material. The validity of the parallel ceramic preparation process was confirmed by synthesizing a group of LiNb_0.6Ti_0.5O₃ ceramics in parallel, which showed the same crystalline structure and close dielectric properties. The ceramic libraries with M-phase-rich samples and Li₂TiO₃-rich samples were prepared using the parallel process, and the microwave dielectric properties and crystal phases were investigated systematically. An excellent microwave ceramic with a composition of 0.55Li₂O-0.05Nb₂O₅-0.40TiO₂ was obtained, which has a dielectric constant of 18.4 and a high quality value (Q × f) of 79000 GHz. This parallel process can be applied extensively to explore a variety of bulk ceramic libraries for discovering new functional materials with high performances.     

Sacrificial template synthesis of core-shell SrTiO3/TiO2 heterostructured microspheres photocatalyst

The core-shell SrTiO₃/TiO₂ heterostructure was obtained via a combined hydrothermal route and calcination treatment using amorphous spherical TiO₂ as both template and reactant. Adjusting the hydrothermal environments can control the morphology of the post-calcined sample when it is hydrothermally treated at 180 °C/3 h and 200 °C/6 h, respectively. Following the heat treatment at 700 °C/4 h, the obtained powder illustrates the core-shell heterostructure with a hierarchical surface, and the diameter of the microsphere is about 700 nm. This synthesizing route facilitates the formation of a concentration gradient of SrTiO₃ and TiO₂, and subsequently constructs a gradient energy level, which helps the samples exhibited an excellent de-colorize activity over the methylene blue. The possible formation mechanism of core-shell SrTiO₃/TiO₂ heterostructures was proposed to guide the further improvement of their photocatalytic activity.     

Synthesis of rod-like β-Si3N4 seed crystals with tailored morphology

β-Si₃N₄ seed crystals were synthesized by sintering (α+β)-Si₃N₄ powders with Y₂O₃+MgO additives at 1800 °C. Full α- to β-phase transformation was achievable at 1800 °C for 1 h. The pre-existing β-Si₃N₄ particles acted as nuclei during a sintering process. The length and mean aspect ratio of β-Si₃N₄ seed grains could be tailored by careful control of α/β-Si₃N₄ ratio, which resulted in various nuclei and driving force. The sample A95B5 with 5% β-nuclei shows a bimodal size distribution containing large amount of abnormal elongated β-Si₃N₄ grains with remarkable large diameter. With increasing the β-phase content from 5 wt% to 100 wt%, the average diameter and aspect ratio of the β-Si₃N₄ single crystals decreased from 1.43 µm to 0.92 µm and from 4.36 to 2.79, respectively.     

A novel Li2TiO3–Li2CeO3 ceramic composite with excellent microwave dielectric properties for low-temperature cofired ceramic applications

A novel low-temperature sinterable (1 ? x)Li₂TiO₃-xLi₂CeO₃ (x = 0.08 ? 0.16 in molar) microwave dielectric ceramic was successfully prepared by a conventional solid-state reaction method. The X-ray diffraction and scanning electron microscopy analysis revealed the coexistence of two phases with different structures owing to their good chemical stability. Their relative content was easily adjusted to achieve near-zero temperature coefficient of the resonant frequency (τ_f) according to the mixing rule of dielectrics. The low-temperature sintering and desirable microwave dielectric properties can be simultaneously achieved by adding Li₂CeO₃ to the Li₂TiO₃ matrix owing to its low-firing characteristic and opposite-sign τ_f. The composite ceramics with x = 0.14 could be well sintered at 850 °C and exhibited excellent microwave dielectric properties of ε_r ～ 21.2, Qxf～ 59,039 GHz and τ_f ～?7.4 ppm/°C. In addition, no chemical reaction was identified between the matrix phase and Ag, suggesting that the Li₂TiO₃-Li₂CeO₃ ceramics might be promising candidates for low-temperature co-fired ceramic applications.     

Optical,thermal and dielectric properties of Bi4(TiO4)3 ceramic powders

Bismuth titanate (Bi₄(TiO₄)₃) ceramic powders have been synthesized by using a solid state reaction method. Prominently intense blue emission at 480 nm has been measured with an excitation at 418 nm. The reason for the observance of such a blue emission from this ceramic powder has been explained. The phase formation has been investigated by X-ray diffraction analysis (XRD). The morphology and composition of the ceramic powders have been studied from the measurement of SEM and EDS profiles. FTIR and Raman spectra have also been recorded to analyze the presence of functional groups and Raman active modes in the Bi₄(TiO₄)₃ ceramic powders. The sintering temperature has been optimized to be 1100 °C based on the measured TG–DTA profiles of the as prepared material. Besides these, dielectric properties of ceramic powder in the frequency range of 200 Hz–3 MHz at 300 K have also been carried out.     

