Solubility and microstructural development of TiO2-containing 3Al2O3·2SiO2 and 2Al2O3·SiO2 mullites obtained from single-phase gels

The interdependence of the titanium oxide amount and the anisotropic growth of mullites prepared from single-phase gels were investigated. Gels with stoichiometries 3(Al_2−xTi_xO₃)·2(SiO₂) and 2(Al_2−xTi_xO₃)·(SiO₂), with 0 ≤ x ≤ 0.15 were prepared by the semialkoxide method. Gels and specimens heated at temperatures between 1200 and 1600 °C were characterized by using infrared spectroscopy (IR), X-ray diffraction (XRD) and transmission and field emission scanning electron microscopies (TEM and FESEM). Al₂TiO₅ as minor impurity was detected in both series of mullites for gel precursor compositions x = 0.10 and x = 0.15, obtained at temperatures between 1200 and 1600 °C. Variations of lattice parameters of mullite, processed at temperatures from the range between 1400 and 1600 °C, with the starting nominal amount of titanium oxide indicated that the solubility limit of titanium oxide was in ranges 3.8–4.1 and 4.1–4.4 wt% TiO₂ for 3:2 and 2:1 mullites series, respectively. The anisotropic growth of titanium-doped mullite crystalline grains was significant only when the nominal amount of titanium oxide exceeded the limit of solubility into the mullite structure (for both mullite series). Stronger anisotropy occurred for the 3:2 series specimens, i.e. for the SiO₂-richer mullites. In both series of mullites, the anisotropic grain growth was observed for the process temperatures higher than 1400 °C; the crystalline grains of mullites processed at lower temperatures were equiaxials and of almost the same size.     

Dielectric Properties of Ba0.8Ca0.2TiO3–Bi(Mg0.5,Ti0.5)O3–NaNbO3 Ceramics

Ceramics in the system 0.45Ba_0.8Ca_0.2TiO₃–(0.55?x)Bi(Mg_0.5Ti_0.5)O₃–xNaNbO₃, x = 0–0.02 were fabricated by a conventional solid‐state reaction route. X‐ray powder diffraction indicated cubic or pseudocubic symmetry for all samples. The parent 0.45Ba_0.8Ca_0.2TiO₃–0.55Bi(Mg_0.5Ti_0.5)O₃ composition is a relaxor dielectric with a near‐stable temperature coefficient of relative permittivity, ε_r = 950 ± 10% across the temperature range 80°C–600°C. Incorporation of NaNbO₃ at x = 0.2 extends the lower working temperature to ≤25°C, with ε_r = 575% ± 15% from temperatures ≤25°C to >400°C, and tan δ < 0.025 from 25°C to 400°C. Values of dc resistivity ranged from ~10⁹ Ω·m at 250°C to ~10⁶ Ω·m at 500°C. The properties suggest that this material may be of interest for high‐temperature capacitor applications.     

Experimental study and DFT calculations of improved giant dielectric properties of Ni2+/Ta5+ co-doped TiO2 by engineering defects and internal interfaces

High-performance ceramics with chemical formula (Ni_1/3Ta_2/3)_xTi_1?xO₂ with excellent dielectric properties are demonstrated. The dopants of Ni²⁺ and Ta⁵⁺ in TiO₂ caused the formation of oxygen vacancies and free electrons. The (Ni_1/3Ta_2/3)_xTi_1?xO₂ exhibited low loss tangent of 0.046 and a high dielectric permittivity of 3.5–4.5 × 10⁴ with a very weak dependence on temperature (?60 to 200 °C). Broadband dielectric spectroscopy shows at least four dominant sources in the dielectric relaxation response in the temperature range of ? 253–210 °C. DFT calculations indicate the formation of defect clusters, which are the largest contributors to the dielectric response, and these are found to be dominant even at temperatures down to ? 253 °C. Both grain boundary and surface layer mechanisms in the ceramics contribute to the dielectric response at the relatively high temperatures. The sample–electrode contact effect associated with oxygen vacancy diffusion is dominant at high temperatures above 150 °C.     

