Evolution of three-dimensional character across the Lan+1NinO3n+1 homologous series with increase in n

Electrical and magnetic properties of La₃Ni₂O₇ and La₄Ni₃O₁₀ have been investigated in comparison with those of La₂NiO₄, LaNiO₃, and LaSrNiO₄. The results suggest an increasing 3-dimensional character across the homologous series La_n+1Ni_nO_3n+1 with increase in n. Accordingly, the electrical resistivity decreases in the order La₃Ni₂O₇, La₄Ni₃O₁₀, and LaNiO₃ and this trend is suggested to be related to the percolation threshold. Magnetic properties of these oxides also show some interesting trends across the series.     

Oxygen non-stoichiometry of Ln4Ni2.7Fe0.3O10−δ (Ln=La, Pr)

The oxygen deficiency of iron-substituted nickelates Ln₄Ni_2.7Fe_0.3O_10−δ (Ln=La, Pr) with the orthorhombic Ruddlesden-Popper structure was studied by thermogravimetric analysis and coulometric titration in the oxygen partial pressure range 6×10⁻⁵ to 0.7 atm at 973-1223 K. In air, the non-stoichiometry values vary in the relatively narrow ranges (2.4−4.2)×10⁻² for La- and (0.01−2.0)×10⁻² for Pr-containing compositions, increasing with temperature. Due to the smaller size of praseodymium cations, Pr₄Ni_2.7Fe_0.3O_10−δ exhibits a substantially lower thermodynamic stability in comparison with La₄Ni_2.7Fe_0.3O_10−δ and La₄Ni₃O_10−δ, although the oxygen content in Pr₄Ni_2.7Fe_0.3O_10−δ lattice is higher. The partial substitution of iron for nickel has no essential effect on the low-p(O₂) stability limit corresponding to the transition of Pr₄Ni₃O_10−δ into K₂NiF₄-type Pr₂NiO_4+δ. On the contrary, doping of La₄Ni₃O_10−δ with iron decreases the oxygen vacancy concentration and shifts the phase stability boundary towards lower oxygen chemical potentials, suggesting a stabilization of the transition metal-oxygen octahedra in lanthanum nickelate lattice. The Mössbauer spectroscopy showed that the predominant state of iron cations, statistically distributed between the nickel sites, is trivalent.     

Low-Temperature Electronic Properties of the Lan+1NinO3n+1 (n = 2, 3, and ∞) System: Evidence for a Crossover from Fluctuating-Valence to Fermi-Liquid-like Behavior

Measurements of the temperature dependence of the electrical resistivity ρ(T), magnetic susceptibility χ(T), and Seebeck coefficient S(T) have been carried out on the n = 2, 3, and ∞ members of the homologous lanthanum nickel oxide systems La_n+1Ni_nO_3n+1 that were annealed in air. With increasing n, a progressive decrease in the electrical resistivity and a gradual change from insulating to metallic behavior are observed. La₃Ni₂O₇ is nonmetallic, showing a gradual increase in ρ when T decreases (dp/dT < 0) from 300 to 4.2 K, whereas La₄Ni₃O₁₀ and LaNiO₃ exhibit metallic resistivity (dp/dT > 0). A minimum in ρ(T) near 140 K is observed for La₄Ni₃O₁₀, while LaNiO₃ exhibits a T² dependence for ρ(T) below 50 K. The magnetic susceptibility of LaNiO₃ is Pauli-like, but the χ(T) data for La₃Ni₂O₇ and La₄Ni₃O₁₀ below 350 K show a decrease with decreasing temperature. The Seebeck coefficient of all these compounds is negative at high temperatures; La₃Ni₂O₇ and La₄Ni₃O₁₀ exhibit a sign change in S at low temperatures. These results suggest a crossover from a fluctuating-valence to a Fermi-liquid-like behavior with increasing n.     

