Thermodynamic properties of Si(OH)4(g) based on combined experimental and quantum chemistry data

The volatility of silicon‐based ceramics in combustion environments is primarily controlled by the formation of gaseous Si(OH)₄. The heat capacities and entropies of this species at 298.15‐2100 K and P = 0.1 MPa have been studied with the B3LYP density functional theory for the 6‐311+G(d,p) basis set in different approximations: a harmonic oscillator, an anharmonic oscillator, and with corrections for hindered rotors. Experimentally based Gibbs energies of Si(OH)₄(g) at 424‐1661 K have been employed to evaluate the Gibbs energy of formation, , and the entropy, , of Si(OH)₄(g) at = 298.15 K and P = 0.1 MPa. We found that the QC and “experimental” values are very close for the harmonic and anharmonic oscillator approximations, but not for the “hindered rotor” approximation. This conclusion is also supported by calculations of the OH rotational energy for Si(OH)₄ molecule, where the potential barrier was found to exceed 12 kJ/mol. Finally, we recommend the thermodynamic properties of Si(OH)₄ in the ideal gas state at P = 0.1 MPa over the temperature range of 298‐2100 K.     

Defect engineering on phase structure and temperature stability of KNN‐based ceramics sintered in different atmospheres

Lead‐free MnO‐doped 0.955K_0.5Na_0.5NbO₃‐0.045Bi_0.5Na_0.5ZrO₃ (Abbreviated as KNN‐0.045BNZ) ceramics have been prepared by the conventional solid‐state sintering method in reducing atmosphere ( = 1 × 10^?10 atm) and air. For ceramics sintered in reducing atmosphere, only Mn²⁺ ions exist in ceramics who preferentially occupy the cation vacancies in A‐site at x = 0.2‐0.4, whereas Mn²⁺ ions substitute for Zr⁴⁺ ions in B‐site to form defects () at x > 0.4. For ceramics sintered in air, mixed Mn²⁺, Mn³⁺, and Mn⁴⁺ ions coexist here. The Mn²⁺ ions preferentially occupy the cation vacancies in A‐site at x = 0.2‐0.4 and then Mn²⁺ ions substitute for Zr⁴⁺ ions in B‐site at x > 0.4. Meanwhile, the Mn³⁺ ions and Mn⁴⁺ ions substitute for Nb⁵⁺ ions in B‐site to form defects () at x = 0.2‐0.8. The (, , and ) dipolar defects show a positive dipolar defect contribution (DDC) to the , whereas the dipolar defects () show a negative DDC to the . The dipolar defects ( ‐ and ) can help improve the temperature stability of . The 0.4% MnO‐doped KNN‐0.045BNZ ceramics sintered in reducing atmosphere show excellent piezoelectric constant d₃₃ = 300 pC/N and 0.2% MnO‐doped KNN‐0.045BNZ ceramics sintered in air possess optimal piezoelectric constant d₃₃ = 290 pC/N.     

Oxidation Behavior of ZrB2–SiC Composites at Low Pressures

ZrB₂‐60 mol%SiC composite with a eutectic microstructure was oxidized at 1573 to 1873 K with reduced total pressures (P_tot) and low oxygen partial pressures (). The mass change was continuously measured by a thermobalance, and then fit with a multiple paralinear model. Oxidation scale of SiO₂/ZrO₂+SiO₂/ZrO₂/ZrB₂ was formed at  > 0.13 kPa, whereas only porous ZrO₂ remained at  < 0.13 kPa, P_tot < 1.33 kPa and higher than 1773 K. With increasing , the parabolic oxidation constant decreased, whereas the linear oxidation constant increased.     

Microstructure and Magnetic Properties of Metastable RFeO3 (R: Rare‐earth element) Formed from Undercooled Melt

Containerless levitation technique, where the undercooling can be treated as one of the major thermodynamic parameters, was used to study the influence of oxygen partial pressure () on the microstructure and physical properties of rare‐earth orthoferrites RFeO₃ (where R = Rare‐earth element) in the ranges from 10⁵ to 10^?1 Pa. The microstructure of the as‐solidified samples changed into orthorhombic RFeO₃ (o‐RFeO₃), metastable hexagonal RFeO₃ (h‐RFeO₃), and Fe²⁺‐containing RFe₂O₄ and a new metastable R₃Fe₂O₇ phases with decreasing . The effect of on the magnetic properties was indicated as that the saturation magnetization gradually increased for R = La to Yb and decreased for R = Lu with decreasing due to the formation of metastable and magnetic phases such as Fe₃O₄ and Fe.     