Stability of High‐Temperature Dielectric Properties for (1 − x)Ba0.8Ca0.2TiO3–xBi(Mg0.5Ti0.5)O3 Ceramics

Ceramics in the solid solution system, (1 ? x)Ba_0.8Ca_0.2TiO₃–xBi(Mg_0.5Ti_0.5)O₃, were prepared by a conventional mixed oxide route. Single‐phase perovskite‐type X‐ray diffraction patterns were observed for compositions x < 0.6. A change from tetragonal to single‐phase cubic X‐ray patterns occurred at x ≥ 0.1. Dielectric measurements indicated relaxor behavior for x ≥ 0.1. Increasing the Bi(Mg_0.5Ti_0.5)O₃ content improved the temperature sensitivity of relative permittivity ?_r at high temperatures. At x = 0.5, a near‐plateau relative permittivity, 835 ± 40, extended across the temperature range, 65°C–550°C; the permittivity increased at x = 0.6 to 2170 ± 100 for temperatures 160°C–400°C (1 kHz). The corresponding loss tangent, tanδ, was ≤0.025 for temperatures between 100°C and 430°C for composition x = 0.5; at x = 0.6, losses increased sharply at >300°C. Comparisons of dielectric properties with other materials proposed for high‐temperature capacitor applications suggest that (1 ? x)Ba_0.8Ca_0.2TiO₃–xBi(Mg_0.5Ti_0.5)O₃ ceramics are a promising base material for further development.     

Microstructure and High‐temperature Oxidation Behavior of Ti3AlC2/W Composites

Using spark plasma sintering, Ti₃AlC₂/W composites were prepared at 1300°C. They contained “core‐shell” microstructures in which a Ti_xW_1?x “shell” surrounded a W “core”, in a Ti₃AlC₂ matrix. The composite hardness increased with W addition, and the hardening effect is likely achieved by the Ti_xW_1?x interfacial layer providing strong bonding between Ti₃AlC₂ and W, and by the presence of hard W. Microstructural development during high‐temperature oxidation of Ti₃AlC₂/W composites involves α‐Al₂O₃ and rutile (TiO₂) formation ≥1000°C and Al₂TiO₅ formation at ~1400°C while tungsten oxides appear to have volatilized above 800°C. Likely due to exaggerated, secondary grain growth of TiO₂‐doped alumina and the effect of W addition, fine (<1 μm) Al₂O₃ grains formed dense, anisomorphic laths on Ti₃AlC₂/5 wt%W surfaces ≥1200°C and coarsened to large (>5 μm), dense, TiO₂‐doped Al₂O₃ clusters on Ti₃AlC₂/10 wt%W surfaces ≥1400°C. W potentially affects the oxidation behavior of Ti₃AlC₂/W composites beneficially by causing formation of Ti_xW_1?x thus altering the defect structure of Ti₃AlC₂, resulting in Al having a higher activity and by changing the scale morphology by forming dense Al₂O₃ laths in a thinner oxide coating, and detrimentally through release of volatile tungsten oxides generating cavities in the oxide scale. For Ti₃AlC₂/5 wt%W oxidation, the former beneficial effects appear to dominate over the latter detrimental effect.     

Preparation and sealing effects of Mg–Al–Si–Ba–O-based glass-ceramic coatings on NTC thermistors

Herein, Mg–Al–Si–Ba–O-based glass ceramics were studied as potential candidates to protect Mn–Co–Ni–O-based negative temperature coefficient (NTC) thermistors at high temperatures such as 900 °C. The ceramics were prepared in three glass formulations (1#: 15MgO–15Al₂O₃-44.7SiO₂–25BaO, 2#: 17MgO–17Al₂O₃–41SiO₂–25BaO and 3#: 17MgO–17Al₂O₃–41SiO₂–20BaO–5Y₂O₃ (in mol%)) and their glass-transition temperatures (T_g) were determined using the differential scanning calorimetry (DSC) method. Scanning electronic microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the parent glasses and glass-ceramic coatings. The sealing effects of the glass ceramics were examined by conducting an insulation test. The glass-ceramic sealing structures were subjected to 1000 thermal shock cycles at temperatures varying from room temperature to 900 °C. Notably, the sealing structure of glass-ceramic coating 1# was compact at a T_g of 760.9 °C. The glass-ceramic coatings effectively maintained the NTC properties of the sensitive ceramics in all three formulations. Interestingly, the glass-ceramic coating 3# containing Y₂O₃ demonstrated an increase in electrical resistance. Both the NTC thermistors coated with 1# and 2# glass formulations successfully passed 1000 thermal shock cycles without visible failures, and their resistance change ratios were well below the requisite 20%.     