Transport properties and stability of Ni-containing mixed conductors with perovskite- and K2NiF4-type structure

The total conductivity and Seebeck coefficient of a series of Ni-containing phases, including La₂Ni_1−xM_xO_4+δ (M=Co, Cu; x=0.1-0.2) with K₂NiF₄-type structure and perovskite-like La_0.90Sr_0.10Ga_0.65Mg_0.15Ni_0.20O_3−δ and La_0.50Pr_0.50Ga_0.65Mg_0.15Ni_0.20O_3−δ, were studied in the oxygen partial pressure range from 10⁻¹⁸ Pa to 50 kPa at 973-1223 K. Within the phase stability domain, the conductivity of layered nickelates is predominantly p-type electronic and occurs via small-polaron mechanism, indicated by temperature-activated hole mobility and p(O₂) dependencies of electrical properties. In oxidizing conditions similar behavior is characteristic of Ni-containing perovskites, which exhibit, however, significant ionic contribution to the transport processes. The role of ionic conduction increases with decreasing p(O₂) and becomes dominant in reducing atmospheres. All nickelate-based phases decompose at oxygen pressures considerably lower with respect to Ni/NiO boundary. The partial substitution of nickel in La₂Ni(M)O_4+δ has minor effect on the stability limits, which are similar to that of La_0.90Sr_0.10Ga_0.65Mg_0.15Ni_0.20O_3−δ. On the contrary, praseodymium doping enhances the stability of La_0.50Pr_0.50Ga_0.65Mg_0.15Ni_0.20O_3−δ down to p(O₂) values as low as 10⁻¹⁷-10⁻¹⁰ Pa at 1023-1223 K.     

High-temperature transport properties, thermal expansion and cathodic performance of Ni-substituted LaSr2Mn2O7−δ

The substitution of manganese with nickel in LaSr₂Mn₂O_7−δ, where the solubility limit corresponds to approximately 25% Mn sites, enhances the Ruddlesden-Popper phase stability at elevated temperatures and atmospheric oxygen pressure. The total conductivity of LaSr₂Mn_2−yNi_yO_7−δ (y=0-0.4) decreases with nickel additions, whilst the average thermal expansion coefficients calculated from dilatometric data in the temperature range 300-1370 K increase from (11.4-13.7)×10⁻⁶ K⁻¹ at y=0 up to (12.5-14.4)×10⁻⁶ K⁻¹ at y=0.4. The conductivity and Seebeck coefficient of LaSr₂Mn_1.6Ni_0.4O_7−δ, analyzed in the oxygen partial pressure range 10⁻¹⁵-0.3 atm at 600-1270 K, display that the electronic transport is n-type and occurs via a small polaron mechanism. Reductive decomposition is observed at the oxygen pressures close to Ni/NiO boundary, namely ∼2.3×10⁻¹¹ atm at 1223 K. Within the phase stability domain, the electronic transport properties are essentially p(O₂)-independent. The steady-state oxygen permeability of dense LaSr₂Mn_1.6Ni_0.4O_7−δ membranes is higher than that of (La,Sr)MnO_3−δ, but lower if compared to perovskite-like (Sr,Ce)MnO_3−δ. Porous LaSr₂Mn_1.6Ni_0.4O_7−δ cathodes in contact with apatite-type La₁₀Si₅AlO_26.5 solid electrolyte exhibit, however, a relatively poor electrochemical performance, partly associated with strong cation interdiffusion between the materials.     

In situ variable temperature X-ray diffraction studies on the transformations of nano-precursors to La-Ni-O phases

In situ variable temperature XRD (VT-XRD) measurements on the transformation of nano-precursors to LaNiO phases are presented. Experimental results showed that LaNiO₃ and La₂NiO₄ phases were formed at ca. 700 °C via the reaction of La₂O₃ and NiO (from the initial nano-precursors), where a relatively low temperature of 700 °C was found for the synthesis of La₂NiO₄. The formation of La₃Ni₂O₇ at higher temperature (up to 1150 °C) appeared to proceed through a further reaction of La₂NiO₄ with unreacted NiO, whilst the formation of La₄Ni₃O₁₀ (at 1075 °C) proceeded via a further decomposition of LaNiO₃. Although phase pure La₃Ni₂O₇ and La₄Ni₃O₁₀ were not directly obtained under the processing conditions herein, the results of this study allow for a better understanding of formation pathways, particularly for the higher order La-Ni-O phases.     

p(O2)-stability of LaFe1−xNixO3−δ solid solutions at 1100 °C

LaFe_1−xNi_xO_3−δ (x=0.1−1.0) perovskites were synthesized via citrate route. The p(O₂)-stability of the perovskite phases LaFe_1−xNi_xO_3−δ has been evaluated at 1100 °C based on the results of XRD analysis of powder samples annealed at various p(O₂) and quenched to room temperature. The isothermal LaFeO_3−δ-“LaNiO_3−δ” cross-section of the phase diagram of the La-Fe-Ni-O system has been proposed in the range of oxygen partial pressure −15<log p(O₂)/atm≤0.68. The unit cell parameters of orthorhombic perovskites O-LaFe_1−xNi_xO_3−δ increase with decrease in p(O₂) at fixed composition x. This behavior is explained on the basis of size factor. The decomposition temperatures of rhombohedral phases R-LaFe_1−xNi_xO_3−δ for x=0.7, 0.8, 0.9 and 1.0 in air were determined as 1137, 1086, 1060 and 995 °C, respectively.     

