Tailored electrostrain and related properties in (1 − x)BaTiO3–xSrSnO3 Pb-free electroceramics

We report excellent electrostrain properties of (1 − x)BaTiO₃–xSrSnO₃ (BSTS) Pb-free electroceramics (0 ≤ x ≤ 0.15), as well as the corresponding structural, dielectric, and ferroelectric properties. A tailored phase diagram of the pseudo-binary solid solution of BaTiO₃–SrSnO₃, which exhibits a nearly composition-independent orthorhombic–tetragonal polymorphic phase boundary close to room temperature, was obtained, and, in contrast to Ba(Ti_1−xSn_x)O₃, the appearance of the relaxor mode was accelerated in the phase transition of BSTS owing to the additional incorporation of Sr. Using these compositionally modified phase-related characteristics, desirable sets of electrostrain properties for actuator applications were obtained. Based on these results, we propose that BSTS is a promising candidate for Pb-free electroceramics for high-precision actuator applications near room temperature.     

Elastic constants of polycrystalline Ti3AlC2 and Ti3SiC2 measured using coherent inelastic neutron scattering

The magnitude of the single‐crystal elastic constant c₄₄ in the MAX phase Ti₃SiC₂ is under debate. In this paper, estimates for the magnitude of c₄₄ for MAX phases Ti₃AlC₂ and Ti₃SiC₂ are determined from a partially oriented polycrystalline sample via coherent inelastic neutron scattering. The largely quasi‐isotropic nature of these M_n+1AX_n phase elastic constants as previously predicted by density functional theory calculations is confirmed experimentally for Ti₃AlC₂ to be c₄₄=115.3 ± 30.7 GPa. In contrast, Ti₃SiC₂ is confirmed to be shear stiff with c₄₄=402.7 ± 78.3 GPa supporting results obtained by earlier elastic neutron diffraction experiments.     

Structure,mechanical, and thermal properties of Ti1‐xAlxN/CrAlN (x = 0.48, 0.58, and 0.66) multilayered coatings

Nano‐multilayered TiAlN/CrAlN coatings combining advantages of Ti‐Al‐N and Cr‐Al‐N are considered to be promising candidates for advanced machining processes. Here, the structure and thermal properties of Ti_1‐xAl_xN/CrAlN (x = 0.48, 0.58, and 0.66) multilayered coatings as well as referential Ti_1‐xAl_xN and Cr_0.32Al_0.68N monolithic coatings were investigated. Ti_1‐xAl_xN coatings show a structural transformation from cubic structure for x = 0.48 to mixed cubic and wurtzite structure for x = 0.58 and 0.66, and Cr_0.32Al_0.68N coating exhibits a single cubic structure. Through a multilayer arrangement with Cr_0.32Al_0.68N layers, the Ti_0.52Al_0.48N and Ti_0.42Al_0.58N layers can be stabilized in their metastable cubic structure, but the Ti_0.34Al_0.66N layer still tends to crystallize in the mixed cubic and wurtzite structure. The hardness of Ti_0.52Al_0.48N/CrAlN and Ti_0.42Al_0.58N/CrAlN coatings is higher than that of corresponding monolithic coatings regardless of as‐deposited and annealed states. Especially, after annealing at 800°C, the Ti_0.52Al_0.48N/CrAlN and Ti_0.42Al_0.58N/CrAlN coatings reach their peak hardness of ~34.2 and 32.8 GPa due to the spinodal decomposition of Ti_1‐xAl_xN layers. However, the oxidation resistance of Ti_1‐xAl_xN/CrAlN coatings is mainly up to the Al content of Ti_1‐xAl_xN layers, where only the Ti_0.34Al_0.66N/CrAlN coating can survive the 10 h exposure to air at 1000°C.     