Glass-ceramics for joining oxide-based ceramic matrix composites (Al2O3f/Al2O3-ZrO2) operating under direct flame exposure

This work focuses on the joining processes of oxide-based ceramic matrix composites (Al₂O_3f /Al₂O₃-ZrO₂), which are used as radiant tube furnace components in the steel industry. These components have to operate in harsh environments, and under high temperatures, and they therefore have to resist corrosion, humidity, and combustion. Two glass-ceramics systems, which have Y₂Ti₂O₇ as their main crystalline phase, as well as specific and optimized properties to withstand severe operating conditions, including temperatures of 900 °C, are here proposed as joining materials. The adhesion of the glass-ceramics to the composite was found to be excellent after mechanical and thermal tests in which they were in direct contact with a 900 °C flame and thermal cycling of between 400 °C and 900 °C.     

Phase evolution in reaction sintered zirconium titanate based materials

Zirconium titanate materials are proposed for structural components for which fully reacted and relatively large pieces are required. In this work the phase evolution in slip cast compacts constituted by equimolar mixtures of TiO₂ and ZrO₂ stabilized with 3 mol% of Y₂O₃ at high temperature is studied, to establish the basis to design suitable thermal treatments for ZrO₂(Y₂O₃)–TiO₂ materials. The temperatures at which the processes involved in the reaction sintering occurred were identified by constant heating rate experiments. Phase and microstructure analyses have been performed on specimens treated at the identified temperatures and air quenched. Then the adequate temperature range to get fully reacted and dense materials has been deduced. Materials treated at 1500 °C to 2 h were constituted by Zr₅Ti₇O₂₄ as major phase, a solid solution of TiO₂ and Y₂O₃ in c-ZrO₂ as secondary phase and a ZrO₂–TiO₂–Y₂O₃ non-stoichiometric compound with pyrochlore structure as minor phase. Pyrochlore was demonstrated to be a metastable phase at 1500 °C.     

Phase formation and characterization of high Curie temperature xBiYbO3–(1 − x)PbTiO3 piezoelectric ceramics

Novel perovskite xBiYbO₃–(1 ? x)PbTiO₃ (BYPT) crystalline solutions were prepared by conventional ceramic processing. The effect of BiYbO₃ on the microstructure and electrical properties was investigated, and the reaction mechanism of phase formation was discussed. The results show that the proper calcining temperature is 860 °C and the optimum sintering temperature is 1140 °C. It is difficult for BYPT ceramics to obtain phase-pure perovskite structures. Pyrochlore phase Yb₂Ti₂O₇ was formed by Yb₂O₃ and TiO₂ that decomposed from BiYbO₃–PbTiO₃ at high temperature. With increasing BiYbO₃ content, the pyrochlore phase Yb₂Ti₂O₇ increases, which resulted in the decrease of densities and piezoelectric constants. The dielectric constants were in the range of 100–700 at room temperature and tan δ less than 4%. BYPT ceramics with high Curie temperatures of >500 °C are obtained. 0.1BiYbO₃–0.9PbTiO₃ ceramic is a very promising material for high-temperature (up to 550 °C) piezoelectric applications for high T_c, stable d₃₃, and high thermal-depoling temperature.     

Glass-ceramic route to NASICON-type NaxTi2(PO4)3 electrodes for Na-ion batteries

Glass-ceramic processes to prepare NASICON-type Na_xTi₂(PO₄)₃, which is an anode candidate for sodium-ion batteries, from 30Na₂O–40TiO₂–30P₂O₅ glass have been investigated with varied atmospheric conditions. By annealing in the inert (N₂) atmosphere, the glass started crystalizing into NASICON-type NaTi₂(PO₄)₃ with rhombohedral symmetry at ～600 °C followed by crystallization of other phases to be multiphase mixtures at higher temperatures. In contrast, in the reducing (5% H₂/Ar) atmosphere, NASICON-type Na₃Ti₂(PO₄)₃ with triclinic symmetry is crystallized at >～800 °C. The formation of Na₃Ti₂(PO₄)₃ is associated with a loss of excess oxygens in the initial glass composition and a reduction of Ti from Ti⁴⁺ to Ti³⁺. The reduction process upon the glass-to-ceramic conversion was traced by in-situ observation during the thermogravimetric analysis. It is also revealed that the electrochemical Na ⁺ -storage capabilities of the glass-ceramic electrodes are correlated with the Na-ion occupancy between these two phases, and their phase fractions affect the charge-discharge properties of Na-ion cells. Finer glass-ceramic powders could improve the electrochemical properties and achieve almost 80% of its theoretical capacity.     