Estimation of Stress Exponent and Activation Energy for Rapid Densification of 8 mol% Yttria‐Stabilized Zirconia Powder

The rapid densification behavior of 8 mol% Y₂O₃‐stabilized ZrO₂ polycrystalline (8Y‐SZP) powder compacts at the initial stage of pressure sintering (relative density () below 0.92) has been investigated using an electric current‐activated/assisted sintering (ECAS) system. Data points corresponding to a fixed heating rate were extracted from the densification rate () versus ρ and versus temperature (T) curves. These curves were obtained experimentally by consolidation at a fixed current. Under fixed current ECAS, the heating rate () decreases continuously over sintering time. Using a quasi‐ constant heating rate (CHR) method, data points were extracted to plot vs. ρ, vs. T, and ρ vs. T curves at a fixed . The stress exponent (n), estimated from a log‐log plot of grain size (d)‐corrected /ρ and effective stress (σ_eff) at 1300–1400 K, shows an almost constant value of 1. In addition, the activation energy (Q) for rapid densification, estimated from an Arrhenius plot of d‐corrected /ρ also shows an almost constant value of 350 kJ/mol, which is considerably lower than the previously reported value of the activation energy for Zr⁴⁺ lattice diffusion of about 440 kJ/mol. These results suggest that rapid densification of 8Y‐SZP by ECAS seems to proceed by diffusional creep controlled by grain‐boundary diffusion of Zr⁴⁺ ions.     

Effects of K2O Evaporation on the Structural Properties of KSbO3 Compounds

A specimen having a stoichiometric composition of KSbO₃·(KSb) calcined at 800°C has an R rhombohedral structure (RS), and changes to a Pn cubic structure (CS) when calcined at 1100°C. Finally, a <111>‐oriented rhombohedral phase is formed in the specimen calcined at 1230°C. K/Sb ratio decreases from 1.0 in RS, 0.93 in CS, and finally to 0.85 in <111>‐oriented rhombohedral phases. On the other hand, a specimen having a K‐excess composition of K_1.1SbO₃ calcined at 800°C shows a RS that is maintained in the K‐excess specimen calcined at 1230°C. The composition of these specimens is very close to KSb. Therefore, the RS with a space group of R is a stable form of KSbO₃. The formation of Pn cubic and <111>‐oriented R phases can be explained by the evaporation of K₂O during the calcination process at temperatures above 1100°C.     

Temperature stability and electrical properties of MnO‐doped KNN‐based ceramics sintered in reducing atmosphere

Lead‐free MnO‐doped 0.955K_0.5Na_0.5NbO₃‐0.045Bi_0.5Na_0.5ZrO₃ (abbreviate as KNN‐0.045BNZ) ceramics have been prepared by a conventional solid‐state sintering method in reducing atmosphere. The MnO addition can suppress the emergence of the liquid phase and improve the homogenization of grain size. All ceramics sintered in reducing atmosphere show a two‐phase coexistence zone composed of rhombohedral (R) and tetragonal (T) phase. MnO dopant results in the content increase in R phase and slight increase in Curie temperature T_C. For KNN‐0.045BNZ ceramics, Mn²⁺ ions preferentially occupy the cation vacancies in A‐site to decrease oxygen vacancy concentration for 0.2%‐0.4% MnO content, whereas Mn²⁺ ions substitute for Zr⁴⁺ ions in B‐site to form oxygen vacancies at x ≥ 0.5. The defect dipole is formed at the moderate concentration from 0.5 to 0.6, which can provide a preserve force to improve the temperature stability of piezoelectric properties for k_p and . The Mn0.4 ceramics show excellent electrical properties with quasistatic piezoelectric constant d₃₃ = 300 pC/N, electromechanical coupling coefficient k_p = 51.2%, high field piezoelectric constant  = 430 pm/V (at E_max = 25 kV/cm) and T_C = ~345°C, insulation resistivity ρ  =  6.13 × 10¹¹ Ωcm.     