Extension of MAX phases from ternary carbides and nitrides (X = C and N) to ternary borides (X = B,C, and N): A general guideline

Although significant progress has been made on understanding the structure–property relationship of MAX phases, a clear answer has not been given to the outstanding question whether MAX phases can be extended from carbides and nitrides (X = C and N) to borides (X = B). Herein, based on the systematically investigations on the general trend of lattice constants and elastic properties of the experimentally found MX and M₂AX (X = B, C, and N) with the valence electron concentration (VEC), a guideline for the discovery of new MAX borides is given. The MX and M₂AX (X = B, C, and N) compounds are situated in a small range of VEC, and their lattice constants generally decrease with VEC. Second-order elastic constants c₁₁, c₃₃, and bulk modulus B of M₂AX (X = B, C, and N) increase with VEC due to enhanced bonding, c₄₄ and G, however, increase up to some critical values and then decline with the further increase of VEC. Based on the electronic structure–elastic property relationship and the presence of rock salt–structured transition metal monoborides, nine possible MAX phase borides M₂AB (M = Zr, Hf, Nb, A = P, As, and Sb) are predicted. Thus, MAX phases can be extended from X = C and N to X = B, C, and N.     

Synthesis and thermophysical properties of RETa3O9 (RE = Ce,Nd, Sm,Eu, Gd,Dy, Er) as promising thermal barrier coatings

Thermal barrier coatings (TBCs) are one of the most important materials in gas turbine to protect the high temperature components. RETa₃O₉ compounds have a defect‐perovskite structure, indicating that they have low thermal conductivity, which is the critical property of TBCs. Herein, dense RETa₃O₉ bulk ceramics were fabricated via solid‐state reaction. The crystal structure was characterized by X‐ray diffraction (XRD) and Raman Spectroscope. Scanning electron microscope (SEM) was used to observe the microstructure. The thermophysical properties of RETa₃O₉ were studied systematically, including specific heat, thermal diffusivity, thermal conductivity, thermal expansion coefficients, and high‐temperature phase stability. The thermal conductivities of RETa₃O₉ are very low (1.33‐2.37 W/m·K, 373‐1073 K), which are much lower than YSZ and La₂Zr₂O₇; and the thermal expansion coefficients range from 4.0 × 10^?6 K^?1 to 10.2×10^?6 K^?1 (1273 K), which is close to La₂Zr₂O₇ and YSZ. According to the differential scanning calorimetry (DSC) curve there is not phase transition at the test temperature. Due to the high melting point and excellent high‐temperature phase stability with these oxides, RETa₃O₉ ceramics were promising candidate materials for TBCs.     

High-temperature thermal stability of Ti2AlN and Ti4AlN3: A comparative diffraction study

The susceptibility of Ti₂AlN and Ti₄AlN₃ to high-temperature thermal dissociation in a dynamic environment of high-vacuum has been investigated using in situ neutron diffraction. Under high vacuum, these ternary nitrides decomposed above 1400 °C through the sublimation of Al, and possibly Ti, to form a surface coating of TiN_x (0.5 ≤ x ≤ 0.75). The kinetics of isothermal phase decomposition were modelled using the Avrami equation and the Avrami exponents (n) of isothermal decomposition of Ti₂AlN and Ti₄AlN₃ were determined to be 0.62 and 0.18, respectively. The characteristics of thermal stability and phase transitions in Ti₂AlN and Ti₄AlN₃ are compared in terms of the rate of decomposition, phase relations and microstructures.     

(MMgBO3)n (n = 1, M = Li,Na, K,Rb and n = 4, M = Cs): An investigation on the structure transition and optical properties

In crystal engineering, modification of the crystal structure by cation substitution is one of the most important and efficient methods. This paper reveals the origin of the structure transition of a series of (MMgBO₃)_n (n = 1, M = Li, Na, K, Rb and n = 4, M = Cs) compounds. A force-equilibrium model was established with the comparison of different structures of these compounds. After substituted by other alkali metal cations with different atomic radii, the changed bond between oxygen and cations leads to structural transition. The electronic and optical properties of NaMgBO₃, KMgBO₃ and RbMgBO₃ were also investigated by using DFT methods to give more comprehension of these compounds.     