Effect of fuel-to-oxidizer ratios on combustion mode and microstructure of Li2TiO3 nanoscale powders

A single phase Li₂TiO₃ powder has been fabricated through a facile solution combustion process, using citric acid as the fuel and corresponding nitrates as oxidants. The effect of fuel-to-oxidizer ratio (0.5–1.5) on the combustion process, the phase and microstructure of the products was investigated. By using different combinations of citric acid fuel and metal nitrates, the combustion mode could be controlled. When the fuel-to-oxidizer ratio is 0.75, an eruption combustion mode is realized. Thermodynamic analysis of the combustion reaction shows that as the fuel-to-oxidizer ratio increases, the adiabatic flame temperature during combustion also increases, but the measured maximum temperature decreases. The crystallite size of Li₂TiO₃ powders was calculated to be 18–36 nm at different combustion modes. The as-prepared Li₂TiO₃ powders exhibit excellent sinterability and can be sintered to 90.7% of the theoretical density at 800 °C. The grain size of the Li₂TiO₃ ceramics is around 800 nm.     

Crystallization kinetics and magnetic properties of iron oxide contained 25Li2O–8MnO2–20CaO–2P2O5–45SiO2 glasses

With crystallization at 850 °C for 4 h, LiMn₂O₄, β-wollastonite (β-CaSiO₃), lithium silicate (Li₂SiO₃), Ca(Ca, Mn)Si₂O₆ and Li₂Ca₄Si₄O₁₃ phases were found in 25Li₂O–8MnO₂–20CaO–2P₂O₅–45SiO₂ (LMCPS) glass ceramics. The (Li, Mn)ferrite phase was obtained in the iron oxide contained LMFCPS glass ceramic and Li₂FeMn₃O₈ phase was found in that containing 8 at.% Fe₂O₃. TEM investigations showed that (Li, Mn)ferrite particles dispersed in the β-wollastonite matrix (Li, Mn)ferrite particles, with an average size of 40 nm, were found in the glass ceramics containing 4 at.% Fe₂O₃. The (Li, Mn)ferrite particle sizes in the glass ceramics containing 8 at.% Fe₂O₃ varied from a few μm to 5 nm. The SQUID result showed that only the glass ceramic containing 4 at.% Fe₂O₃ exhibited super-paramagnetic behavior at temperature 300 K and ferromagnetic behavior at 4 K. The LMCPS glass ceramic containing 8 at.% Fe₂O₃ exhibited ferromagnetic behavior at both temperatures.     

Fabrication of nanostructured Li2TiO3 ceramic pebbles as tritium breeders using powder particles synthesised via a CTAB-assisted method

Nanostructured Li₂TiO₃ ceramics which may have effective thermal conductivity, excellent tritium release behaviour and good irradiation resistance are regarded as a promising solid tritium breeding material for the fusion reactor blanket of the International Thermonuclear Experimental Reactor (ITER). However, due to the limitations of the preparation technology, reports concerning Li₂TiO₃ nanoceramics have been rare. In this paper, uniform nano-Li₂TiO₃ powder particles which were essential to obtain nanostructured Li₂TiO₃ ceramics pebbles were synthesised via a cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal method, and then rare, homogeneous nanostructured Li₂TiO₃ ceramic pebbles were fabricated with the as-prepared powder particles. The mechanisms by which CTAB can reduce particle agglomeration and be of assistance in achieving a nanostructured Li₂TiO₃ ceramic were also investigated. In addition, systematic experiments on the relationship between the added amount of CTAB and the mechanical properties of the Li₂TiO₃ ceramic structure were also carried out. The results revealed that the desired Li₂TiO₃ nanoceramic could be fabricated when 3% CTAB was introduced, as the Li₂TiO₃ pebbles obtained had a small grain size (90 nm), high relative density (89.71%T.D.) and crush load (99.93 N), which were expected to show favourable potential as a promising tritium breeder material in the fusion reactor blanket.     