Oxygen Nonstoichiometry and Thermodynamic Quantities of La2Ni0.95Al0.05O4.025 + δ

The oxygen nonstoichiometry of La₂Ni_0.95Al_0.05O_4.025 + δ (LNAO) is measured as a function of oxygen partial pressure (pO₂) and temperature by coulometric titration method and thermogravimetric analysis (TGA) in 800°C–1000°C temperature range and 10^?16‐1 atm pO₂ range. The partial molar quantities for mixing of oxygen were calculated and results were compared with the literature results on La₂NiO_4 + δ (LNO). The variation in activity coefficient of holes versus oxygen nonstoichiometry illustrated an early positive deviation of the activity coefficient of holes from unity, leading to  ≈  7 at δ  ≈  0.08, which was lower than the literature value of  ≈  14 for La₂NiO_{4  +  δ} at δ  ≈  0.08, indicating lesser deviation of LNAO from ideal solution behavior. The effective mass of holes () was 1.02–1.21 times the rest mass (m_o), which indicated the band‐like conduction and allowed the effect of the small degree of polaron hopping to be ignored. The comparison of oxygen nonstoichiometry and partial molar quantities showed that incorporation of interstitial oxygen is less favorable in LNAO in comparison to LNO.     

Diffusion Kinetics of Indium in TiO2 (Rutile)

This work determines the self‐diffusion coefficients of indium in TiO₂ single crystal (rutile). Diffusion concentration profiles were imposed by deposition of a thin surface layer of InCl₃ on the TiO₂ single crystal and subsequent annealing in the temperature range 1073–1573 K. The diffusion‐induced concentration profiles of indium as a function of depth were determined using secondary ion mass spectrometry (SIMS). These diffusion profiles were used to calculate the self‐diffusion coefficients of indium in the polycrystalline In₂TiO₅ surface layer and the TiO₂ single crystal. The temperature dependence of the respective diffusion coefficients, in the range 1073–1573 K, can be expressed by the following formulas: and The obtained activation energy for bulk diffusion of indium in rutile (316 kJ/mol) is similar to that of zirconium in rutile (325 kJ/mol). The determined diffusion data can be used in selection of optimal processing conditions for TiO₂–In₂O₃ solid solutions.     

Effect of the (Ba + Sr)/Ti ratio on the microwave‐tunable properties of Ba0.6Sr0.4TiO3 ceramics

The impact of the (Ba + Sr)/Ti (A/B) ratio on the microwave‐tunable characteristics of diffuse phase transition (DPT) ferroelectric Ba_0.6Sr_0.4TiO₃ (0.6‐BST) ceramics was investigated. The reduction in the lattice constant with increasing nonstoichiometry was attributed to introduced partial Schottky defects, i.e., and . The magnitude of the dielectric constant, ε′, at room temperature in the absence of an applied electric field was governed by the shift in the dielectric maximum temperature, T_m, because T_m was close to room temperature for the 0.6‐BST. The dielectric loss, tanδ, diminished as the ε′ decreased for 0.98≤A/B≤1.05, while the tanδ was much higher for A/B=0.95 having the greatest A‐site vacancy loading. The negatively charged and were mainly compensated by oxygen vacancies and likely partly compensated by holes, h^?, which contributed to the electrical conduction. The tunability, T, at 100 MHz was almost constant at 20%–25% for A/B≥1.00 despite the reduction of the ε′, whereas T decreased for A/B<1.00 to ca. 10% for A/B=0.95 having the greatest A‐site vacancy loading. The results implied that the for larger A/B values was more efficient in generating nucleation sites in the polar nanoregions (PNRs) than the for smaller A/B values, thereby providing greater dipole polarization. Consequently, the figure of merit, FOM, reached its maximum of 250 at A/B=0.9875, which was ca. 155% higher than that of the stoichiometric BST.     

Lattice and Grain‐Boundary Diffusion of Al in Tetragonal Yttria‐Stabilized Zirconia Polycrystalline Ceramics (3Y‐TZP) Analyzed Using SIMS

Aluminum oxide was deposited on the surface of 3 mol% yttria‐stabilized tetragonal zirconia polycrystals (3Y‐TZP). The samples were annealed at temperatures from 1523 to 1773 K. Diffusion profiles of Al in the form of mean concentration vs. depth in B‐type kinetic region were investigated by secondary ion mass spectroscopy. The experimental results for the lattice diffusion (D_B) and grain boundary diffusion (D_GB) are as follows: and where δ is the grain‐boundary width and s is the segregation factor.     

Composition‐induced structural transitions and enhanced strain response in nonstoichiometric NBT‐based ceramics

In this work, the nonstoichiometric 0.99Bi_0.505(Na_0.8K_0.2)_0.5‐xTiO₃‐0.01SrTiO₃ (BNKST(0.5‐x)) ceramics with x=0‐0.03 were synthesized by conventional solid‐state reaction method. The composition‐induced structural transitions were investigated by Raman spectra, dielectric analyses, and electrical measurements. It is found that the relaxor phase can be induced through the modulation of the (Na, K) content. The (Na, K) deficiency in BNKST(0.5‐x) ceramics favors a more disordered local structure and can result in the loss of long‐range ferroelectricity. The x=0.015 critical composition possesses relatively high positive strain S_pos of 0.42% and large signal piezoelectric constant d₃₃* of 479 pm V^?1 at 6 kV mm^?1, along with the good temperature (25‐120°C) and frequency (1‐20 Hz) stability. The recoverable large strain responses in nonstoichiometric ceramics can be attributed to the reversible relaxor‐ferroelectric phase transition, which is closely related to the complex defects (, , and ) and the local random fields. This work may be helpful for the exploration of high‐performance NBT‐based lead‐free materials by means of A‐site compositional modification.     