Mechanical and thermal properties of δ-RE4Hf3O12 (RE = Yb,Lu)

Rare-earth (RE) hafnates are promising thermal and environmental barrier coating (TEBC) materials for SiC_f/SiC ceramic matrix composites. In this study, pure-phase and dense δ-RE₄Hf₃O₁₂ (RE = Yb, Lu) bulk ceramics have been fabricated via a hot-pressing method. The crystal structure, microstructure, mechanical, and thermal properties of δ-RE₄Hf₃O₁₂ were systematically investigated in order to probe their potential application as TEBCs. The high-temperature elastic moduli of δ-Yb₄Hf₃O₁₂ and δ-Lu₄Hf₃O₁₂ are measured to be 185 and 188 GPa at 1673 K, respectively, which are over 85% values of room temperature. The coefficients of thermal expansion are 7.64 × 10⁻⁶ and 7.46 × 10⁻⁶ K⁻¹ for δ-Yb₄Hf₃O₁₂ and δ-Lu₄Hf₃O₁₂, respectively. The relatively low coefficient of thermal expansion and thermal conductivity as well as their excellent high-temperature stability endow these hafnates as potential TEBC candidates.     

Anisotropic corrosion of Ti2AlC and Ti3AlC2 in supercritical water at 500 ºC

Textured and untextured M_n+1AX_n compounds, Ti₂AlC and Ti₃AlC₂, namely MAX phases have been synthesized and examined with respect to their corrosion resistance in static supercritical water at 500 °C. The textured ceramics were obtained by hot forging process at high temperatures. Both X-ray diffraction and SEM analysis revealed well alignment of c-plane of MAX phases parallel to the hot-forging surface. Better corrosion resistance on the surface perpendicular to the hot-forged direction was verified by SEM. On the other hand, the side surfaces of the samples showed thick oxidation layers and abundant cracks. The (00l) faces consist of strongly bonded Ti₃C₂ and Ti₂C layers in Ti₃AlC₂ and Ti₂AlC, respectively, hence exhibit higher resistance to water corrosion. On the contrary, the side surfaces where most of weakly bonded interlayers of these hexagonal phases were exposed tend to be easily corroded especially through Al-layers. The corrosion process involved a phase transition of oxidized product, i.e. TiO₂ from anatase to rutile phase, which gave rise to the formation of cracks due to accompanied volume changes.     

Theoretical Study on the Mechanism of Anisotropic Thermal Properties of Ti2AlC and Cr2AlC

Temperature dependences of thermal and elastic properties, such as the Grüneisen parameters, thermal expansion, bulk modulus, and heat capacity of Ti₂AlC and Cr₂AlC, are studied by combining first‐principles method and lattice dynamic calculation based on the quasi‐harmonic model. Experimental thermal expansion coefficient is also measured for comparison. Thermal expansion coefficients of Ti₂AlC and Cr₂AlC show different trends: Ti₂AlC exhibits anisotropic thermal expansion while Cr₂AlC shows generally isotropic character. The mechanism is explored by investigating the isotropy or anisotropy of Grüneisen parameters (phonon anharmonicity and thermal pressure) and elastic stiffness (response to thermal pressure) of Ti₂AlC and Cr₂AlC. In addition, the calculated bulk modulus of Cr₂AlC is higher at ambient temperature but decreases faster than the value of Ti₂AlC as temperature increasing.     

Microwave dielectric properties of BaxLa4Ti3 + xO12 + 3x (x = 0.0–1.0) ceramics

In the BaO–La₂O₃–TiO₂ system, the Ba_nLa₄Ti_3 + nO_12 + 3n homologous compounds exist on the tie line BaTiO₃–La₄Ti₃O₁₂ besides tungstenbronze-type like Ba_6 − 3xR_8 + 2xTi₁₈O₅₄ (R = rare earth) solid solutions. There are four kinds of compounds in the homologous series: n = 0, La₄Ti₃O₁₂; n = 1, BaLa₄Ti₄O₁₅; n = 2, Ba₂La₄Ti₅O₁₈; n = 4, Ba₄La₄Ti₇O₂₄. These compounds have the layered hexagonal perovskite-like structure, which has a common sub-structure in the crystal structure. These compounds have been investigated in our previous studies. In this study, we have investigated the phase relation and the microwave dielectric properties of Ba_xLa₄Ti_3 + xO_12 + 3x ceramics in the range of x between 0.2 and 1.0. With the increase in x, the dielectric constant ɛ_r locates around 45, the quality factor Q × f shows over 80,000 GHz at x = 0.2 and the minimum value of 30,000 GHz at x = 0.9, and the temperature coefficients of resonant frequency τ_f is improved from −17 to −12 ppm/°C. At x = 0.2, the ceramic composition obtained has dielectric constant ɛ_r = 42, the temperature coefficient of the resonant frequency τ_f  = −17 ppm/°C and a high Q × f of 86,000 GHz.     