Mixed conductivity, oxygen permeability and redox behavior of K2NiF4-type La2Ni0.9Fe0.1O4+δ

The total conductivity and Seebeck coefficient of La₂Ni_0.9Fe_0.1O_4+δ with K₂NiF₄-type structure, studied in the oxygen partial pressure range from 10⁻⁵ to 0.5 atm at 973-1223 K, were analyzed in combination with the steady-state oxygen permeability, oxygen non-stoichiometry and Mössbauer spectroscopy data in order to examine the electronic and ionic transport mechanisms. Doping of La₂NiO_4+δ with iron was found to promote hole localization on nickel cations due to the formation of stable Fe³⁺ states, although the electrical properties dominated by p-type electronic conduction under oxidizing conditions exhibit trends typical for both itinerant and localized behavior of the electronic sublattice. The segregation of metallic Ni on reduction, which occurs at oxygen chemical potentials close to the low-p(O₂) stability boundary of undoped lanthanum nickelate, is responsible for the high catalytic activity towards partial oxidation of methane by the lattice oxygen of La₂Ni_0.9Fe_0.1O_4+δ as revealed by thermogravimetry and temperature-programmed reduction in dry CH₄-He flow at 573-1173 K. A model for the oxygen permeation fluxes through dense La₂Ni_0.9Fe_0.1O_4+δ ceramics, limited by both bulk ionic conduction and surface exchange kinetics, was proposed and validated.     

Phase stability of La1−xCaxCrO3−δ in oxidizing atmosphere

The chemical stability of perovskite-type La_1−xCa_xCrO_3−δ (x=0.1, 0.2, 0.3) in high oxygen partial pressure, P_O2, was investigated with three methods: thermogravimetry, XRD analysis, and thermodynamic calculation. The second phase, CaCrO₄ was observed by XRD analysis on the powder equilibrated in high P_O2. Thermogravimetry under fixed temperatures sensitively detected the segregation of the second phase in the form of oxygen incorporation, because oxidation of chromium ion accompanies the segregation. The second phase tended to appear in high P_O2 and at low temperature. The single-phase regions of La_1−xCa_xCrO_3−δ obtained from the two experimental methods well agreed with each other. The results of thermodynamic calculation on the assumption of ideality of the solid solution also agreed with the experimental results. These results suggested the sufficient chemical stability of La_1−xCa_xCrO_3−δ in high P_O2 concerning the application to an interconnector of high-temperature solid oxide fuel cells; for example, La_0.7Ca_0.3CrO_3−δ is stable at 1273 K in air.     

Direct syntheses of Lan+1NinO3n+1 phases (n=1, 2, 3 and ∞) from nanosized co-crystallites

A new direct route for the “bottom up” syntheses of phases in the La_n+1Ni_nO_3n+1 series (n=1, 2, 3 and ∞) has been achieved via single-step heat treatments of nanosized co-crystallized precursors. The co-crystallized precursors were prepared using a continuous hydrothermal flow synthesis system that uses a superheated water flow at ca. 400 °C and 24.1 MPa to produce nanoparticulate slurries. Overall, a significant reduction in time and number of steps for the syntheses of La₃Ni₂O₇ and La₄Ni₃O₁₀ was achieved compared with more conventional synthesis methods, which typically require multiple homogenization and reheating steps over several days.     