Enhanced activity of MnxW0.05Ti0.95 − xO2 − δ for selective catalytic reduction of NOx with ammonia by self-propagating high-temperature synthesis

A series of TiO₂ supported MnWO_x catalysts Mn_xW_0.05Ti_0.95 − xO_2 − δ (x = 0.05, 0.1, 0.15) were synthesized by solution combustion method. The Mn_0.10W_0.05Ti_0.85O_2 − δ catalyst showed highest activity in NH₃-SCR reaction within a broad temperature range of 200 °C–400 °C. XRD and TEM results indicate that the active Mn and W species are highly dispersed over TiO₂ support in the form of nanoparticles (4–7 nm). The TEM and H₂-TPR results also suggest that a MnWO_x phase has been formed on the TiO₂, which is beneficial for the activity of the Mn_xW_0.05Ti_0.95 − xO_2 − δ catalysts in the high temperature range of 280 °C–400 °C.     

Characterization of single crystalline a-TiO2 films on MgAl2O4(100) substrates by MOCVD

Anatase phase TiO₂ (a-TiO₂) films have been deposited on MgAl₂O₄(100) substrates at the substrate temperatures of 500–650 °C by the metal organic chemical vapor deposition (MOCVD) method using tetrakis-dimethylamino titanium (TDMAT) as the organometallic (OM) source. The structural analyses indicated that the TiO₂ film prepared at 600 °C had the best single crystalline quality with no twins. The out-of-plane and in-plane epitaxial relationships of the film were a-TiO₂(001)||MgAl₂O₄(100) and TiO₂[100]||MgAl₂O₄[100], respectively. A uniform and compact surface with stoichiometric composition was also obtained for the 600 °C-deposited sample. The average transmittance of all the TiO₂ films in the visible range exceeded 91% and the optical band gap of the films varied from 3.31 to 3.41 eV.     

Oxidation Behavior of MAX Phase Ti2Al(1−x)SnxC Solid Solution

MAX phase Ti₂Al_(1?x)Sn_xC solid solution with x = 0, 0.32, 0.57, 0.82, and 1 was synthesized by pressureless sintering of uniaxially pressed Ti, Al, Sn, and TiC powder mixtures. Annealing in air atmosphere at 200°C–1000°C triggered a sequence of oxidation reactions which reveal a distinct influence of solid solution composition on the oxidation process. With decreasing Al/Sn ratio, the characteristic temperature of accelerated oxidation reaction of A‐element was reduced from 900°C (x = 0) to 460°C (x = 1). SnO₂ was formed at temperatures significantly lower than TiO₂ (rutile) and Al₂O₃. Substitution of A‐element in MAX phase solid solution by low‐melting elements such as Sn may offer potential for reducing oxidation‐induced crack healing temperatures.     

Annealed Ti3C2Tx: A green and tunable electromagnetic interference shielding material

Electromagnetic interference (EMI) shielding materials are receiving more and more attentions and becoming a hot research topic because of their wide range of applications in life, defense and other fields. The development of green EMI shielding materials with tunable shielding effectiveness (SE) is a high pursuit and a great challenge for researchers. Here, we restricted the growth of TiO₂ on the Ti₃C₂T_x surface by adjusting the annealing temperature. This regulated the dipole and interface polarization and the construction of the conductive network, and improved the impedance matching. The Ti₃C₂T_x/TiO₂ heterostructured material was rationally designed and achieved an efficient EMI SE of 35.1 dB at 18 GHz when the annealing temperature was 600 °C. This work develops new avenues for the future design of efficient, controllable green EMI shielding materials. Simultaneously, this heterostructured material has great potential as a versatile green shielding material for civil, commercial and military aerospace applications.     