A comparative study on the properties of Li2TiO3 powders and pebbles fabricated by different routes

Lithium titanate (Li₂TiO₃) is one of the promising candidate breeders for tritium self-sufficiency of deuterium(D)-tritium(T) fusion reaction. The differences in powder synthesis methods have a great impact on the properties of Li₂TiO₃ powders and the performance of Li₂TiO₃ ceramic pebbles. In this study, the Li₂TiO₃ powders were successfully synthesized by hydrothermal method and solid-state method, and then the pebbles were fabricated by the agar-based wet method. The mechanism of hydrothermal synthesis of Li₂TiO₃ powder was discussed. For the hydrothermal method, the Li₂TiO₃ powder with single phase can be obtained when the rate of Li/Ti = 2.4, and the powder presented two different morphology, which involved two reaction mechanisms, including in-situ phase transformation mechanism and dissolution-precipitation mechanism, the phase transformation from α-Li₂TiO₃ to β-Li₂TiO₃ accomplished at 400°C, which is lower than that of 750°C for solid-state method. Li₂TiO₃ pebbles prepared by the hydrothermal-wet method had a uniform pore distribution, an optimal grain size of 2.7 μm, a crushing load of 58.6 N, and relative density of 90.2%, respectively. In comparison, pebbles prepared by the solid-state-wet method also had better mechanical properties, which the crushing load and relative density were 53.9 N and 86.9% respectively under the optimal fabrication conditions.     

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.     

Low-temperature sintered Bi0.5Na0.5TiO3-SrTiO3 incipient piezoceramics and the co-fired multilayer piezoactuator thereof

Lead-free Bi_0.5Na_0.5TiO₃-SrTiO₃ incipient piezoceramics with Li₂CO₃ and MnO₂ additives were successfully fabricated at low firing temperature for applications in co-fired multilayer piezoactuators. The addition of Li₂CO₃ effectively shifted the sintering temperature from 1230 °C down to 1075 °C, where the ceramics were co-fired with a Ag/Pd (75/25) inner electrode. The prototype actuators were prepared by tape-casting method using ceramics with the composition of 0.74Bi_0.5Na_0.5TiO₃-0.26 SrTiO₃ + 0.15 wt%MnO₂ + 0.45 wt%Li₂CO₃. The total number of active layers was 13, and each ceramic layer had a thickness of 60 μm. The actuator output a large strain up to ∼0.20% at a driving field of 4 kV/mm, due to the field-induced phase transition between the ergodic relaxor and ferroelectric phases. The excellent voltage-displacement performance of the prototype actuator demonstrates the potential for industrial applications.     

Graphite–lithium–europium system: Modulation of the structural and physical properties of the lamellar phases as a consequence of their chemical composition

This paper summarizes the whole chemical, structural and magnetic properties collected in the graphite–lithium–europium system. The intercalation mechanisms which occur during reactions between graphite and lithium–europium liquid alloys have been identified. The investigation of the experimental parameters leads to the optimized conditions to isolate europium-based graphite intercalation compounds (GICs) denoted α-phase and γ-phase. The ion beam analysis has been carried out to simultaneously quantify the amount of carbon, lithium and europium in a same sample. The α-phase shows a homogeneous distribution of the elements laterally and in depth, with a Li_0.2Eu₂C₆ chemical formula. The unexpected presence of lithium has been revealed in the γ-phase but the EuC₆ GIC is clearly detected, in agreement with X-ray diffraction experiments. The structural properties of Li_0.2Eu₂C₆ have been studied and a Li–Eu–Eu–Eu–Li poly-layered sheet intercalated between graphene planes has been showed along the c-axis, with c = 3.I_C = 2400 pm. The presence of lithium allows the building of a poly-layered metallic structure leading to specific magnetic properties different from those of EuC₆. In the latter case, lithium does not affect either the structural or the magnetic properties of the intercalation compound.     

Microwave dielectric properties of CaWO4–Li2TiO3 ceramics added with LBSCA glass for LTCC applications

In this work, 0.86CaWO₄–0.14Li₂TiO₃ ceramics were prepared via a traditional solid-state process. The effects of Li₂O–B₂O₃–SiO₂–CaO–Al₂O₃ (LBSCA) addition on the phase formation, sintering character, microstructure and microwave dielectric properties of the ceramics were investigated. A small amount of LBSCA addition could effectively lower the sintering temperature of the ceramics. X-ray diffraction analysis revealed that CaWO₄ and Li₂TiO₃ phases coexisted without producing any other crystal phases in the sintered ceramics. The dielectric constant and Qf values were related to the amount of LBSCA addition and sintering temperatures. All specimens could obtain near-zero temperature coefficient (τ_f) values through the compensation of the positive τ_f of Li₂TiO₃ and the negative τ_f of CaWO₄. The 0.86CaWO₄–0.14Li₂TiO₃ ceramic with 0.5 wt% LBSCA addition and sintered at 900 °C for 3 h exhibited excellent microwave dielectric properties of ε_r=12.43, Qf=76,000 GHz and τ_f=−2.9 ppm/°C.     