Comparison of the Chemical Stability of Li1−xCoO2 and Li1−xNi0.85Co0.15O2 Cathodes

The chemical stability of the layered Li_1−xCoO₂ and Li_1−xNi_0.85Co_O.15O₂ cathodes is compared by monitoring the oxygen content with lithium content (1−x) in chemically delithiated samples. The Li_1−xCoO₂ system tends to lose oxygen from the lattice at deep lithium extraction while the Li_1−xNi_0.85Co_0.15O₂ system does not lose oxygen at least for (1−x)>0.3. This difference seems to result in a lower reversible (practical) capacity (140 mA h/g) for LiCoO₂ compared to that for LiNi_0.85Co_0.15O₂ (180 Ma h/g). The loss of significant amount of oxygen leads to a sliding of oxide layers and the formation of a major P3 and a minor O1 phase for the end member CoO_2−δ with δ=0.33. In contrast, Ni_0.85Co_0.15O_2−δ with a small amount of δ=0.1 maintains the initial O3 layer structure.     

Oxygen nonstoichiometry and chemical stability of Nd2−xSrxNiO4+δ

Nonstoichiometric variation of oxygen content in Nd_2−xSr_xNiO_4+δ (x=0, 0.2, 0.4) and decomposition P(O₂) were determined by means of high temperature gravimetry and coulometric titration. The measurements were carried out in the temperature range from 873 to 1173 K and the P(O₂) range from 10⁻²⁰ to 1 bar. Nd_2−xSr_xNiO_4+δ shows the oxygen excess and the oxygen deficient composition depending on P(O₂), temperature, and the Sr content. To evaluate the characteristics of oxygen nonstoichiometric behavior, partial molar enthalpy of oxygen was calculated. The value of partial molar enthalpy of oxygen slightly approaches zero as δ increases in the oxygen excess region while that is independent of δ in the oxygen deficient region. Discussion was made by comparing data of this study with nonstoichiometric and thermodynamic data of La_2−xSr_xNiO_4+δ: Nd_2−xSr_xNiO_4+δ show more oxygen excess than La_2−xSr_xNiO_4+δ in the higher P(O₂) region, while the nonstoichiometric behavior in the oxygen deficient composition is almost the same. The variation of partial molar enthalpy of oxygen with δ for Nd_2−xSr_xNiO_4+δ in the oxygen excess region is much smaller than that of La_2−xSr_xNiO_4+δ. The oxygen nonstoichiometric behavior of Nd_2−xSr_xNiO_4+δ is more ideal-solution-like than that of La_2−xSr_xNiO_4+δ.     

Mixed conductivity and Mössbauer spectra of (La0.5Sr0.5)1−xFe1−yAlyO3−δ (x=0-0.05, y=0-0.30)

Aluminum incorporation in the rhombohedrally distorted perovskite lattice of (La_0.5Sr_0.5)_1−xFe_1−yAl_yO_3−δ (x=0-0.05, y=0-0.30) decreases the unit cell volume and partial ionic and p-type electronic conductivities, while the oxygen nonstoichiometry and thermal expansion at 900-1200 K increase on doping. The creation of A-site cation vacancies has an opposite effect on the transport properties of Al-substituted ceramics. The maximum A-site deficiency tolerated by the (La,Sr)(Fe,Al)O_3−δ structure is however limited, close to 3-4%. The Mössbauer spectroscopy revealed progressive localization of electron holes and a mixed charge-compensation mechanism, which results in higher average oxidation state of iron when Al³⁺ concentration increases. The average thermal expansion coefficients of (La_0.5Sr_0.5)_1−xFe_1−yAl_yO_3−δ are (12.2-13.0)×10⁻⁶ K⁻¹ at 300-900 K and (20.1-30.0)×10⁻⁶ K⁻¹ at 900-1200 K in air. The steady-state oxygen permeability (OP) of dense Al-containing membranes is determined mainly by the bulk ionic conductivity. The ion transference numbers at 973-1223 K in air, calculated from the oxygen permeation and faradaic efficiency (FE) data, vary in the range 1×10⁻⁴-3×10⁻³, increasing with temperature.     

Oxygen Nonstoichiometry, Conductivity, and Seebeck Coefficient of La0.3Sr0.7Fe1−xGaxO2.65+δ Perovskites