Sintering behavior,structure and dielectric properties of CuO-ZnO-MgO-B2O3 glass-ceramics for ULTCC applications

High performance ultra-low temperature co-fired ceramic (ULTCC) materials were prepared from CuO- MgO- ZnO- Al₂O₃- B₂O₃- Li₂O glass-ceramics. The sintering behaviors, crystalline phase evolution, microstructure and dielectric properties, as well as their compatibility with Ag and Al electrodes, were investigated. With the suitable substitution of MgO for ZnO, the dielectric properties of glass-ceramics were improved. It is mainly associated with the fine microstructure, highly crystallinity, and decrease in tetrahedral distortion in the crystal lattice. All the glasses completed the densification at 575–600 °C, and ZnB₄O₇ is the only crystalline phase precipitated from the glasses. Moreover, the glass-ceramic with 1 wt% MgO sintered at 575 °C for 5 h, exhibited low relative permittivity ~ 7.1 and low dielectric loss ~ 6.40 × 10^?4. And the glass-ceramic with 4 wt% MgO sintered at 600 °C for 5 h, also displayed low relative permittivity ~ 7.1 and low dielectric loss ~ 5.77 × 10^?4. Both two glasses have good sintering compatibility with silver and aluminum electrodes, which provided high potential for ULTCC application.     

Tribological behavior of Ti3SiC2 and Ti3SiC2/Pb composites sliding against Ni-based alloys at elevated temperatures

The Ti₃SiC₂ and Ti₃SiC₂/Pb composites were tested under dry sliding conditions against Ni-based alloys (Inconel 718) at elevated temperatures up to 800 °C using a pin-on-disk tribometer. Detailed tribo-chemical changes of Pb on sliding surface were discussed. It was found that the tribological behavior were insensitive to the temperature from 25 °C (RT) to 600 °C (friction coefficient ≈0.61–0.72, wear rate ≈10⁻³ mm³ N m⁻¹). An amount of Pb in the composites played a key role in lubricating with the temperature below 800 °C. The friction coefficient (≈0.22) and wear rate (≈10⁻⁷ mm³ N m⁻¹) at elevated temperatures were both decreased by the added PbO. The wear mechanisms of Ti₃SiC₂/Pb-Inconel 718 tribo-pair at elevated temperatures were believed to be the combined effect of abrasive wear and tribo-oxidation wear. During the sliding, two oxidization reactions proceed, 2Pb+O₂=2PbO (below 600 °C) and 6PbO+O₂=2Pb₃O₄ (800 °C). The friction coefficient and wear rate of the composites were reduced due to the self-lubricating effect of the tribo-oxidation products.     

Mechanism on reduction and nitridation of micrometer-sized titania with ammonia gas

Ammonia gas can be simultaneously used as a reductant and nitrogen source to prepare TiN from titania. In this work, the mechanisms on reduction and nitridation of micrometer-sized anatase with ammonia gas have been investigated, using both thermodynamic and experimental studies. The thermodynamic analysis indicated that reduction and nitridation of TiO₂ by NH₃ was feasible. Anatase will undergo different paths to form TiN, depending on the reaction temperature. Upon heating, NH₃ was seen to partially decompose into N₂ and H₂, although the actual NH₃ decomposition ratio was less than the theoretical value. The experimental results indicated that the obtained titanium nitride was non-stoichiometric (TiN_xO_1−x, x ≤ 1), as it contained a certain amount of oxygen. Based on the phase transformation and X-ray photoelectron spectroscopy analysis, the reduction and nitridation routes were deduced: TiO₂ reacted with NH₃ to form TiN_xO_1−x directly, at lower temperatures, and followed the path TiO₂ → Ti_nO_2n−1 → TiN_xO_1−x, at higher temperatures. Ti_nO_2n−1 was determined to be Ti₄O₇ and Ti₃O₅ at 1100°C and 1200°C, respectively. Reaction temperature and time significantly affected the oxygen and nitrogen contents in TiN_xO_1−x, with the lattice parameter of roasted products gradually increasing—approaching those of pure TiN—with an increase in reaction temperature and holding time. At the same time, the content of oxygen in TiN_xO_1−x decreased, and its nitrogen content correspondingly increased.     