Synthesis of Ti2(InxAl1-x)C (x = 0–1) solid solutions with high-purity and their properties

Herein, high-purity Ti₂(In_xAl_1-x)C (x = 0–1) solid solutions were successfully synthesized. The crystal structure and actual composition of solid solutions were confirmed using XRD, SEM, and TEM analyses, and their formation mechanism was revealed by thermal analysis. On the In-rich side (x ≥ 0.5), primary Ti₂InC first formed and then acted as a crystalline seed for the subsequent solid solutions, resulting in a cluster-like morphology. The lattice constants of Ti₂(In_xAl_1-x)C were found to well follow Vegard’s law. The examined properties of Ti₂(In_xAl_1-x)C also greatly depended on their A-site compositions. Ti₂AlC exhibited the highest hardness and elastic moduli, while the best corrosion resistance was achieved at Ti₂InC, and all Ti₂(In_xAl_1-x)C displayed active dissolution in 0.5 M HCl solution. Thus, adjusting the In/Al ratio at A-site can yield a desired set of performances, which provides a good example for regulating the performance of MAX phases via A-site solid solution strategy.     

High‐Temperature Neutron Diffraction,Raman Spectroscopy,and First‐Principles Calculations of Ti3SnC2 and Ti2SnC

Herein, we report—for the first time—on the additive‐free bulk synthesis of Ti₃SnC₂. A detailed experimental study of the structure of the latter together with a secondary phase, Ti₂SnC, is presented through the use of X‐ray diffraction (XRD), and high‐resolution transmission microscopy (HRTEM). A previous sample of Ti₃SnC₂, made using Fe as an additive and Ti₂SnC as a secondary phase, was studied by high‐temperature neutron diffraction (HTND) and XRD. The room‐temperature crystallographic parameters of the two MAX phases in the two samples are quite similar. Based on Rietveld analysis of the HTND data, the average linear thermal expansion coefficients of Ti₃SnC₂ in the a and c directions were found to be 8.5 (2)·10^?6 K^?1 and 8.9 (1)·10^?6 K^?1, respectively. The respective values for the Ti₂SnC phase are 10.1 (3)·10^?6 K^?1 and 10.8 (6)·10^?6 K^?1. Unlike other MAX phases, the atomic displacement parameters of the Sn atoms in Ti₃SnC₂ are comparable to those of the Ti and C atoms. When the predictions of the atomic displacement parameters obtained from density functional theory are compared to the experimental results, good quantitative agreement is found for the Sn atoms. In the case of the Ti and C atoms, the agreement is more qualitative. We also used first principles to calculate the elastic properties of both Ti₂SnC and Ti₃SnC₂ and their Raman active modes. The latter are compared to experiment and the agreement was found to be good.     

Physical Properties of La1−xEuxPO4,0 ≤ x ≤ 1, Monazite‐Type Ceramics

Synthetic La_1?xEu_xPO₄ monazite‐type ceramics with 0 ≤ x ≤ 1 have been characterized by ultrasound techniques, dilatometry, and micro‐calorimetry. The coefficients of thermal expansion and the elastic properties are, to a good approximation, linearly dependent on the europium concentration. Elastic stiffness coefficients range from 182(1) to 202(1) GPa for c₁₁ and from 53.8(7) to 61.1(4) GPa for c₄₄. They are strongly dependent on the density of the sample. The coefficient of thermal expansion at 673 K is 8.4(3)  × 10^?6 K^?1 for LaPO₄ and 9.9(3)  × 10^?6 K^?1 for EuPO₄, respectively. The heat capacities at ambient temperature are between 101.6(8) J·(mol·K)^?1 for LaPO₄ and 110.1(8) J·(mol·K)^?1 for EuPO₄. The difference between the heat capacity of LaPO₄ and the Eu‐containing solid solutions is dominated by electronic transitions of the 4f‐electrons at temperatures above 75 K.     