The total electrical conductivity and the Seebeck coefficient of perovskite phases La_0.3Sr_0.7Fe_1−xGa_xO_2.65+δ (x=0-0.4) were determined as functions of oxygen nonstoichiometry in the temperature range 650-950°C at oxygen partial pressures varying from 10⁻⁴ to 0.5 atm. Doping with gallium was found to decrease oxygen content, p-type electronic conduction and mobility of electron holes. The results on the oxygen nonstoichiometry and electrical properties clearly show that the role of gallium cations in the lattice is not passive, as it could be expected from the constant oxidation state of Ga³⁺. The nonstoichiometry dependencies of the partial molar enthalpy and entropy of oxygen in La_0.3Sr_0.7(Fe,Ga)O_2.65+δ are indicative of local inhomogeneities, such as local lattice distortions or defect clusters, induced by gallium incorporation. Due to B-site cation disorder, this effect may be responsible for suppressing long-range ordering of oxygen vacancies and for enhanced stability of the perovskite phases at low oxygen pressures, confirmed by high-temperature X-ray diffraction and Seebeck coefficient data. The values of the electron-hole mobility in La_0.3Sr_0.7(Fe,Ga)O_2.65+δ, which increases with temperature, suggest a small-polaron conduction mechanism.     

Synthesis, crystal structure, and magnetic properties of the manganate La2Ca2MnO6(O2) related to the hexagonal perovskite-type structure

The compound La₂Ca₂MnO₆(O₂) has been synthesized from La₂Ca₂MnO₇ heated at 1123 K under high pressure (4 GPa) with KClO₃ as oxygen source. The crystal structure has been refined from X-ray powder data in the space group. The unit-cell parameters are a=5.6335(2) Å and c=17.4879(8) Å. Perpendicular to the c-axis, the structure is built up by the periodic stacking of two close packed [LaO₃] layers separated by a layer of composition [Ca₂O₂] containing (O₂)²⁻ peroxide ions. This oxide belongs to the family of compounds formulated as [A′₂O_2−δ][A_nB_n−1O_3n] for n=2 and δ=0. It is the first member of the series where the thickness of the perovskite slab corresponds to one [BO₆] (B=Mn) octahedron. The structural relationships with La₂Ca₂MnO₇ are discussed and the magnetic properties show that in both phases manganese is tetravalent.     

Phase equilibria in the pseudo-binary system SrO-Fe2O3

The phase relations in the pseudo-binary system SrO-Fe₂O₃ have been investigated in air up to 1150°C by means of powder X-ray diffraction and thermal analysis. Sr₃Fe₂O_7−δ, SrFeO_3−δ and SrFe₁₂O₁₉ are stable phases in the entire investigated temperature region, whereas Sr₂FeO_4−δ and Sr₄Fe₃O_10−δ decompose above 930±10°C and 850±25°C, respectively. Sr₄Fe₆O_13±δ is entropy-stabilized relative to SrFeO_3−δ and SrFe₁₂O₁₉ above 775±25°C. Extended solid-solution Sr_1±xFeO_3−δ was demonstrated. On the Fe-deficient side, the extent of solid solubility appeared to decrease gradually with temperature, whereas an abrupt decrease due to formation of Sr₄Fe₆O_13±δ was observed above 775°C on the Sr-deficient side.     

Electronic state of Fe used as Mössbauer probe in the perovskites LaMO3 (M=Ni and Cu)

For the first time a comparative study of rhombohedral LaNiO₃ and LaCuO₃ oxides, using ⁵⁷Fe Mössbauer probe spectroscopy (1% atomic rate), has been carried out. In spite of the fact that both oxides are characterized by similar crystal structure and metallic properties, the behavior of ⁵⁷Fe probe atoms in such lattices appears essentially different. In the case of LaNi_0.99Fe_0.01O₃, the observed isomer shift (δ) value corresponds to Fe³⁺ (3d⁵) cations in high-spin state located in an oxygen octahedral surrounding. In contrast, for the LaCu_0.99Fe_0.01O₃, the obtained δ value is comparable to that characterizing the formally tetravalent high-spin Fe⁴⁺(3d⁴) cations in octahedral coordination within Fe(IV) perovskite-like ferrates. To explain such a difference, an approach based on the qualitative energy diagrams analysis and the calculations within the cluster configuration interaction method have been developed. It was shown that in the case of LaNi_0.99Fe_0.01O₃, electronic state of nickel is dominated by the d⁷ configuration corresponding to the formal ionic “Ni³⁺-O²⁻” state. On the other hand, in the case of LaCu_0.99Fe_0.01O₃ a large amount of charge is transferred via Cu-O bonds from the O:2p bands to the Cu:3d orbitals and the ground state is dominated by the d⁹L configuration (“Cu²⁺−O” state). The dominant d⁹L ground state for the (CuO₆) sublattice induces in the environment of the ⁵⁷Fe probe cations a charge transfer Fe³⁺+O⁻(L)→Fe⁴⁺+O²⁻, which transforms “Fe³⁺” into “Fe⁴⁺” state. The analysis of the isomer shift value for the formally “Fe⁴⁺” ions in perovskite-like oxides clearly proved a drastic influence of the 4s iron orbitals population on the Fe−O bonds character.     