Phase Equilibria in the ZrO2–MgO–MnOx System

Phase equilibria were experimentally investigated in the MgO–MnO_x and the ZrO₂–MgO–MnO_x systems for different oxygen partial pressures by powder X‐ray diffractometry, scanning electron microscopy, and differential thermal analysis. The formation of two compositionally and structurally different β‐spinel solid solutions was observed in the MgO–MnO_x system in air in the temperature interval 1473–1713 K. Isothermal sections of the ZrO₂–MgO–MnO_x phase diagram were constructed for air conditions ( = 0.21 bar) at 1913, 1813, 1713, 1613, and 1523 K. In addition, isothermal sections at 1913 and 1523 K were constructed for = 10^?4 bar. The β‐spinel and halite phases of the MgO–MnO_x system were found to dissolve up to 2 and 5 mol% ZrO₂. A continuous c‐ZrO₂ solid solution forms between the boundary ZrO₂–MnO_x and ZrO₂–MgO systems. It stabilizes in the ZrO₂–MgO–MnO_x system down to at least 1613 K in air and down to 1506 K at = 10^?4 bar.     

A piezomicrobalance system for high‐temperature mass relaxation characterization of metal oxides: A case study of Pr‐doped ceria

A system for mass relaxation studies based on a gallium phosphate piezocrystal microbalance has been developed, built, and successfully used to characterize a representative mixed ionic and electronic conducting material. The apparatus is constructed to achieve reactor gas exchange times as short as 2 seconds and temporal resolution in mass measurement of 0.1 seconds. These characteristics enabled evaluation of mass relaxations that occurred on the 6 seconds time scale. Proof of concept for materials characterization capabilities of the system was carried out using 10% praseodymium‐doped cerium oxide (PCO), a material that undergoes, at selected temperatures and oxygen partial pressures, changes in mass but not in conductivity. Thin films were deposited on the piezocrystals via pulsed laser deposition (PLD). Mass relaxation curves were collected at 700°C upon application of a small step change in oxygen partial pressure, . Using two different films, the surface reaction constant, k_S, was obtained over the range from 10^?4 to 0.1 atm. Its value is found to vary between 9.7 × 10^?6 and 1.7 × 10^?4 cm/s, displaying a power law dependence on , with a law exponent of 0.67 ± 0.02, as averaged over the two sets of results. This steep dependence of k_S on is surprisingly independent of a change in dominant defect type within the range of measurement.     

First‐principles investigation of the thermodynamic stability of MB2 materials surfaces (M = Ti/Zr/Hf)

Some of the renewed interest in transition metal diborides (MB₂, M = Ti/Zr/Hf) arises from their potential use as matrices in ultrahigh‐temperature ceramic matrix composites (UHTCMCs). Crucial to the understanding of such composites is the study of the fiber/matrix interfaces, which in turn requires a deep knowledge of the surface structures and the thermodynamics of the matrix material. Here we investigate the surface stability of MB₂ compounds by first‐principles calculations. Five surfaces are stabilized when going from a M‐rich to a B‐rich environment, respectively (0001)_M, (100)_M, (101)_B(M), (113)_M and (0001)_B, with the highly stable (100)_M, (101)_B(M) and (113)_M surfaces being discussed here for the first time. The mechanism behind the surface stability is analyzed in terms of cleavage energy, surface strain and surface bonding states. Our results provide important information for a better understanding of the most likely surfaces exposed to the fibers in UHTCMCs, thereby for the construction of reliable interfaces and ultimately UHTCMCs models.     

Solute Diffusion of Platinum in Rutile Titanium Dioxide

¹⁹⁵Pt solute diffusion coefficients in undoped single‐crystal rutile TiO₂ have been determined parallel to the c‐axis over the temperature range of 1073–1523 K and oxygen partial pressure of 101 kPa. This has yielded the following temperature dependence: On the basis of this result, it has been concluded that ¹⁹⁵Pt diffuses via an interstitial mechanism involving rapid transport parallel to the c‐axis through open interstitial diffusion channels. While other divalent cations have also displayed diffusion via the same mechanism, and report diffusion rates that greatly exceed that for cation self‐diffusion, the overall rate of ¹⁹⁵Pt diffusion is slow. This has been attributed to the size of Pt²⁺ (0.80 Å) which is comparative to the dimension of interstitial channels (0.77 Å) through which transport is believed to be taking place.     