Synthesis and Microstructural Characterization of Substoichiometric Ti2Al(CxNy) Solid Solutions and Related Ti2AlCx and Ti2AlN End‐Members

Ti, TiC, Al and AlN powders were mixed to synthesize Ti₂Al(C_xN_y) (x + y < 1) solid solutions, Ti₂AlC_x (x < 1) and Ti₂AlN‐related end‐members by hot isostatic pressing at 1400°C/80 MPa for 4 h. For the pure carbides, it is demonstrated that single‐phased samples can only be obtained when about 15% of substoichiometry on the carbon site is applied. Such a result likely implies that Ti₂AlC_x can only exist in a narrow range of carbon composition. Ti₂AlN nitride can be synthesized with y = 1. Assuming that vacancy content varies linearly from 0 to 0.15 going from Ti₂AlN to Ti₂AlC_0.85 in the solid solutions, element concentrations have been calculated to synthesize different solid solutions. Thus, it is demonstrated that single‐phased and fully dense Ti₂Al(C_0.23N_0.71), Ti₂Al(C_0.45N_0.45), and Ti₂Al(C_0.66N_0.22) carbonitrides can be synthesized.     

Effects of structural characteristics on microwave dielectric properties of (1 − x)Ca0.85Nd0.1TiO3–xLnAlO3 (Ln = Sm,Er and Dy) ceramics

Dependence of microwave dielectric properties on the structural characteristics of (1 − x)Ca_0.85Nd_0.1TiO₃–xLnAlO₃ (Ln = Sm, Dy and Er) ceramics were investigated as a function of LnAlO₃ content (0.05 ≤ x ≤ 0.25). For the specimens with SmAlO₃, a single phase with orthorhombic perovskite was obtained through the entire composition, however, Dy₂Ti₂O₇ and Er₂Ti₂O₇ were detected as a secondary phase along with the orthorhombic perovskite phase for the specimens with DyAlO₃ (x = 0.25) and ErAlO₃ (0.10 ≤ x ≤ 0.25), respectively. With an increase of LnAlO₃ content, the dielectric constant decreased due to the smaller ionic polarizability of LnAlO₃ than Ca_0.85Nd_0.1TiO₃. The temperature coefficient of the resonant frequency (TCF) decreased with LnAlO₃ content resulted from an increase of oxygen octahedral distortion.     

High-pressure structural investigation on lead-free piezoelectric 0.5Ba(Ti0.8Zr0.2)O3 - 0.5(Ba0.7Ca0.3)TiO3

The solid solution 0.5Ba(Ti_0.8Zr_0.2)O₃ − 0.5(Ba_0.7Ca_0.3)T iO₃ (BCZT) has become a promising member of the lead-free piezoelectric materials because of its exceptionally high piezoelectric properties. In this study, we focus on studying pressure-dependent Raman spectroscopy, powder x-ray diffraction, and dielectric constant measurements on BCZT. The data show several structural transitions are present, where the system from ambient mixed phase (tetragonal P4mm + orthorhombic Amm2) transforms into single phase (P4mm) at 0.3 GPa, then converts into cubic phase (Pm3m) at 4.8 GPa followed by another possible structural re-ordering around 10 GPa. Although there have been a lot of unanimity with the ambient crystallographic state of BCZT, our analysis justifies the presence of an intermediate orthorhombic phase in the Morphological Phase Boundary (MPB) of BCZT phase diagram. The transformation tetragonal to cubic is indicated by the Raman mode softening, unit cell volume change, and the (Ti/Zr)O₆ octahedra distortion, which coincides with the well-known ferroelectric-paraelectric transition of the system. The sudden drop in the dielectric constant value at 4.7 GPa also confirms the loss of ferroelectric nature of the BCZT ceramic.     