Sintering Process and Microwave Dielectric Properties of Bi8TiO14 Ceramics

The formation of a homogeneous Bi₈TiO₁₄ phase was successfully achieved in a specimen calcined at 600°C. However, a Bi₄Ti₃O₁₂ secondary phase also developed in specimens calcined at temperatures higher than 600°C, probably because of Bi₂O₃ evaporation. For specimens sintered above 800°C, a small amount of the Bi₈TiO₁₄ phase melted during sintering, with the liquid phase contributing to the densification of the specimens; however, Bi₄Ti₃O₁₂ and Bi₁₂TiO₂₀ secondary phases were still formed in these specimens. The microwave dielectric properties of the Bi₈TiO₁₄ phase were considerably affected by variations in the microstructure of the specimens. When the sintering temperature exceeded 825°C, the amount of secondary phases increased, and this decreased the density and Q×f values of the specimens. Bi₈TiO₁₄ ceramics sintered at 825°C exhibited promising microwave dielectric properties, with ε_r = 47.4, Q×f = 5370 GHz, and τ_f = ?16.01 ppm/°C.     

Tuning of electrical properties of xBi(Zn0.5Ti0.5)O3-(1-x) (Ba0.5Sr0.5)TiO3 ceramics by composition design and bandgap engineering

Herein, the xBi(Zn_0.5Ti_0.5)O₃-(1-x) (Ba_0.5Sr_0.5)TiO₃ (x = 0.05, 0.10, 0.15, 0.20) novel negative temperature coefficient (NTC) ceramic materials were fabricated by solid-state method. X-ray diffraction revealed that xBi(Zn_0·5Ti_0.5)O₃-(1-x) (Ba_0.5Sr_0.5)TiO₃ successfully formed solid solution. The UV–vis diffuse spectra of the samples indicate that the band gap increases with the increasing Bi(Zn_0·5Ti_0.5)O₃ content. The resistance temperature curve showed that with the increase of Bi(Zn_0·5Ti_0.5)O₃ content, the resistivity ρ of the ceramics at 400 °C increased from 5.96 × 10⁶ to 2.67 × 10⁷ Ω cm, as well as an increase in the B_400/800 from 12374.6 to 13469.1 K. The enhanced resistivity is attributed to the increased band gap and reduced carrier pairs caused by the Bi(Zn_0.5Ti_0.5)O₃ modification. The impedance data indicates that the conduction process is activated by thermal. The ceramic samples exhibit the excellent NTC characteristics over a range of 400 °C–1000 °C. Hence, the xBi(Zn_0.5Ti_0.5)O₃-(1-x) (Ba_0.5Sr_0.5)TiO₃ ceramics have the potential to become high temperature NTC ceramics that can operate in a wide temperature range.     

Phase transformation and dielectric properties of sputtering-prepared Zn–Ti–O thin films

Zn–Ti–O films were co-sputtered from Zn and Ti targets and then annealed at temperatures ranging from 600 °C to 900 °C for 2 h under an air atmosphere. The [Ti]/([Ti]+[Zn]) ratio decreased from 75.52 to 28.26 as the Zn-target power increased from 25 W to 75 W. The phase transition of the films strongly depended on the [Ti]/([Ti]+[Zn]) ratio. High [Ti]/([Ti]+[Zn]) ratios led to the coexistence of ZnTiO₃, Zn₂Ti₃O₈, and rutile TiO₂ phases. Zn₂Ti₃O₈ gradually became the major crystalline phase as the [Ti]/([Ti]+[Zn]) ratio and rutile TiO₂ and ZnTiO₃ phases decreased. The aforementioned phases disappeared when the [Ti]/([Ti]+[Zn]) ratio was especially low. In their place, Zn₂TiO₄ and even ZnO phases developed. The dielectric constant of the films increased with increasing [Ti]/([Ti]+[Zn]) ratio. However, extremely high [Ti]/([Ti]+[Zn]) ratios increased the dielectric loss of the films. The film mainly composed of the Zn₂Ti₃O₈ phase exhibited optimal dielectric properties, including a dielectric constant and loss equal to 40.1 and 0.0304, respectively, at 1 MHz.