Stability and Decomposition of Ca‐Substituted Lanthanum Ferrite in Reducing Atmospheres

Calcium‐substituted lanthanum ferrites (La_1?xCa_xFeO_3?δ x = 0, 0.1, 0.2, 0.3, 0.4) were synthesized in air and subsequently decomposed in reducing atmospheres. The partial pressure of oxygen () was controlled by varying the H₂/H₂O ratio by bubbling hydrogen/argon mixtures through water baths at controlled temperatures. Three regions of mass loss were identified as the was reduced, two of which were determined to be associated with decomposition reactions. Calcium was shown to decrease the thermal stability of the perovskite compound, but rather than incrementally increasing the required for decomposition proportional to calcium concentration, all samples partially decomposed at a single . The extent of the partial decomposition was dependent on the amount of calcium substitution and temperature. The perovskite phase remaining after the partial decomposition was found to fully decompose at the same oxygen partial pressure as pure lanthanum ferrite.     

Grain Boundary Curvatures Measurements in Annealed Yttria‐Stabilized Zirconia (3Y‐TZP) and Their Relation to Mean Grain Size

It was determined that the mean grain boundary radius of curvature in 3 mol% yttria‐stabilized zirconia isothermally annealed without and with a DC electric field  = 18 V/cm was uniquely proportional to the mean linear intercept grain size , the proportionality constant α = 3/2 being in accord with the Rios‐Fonseca stereological model.     

Enhanced O2 Flux of CaTi0.85Fe0.15O3−δ Based Membranes by Mn Doping

Dense symmetric membranes of CaTi_0.85?xFe_0.15Mn_xO_3?δ (x = 0.1, 0.15, 0.25, 0.4) are investigated in order to determine the optimal Mn dopant content with respect to highest O₂ flux. O₂ permeation measurements are performed as function of temperature between 700°C–1000°C and as function of the feed side ranging between 0.01 and 1 bar. X‐ray photoelectron spectroscopy is utilized to elucidate the charge state of Mn, and synchrotron radiation X‐ray powder diffraction (SR‐XPD) is employed to investigate the structure symmetry and cell volume of the perovskite phase at temperatures up to 800°C. The highest O₂ permeability is found for x = 0.25 over the whole temperature and ranges, followed by x = 0.4 above 850°C. The O₂ permeability for x = 0.25 reaches 0.01 mL(STP) min^?1 cm^?1 at 925°C with 0.21 bar feed side and Ar sweep gas. X‐ray photoelectron spectroscopy indicates that the charge state of Mn changes from approx. +3 to +4 when x > 0.1, which implies that Mn mainly improves electronic conductivity for x > 0.1. The cell volume is found to decrease linearly with Mn content, which coincides with an increase in the activation energy of O₂ permeability. These results are consistent with the interpretation of the temperature and dependency of O₂ permeation. The sintering behavior and thermal expansion properties are investigated by dilatometry, which show improved sinterability with increasing Mn content and that the thermal expansion coefficient decreases from 12.4 to 11.9 × 10^?6 K^?1 for x = 0 and x = 0.25, respectively.     

Dielectric Relaxation in Zr‐Doped SrTiO3 Ceramics Sintered in N2 with Giant Permittivity and Low Dielectric Loss

SrTiZr_xO₃ (x = 0, 0.002, 0.006, 0.01, and 0.014) ceramics with a weak temperature‐dependent giant permittivity (>10⁴) and a very low dielectric loss (<0.01) were fabricated using the conventional solid‐state reaction method by sintering them in N₂ at 1500°C. With increasing Zr content, the permittivity decreased from approximately 48 000 to 18 000 and the dielectric loss decreased from approximately 0.005 to 0.003. According to the XRD, XPS, and ac conductivity analysis, the dielectric properties of pure SrTiO₃ ceramics sintered in N₂ were due to the existence of the giant defect dipoles generated by the fully ionized oxygen vacancies and Ti³⁺ ions, while the dielectric properties of SrTiZr_xO₃ (x > 0) ceramics were also influenced by the defect dipoles (). The giant permittivity and low dielectric loss phenomenon could be explained by giant defect dipoles related to oxygen vacancies.