First principles calculation of single‐crystal elastic constants of titanium tetraboride (Ti3B4) and experimental validation

The nine independent single‐crystal elastic constants of a new ceramic, titanium tetraboride (Ti₃B₄), have been determined by first principles calculations, and the data were validated experimentally through nanoindentation testing. The independent elastic constants, which are specific to the crystal structure, are important for the fundamental characterization of mechanical and physical properties of the group of hard compounds such as the transition metal borides. The elastic constants of Ti₃B₄ were determined from crystal strain energies that were calculated by applying specific deformations within WIEN2k platform utilizing full‐potential linear augmented plane wave (FLAPW) and generalized gradient approximation (GGA). The WIEN2K package is based on all‐electron calculations, and hence is considered as the most accurate for first principles calculations. It has been found that the polycrystalline elastic moduli, determined as the Voigt‐Reuss‐Hill averages of the independent elastic constants, are quite impressive (E = 492 GPa, G = 217 GPa, B = 224 GPa, ν = 0.13) placing the tetraboride very close to the well‐known titanium diboride (E = 570 GPa, G = 254 GPa, B = 249 GPa, ν = 0.12). The strong B‐B chains were found to be largely responsible for the high values of elastic stiffness constants, in particular the c₃₃ describing stiffness in the [001] direction. The electron charge densities were found to be accumulated to a higher degree along the B‐B bonds, resulting in strengthening of the B‐B chains in the lattice. The promising data motivated the first experimental synthesis of Ti₃B₄ in a bulk form, which is also described in this work. To validate the elastic constants determined from first principles, elastic moduli were determined by nanoindentations in multiple grains of a polycrystalline Ti₃B₄, synthesized by electric field‐activated reaction sintering. The range of elastic moduli determined from nanoindentation was found to agree well with the range determined by computation. The calculations and experiments demonstrate that Ti₃B₄ has the potential to be one of the leading structural ceramics.     

Thermal Properties of (Zr,TM)B2 Solid Solutions with TM = Hf,Nb, W,Ti, and Y

The thermal properties were investigated for hot‐pressed zirconium diboride—transition‐metal boride solid solutions. The transition‐metal additives included hafnium, niobium, tungsten, titanium, and yttrium. The nominal additions were equivalent to 3 at.% of each metal with respect to zirconium. Powders were hot‐pressed to nearly full density at 2150°C using 0.5 wt% carbon as a sintering aid. Thermal diffusivity was measured using the laser flash method. Thermal conductivity was calculated from the thermal diffusivity results using temperature‐dependent values for density and heat capacity. At 25°C, the thermal conductivity ranged from 88 to 34 W·(m·K)^?1 for specimens with various additives. Electrical resistivity measurements and the Wiedemann–Franz law were used to calculate the electron contribution of the thermal conductivity and revealed that thermal conductivity was dominated by the electron contribution. The decrease in thermal conductivity correlated with a decrease in unit cell volume, indicating that lattice strain may affect both phonon and electron transport in ZrB₂.     

Iron and chromium doped perovskite (CaMO3 M = Ti,Zr) ceramic pigments,effect of mineralizer

Solid solutions Ca(D_xM_1?x)O₃ (M = Ti, Zr and D = Fe,Cr), have been studied as ceramic pigment in conventional ceramic glazes using 0.5 mol/mol of NH₄Cl as flux agent by solid state reaction and by ammonia coprecipitation route. Ca(Cr_xTi_1?x)O₃ compositions obtained without addition of NH₄Cl as mineralizer, produce pink color in glazes at low x but CaCrO₄ crystallizes when x increases, producing undesired green colors. The crystallization of chromates can be avoided using NH₄Cl as mineralizer, giving a complete solid solution that produce pink color in glazes at low x and dark blue shades at high x. Coprecipitated sample produce blue colors at low x and at low temperature than ceramic sample (1000 °C instead 1200 °C for CE sample). Cr⁴⁺ ion acts as red chromophore, but at higher x values (blue samples) Cr³⁺ ion entrance affects the color. Ca(Fe_xTi_1?x)O₃ system crystallizes perovskite CaTiO₃ and pseudobrookite Fe₂TiO₅ together with rutile as residual crystalline phase, glazed samples change from a yellow to a pink color associated to the increase of pseudobrookite with firing temperature. Ca(Fe_xTi_1?x)O₃ and Ca(Cr_xZr_1?x)O₃ systems crystallize perovskite CaZrO₃ and zirconia (ZrO₂) in both monoclinic and cubic polymorphs, but iron or chromium oxides are not detected in the powders. Coprecipitated sample stabilises cubic form. The solid solution is not reached completely in these samples and is not stable in glazes.