Perovskites as Precursors for Ni/La2O3 Catalysts in the Dry Reforming of Methane: Synthesis by Constant pH Co‐Precipitation,Reduction Mechanism and Effect of Ru‐Doping

LaNiO₃ perovskite is an interesting precursor for Ni/La₂O₃ catalysts for the dry reforming of methane at high temperatures. Precursors have been synthesized by co‐precipitation without, with 2.5 at %, and with 5 at % Ru doping. The presence of Ru leads to a stabilization of the perovskite structure and hinders the decomposition into NiO and Ruddlesden‐Popper mixed oxides La_n+1Ni_nO_3n+1, which was observed for the Ru‐free sample upon calcination at 1000 °C (n = 3). Upon reduction in hydrogen, a mechanism involving at least two steps was observed and the first major step was identified as the partial reduction of the precursor leading to a LaNiO_2.5‐like intermediate. The second major step is the reduction to Ni metal supported on La₂O₃ independent of the Ru content of the catalyst. In the presence of Ru, indications for Ni‐Ru alloy formation and for a higher dispersion of the metallic phase were found. The catalytic activity in DRM of the catalyst containing 2.5 % Ru was superior to the catalysts with more or without Ru. Furthermore, the propensity of coke formation was reduced by the presence of Ru.     

Ca3−xLaxCo4O9+δ (x=0, 0.3): New cobaltite materials as cathodes for proton conducting solid oxide fuel cell

Misfit-type Ca_3−xLa_xCo₄O_9+δ (x=0, 0.3) oxides were synthesised to be evaluated as possible cathode materials for proton conducting fuel cells (PCFCs) based on BaCe_0.9Y_0.1O_3−δ (BCY10) dense ceramic electrolyte. The electrical conductivity value of Ca_2.7La_0.3Co₄O_9+δ (σ≈53 S cm^-1 at 600 °C) is in the range of usually required value for a cathode application (about 50-100 S cm^-1). In order to test the performance of each compound as cathode material, impedance measurements were carried out on Ca_3−xLa_xCo₄O_9+δ/BaCe_0.9Y_0.1O_3−δ/Ca_3−xLa_xCo₄O_9+δ symmetrical half cells over the temperature range 400-800 °C under wet air. A promising electrocatalytic activity has been observed with both compounds Ca₃Co₄O_9+δ and Ca_2.7La_0.3Co₄O_9+δ. Factually, the area specific resistance obtained was about 2.2 Ω cm² at 600 °C.     

Ionic and electronic transport in La2Ti2SiO9-based materials

The total conductivity of monoclinic La₂Ti₂SiO₉ is mixed oxygen-ionic and n-type electronic, and increases on reduction of the oxygen partial pressure down to 10⁻²¹ atm at 973-1223 K. The substitution of Ti⁴⁺ with Nb⁵⁺ decreases both contributions to the conductivity, whilst Pr doping and reducing p(O₂) have opposite effects. The oxygen ion transference numbers of La₂Ti₂SiO_9−δ, LaPrTi₂SiO_9±δ and La₂Ti_1.8Nb_0.2SiO_9±δ ceramics, measured by the faradaic efficiency and e.m.f. methods, vary in the range 0.15-0.32, increasing when temperature decreases. In air, the activation energies for the ionic and electronic transport are 1.23-1.40 and 1.59-1.74 eV, respectively. Protonic contribution to the conductivity in wet atmospheres becomes significant at temperatures below 1000 K. The experimental data and the results of atomistic computer simulations suggest that the oxygen-ionic and electronic transport is primarily determined by processes involving TiO₆ octahedra. The ionic conduction may occur via both the vacancy and interstitial migration mechanisms, but the former is more favorable energetically and should dominate, at least, in reducing atmospheres. The average thermal expansion coefficients of La₂Ti₂SiO₉-based ceramics, calculated from dilatometric data in air, are (8.7−9.5)×10⁻⁶ K⁻¹ at 300-1373 K. The lattice of lanthanum titanate-silicate is almost intolerant with respect to A-site deficiency and to doping with lower-valence cations, such as Sr and Fe.