Investigation of a high stable β-cristobalite ceramic powder from CaO–Al2O3–SiO2 system

The room temperature stabilized β-cristobalite ceramic powder has great potential for use in production of engineering ceramic materials due to its high resistance to thermal shock, low expansion coefficient, high chemical resistance and low density. However, the use of this material is not common in ceramic industries. The problem is shown to be the instability of β-phase during milling. The applied external force leads to phase transformation to α-cristobalite and thus the material shows poor thermal stability and so on. In this study, a reliable β-cristobalite ceramic powder from CaO–Al₂O₃–SiO₂ ternary system was investigated at different compositions and under various sintering temperatures and sintering times. The phase stability of the powder sample was investigated by milling for 50 h using a planetary mill. The crystalline phases were examined by X-ray and FTIR analysis and the results were discussed with respect to the phase homogeneity through the particle mass.     

Efficient α/β-Bi2O3 composite for the sequential photodegradation of two-dyes mixture

A mixture of α/β-Bi₂O₃ and α-Bi₂O₃ powders were obtained by a simple solid state reaction–annealing route at 550 °C. The structure, optical properties and surface area of the commercial α and β-Bi₂O₃ and the synthesized α-phase and α/β-composite were well characterized by X-ray diffraction, diffuse reflectance spectra and N₂ physisorption. The annealed sample at 550 °C showed 20% of β-phase, forming a heterojunction of α/β-Bi₂O₃ whereas annealing at elevated temperature (650 °C) lead to the α-phase. Optical properties showed that the presence of the β-phase is mainly responsible for narrowing the energy band gap. The photocatalytic activity of the commercial α and β-Bi₂O₃ and the synthesized α-phase and α/β-composite were investigated in degradation of single dyes, Indigo Carmine (IC) and Rhodamine-B (RhB) under both UV and visible light-induced photocatalysis. For the best photocatalyst, the photodegradation in a two-dye mixture solution was systematically studied considering the type of dye, the adsorption capacity of the samples and the behavior of dye photodegradation. The photocatalytic performance of α/β-Bi₂O₃ was comparatively much higher than the commercial α and β-Bi₂O₃, indicating that better performance of efficient charge separation and transfer across α/β-Bi₂O₃ composite was obtained. Possible mechanism of the single dye and two-dye mixture degradation was given by using α/β-Bi₂O₃ composite.     

Raman spectra and extended X-ray absorption fine structure characterization of La(2−x)/3NaxTiO3 and Nd(2−x)/3LixTiO3 microwave ceramics

A-site deficient perovskite compounds, La_(2?x)/3Na_xTiO₃ (0.02 ≤ x ≤ 0.5) and Nd_(2?x)/3Li_xTiO₃ (0.1 ≤ x ≤ 0.5) microwave ceramics, were investigated by Raman scattering. Nd_(2?x)/3Li_xTiO₃ (0.1 ≤ x ≤ 0.5) was also investigated by extended X-ray absorption fine structure (EXAFS) measurement. The Raman shifts of the E (239 cm^?1) and A₁ (322 cm^?1) modes of La_(2?x)/3Na_xTiO₃ were found to decrease with x. However, the E (254 cm^?1) and A₁ (338 cm^?1) of Nd_(2?x)/3Li_xTiO₃ were found to blueshift with x, which was caused by Li substitution. The redshift of the A₁ (471 cm^?1) phonon of Nd_(2?x)/3Li_xTiO₃ (0.1 ≤ x ≤ 0.3) indicates that O–Ti–O bonding forces lessen with Li concentration, which is consistent with the EXAFS result that Ti–O bond lengths increase for 0.1 ≤ x ≤ 0.3. For x > 0.3, the EXAFS result shows that Ti–O bond lengths decrease. Moreover, Ti–O bond lengths show strong correlation with the microwave dielectric constants of Nd_(2?x)/3Li_xTiO₃.