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Structural evolution of Nd2NiO4.23 with temperature, indicating several 1st order phase transitions with sub-mesoscopic oxygen ordering and instant ordering kinetics below 800 K.

For oxygen conducting materials applied in solid oxide fuel cells and chemical-looping processes, the understanding of the oxygen diffusion mechanism and the materials' crystal structure at different stages of the redox reactions is a key parameter to control their performance. In this paper we report the first ever in situ 3D electron diffraction (ED) experiment in a gas environment and with it uncover the structure evolution of SrFeO2.5 as notably different from that reported from in situ X-ray and in situ neutron powder diffraction studies in gas environments. Using in situ 3D ED on submicron sized single crystals, we observe the transformation under O-2 flow of brownmillerite SrFeO2.5 with an intra- and interlayer ordering of the left and right twisted (FeO4)(infinity) tetrahedral chains (space group Pcmb) into consecutively SrFeO2.75 with space group Cmmm (at 350 degrees C, 33% O-2) and SrFeO3-delta with space group Pm3m (at 400 degrees C, 100% O-2). Upon reduction in H-2 flow, the crystals return to the brownmillerite structure with intralayer order, but without regaining the interlayer order of the pristine crystals. Therefore, redox cycling of SrFeO2.5 crystals in O-2 and H-2 introduces stacking faults into the structure, resulting in an I2/m(0 beta gamma)0s symmetry with variable beta.

For oxygen conducting materials applied in solid oxide fuel cells and chemical-looping processes, the understanding of the oxygen diffusion mechanism and the materials’ crystal structure at different stages of the redox reactions is a key parameter to control their performance. In this paper we report the first ever in situ 3D ED experiment in a gas environment and with it uncover the structure evolution of SrFeO2.5 as notably different from that reported from in situ X-ray and in situ neutron powder diffraction studies in gas environments. Using in situ 3D ED on submicron sized single crystals obtained from a high quality monodomain SrFeO2.5 single crystal, we observe the transformation under O2 flow of SrFeO2.5 with an intra- and interlayer ordering of the left and right twisted (FeO4) tetrahedral chains (space group Pcmb) into consecutively SrFeO2.75 (space group Cmmm) and SrFeO3- (space group Pm3 ̅m). Upon reduction in H2 flow, the crystals return to the brownmillerite structure with intralayer order, but without regaining the interlayer order of the pristine crystals. Therefore, redox cycling of SrFeO2.5 crystals in O2 and H2 introduces stacking faults into the structure, resulting in an I2/m(0βγ)0s symmetry with variable β.

To understand oxygen diffusion mechanisms in non-stoichiometric oxides, the possibility to explore structural changes as a function of the oxygen partial pressure with temperature and related oxygen bulk stoichiometry is mandatory. This article reports on the realization of a high-temperature furnace, suitable for single-crystal neutron diffraction, working continuously at temperatures of up to 1000°C at different and adjustable partial gas pressures of up to 2 bar (1 bar = 100 kPa). This allows exploration of the phase diagrams of non-stoichiometric oxides under in situ conditions and controlled oxygen partial pressure. As a pilot study, the structural changes of Pr2NiO4+δ were explored at room temperature (δ ≃ 0.24) and at 900°C under 1 bar P(O2) (δ ≃ 0.13) as well as under secondary vacuum (approximately 10−5 mbar) conditions yielding a δ close to zero. The strong anharmonic displacements of the apical oxygen atoms along the [110] shallow diffusion pathway, which were previously observed at room temperature and 400°C, become more isotropic at 900°C. The study shows that the anisotropic oxygen displacements, here related to lattice instabilities, play a major role in understanding oxygen diffusion pathways and related activation energies at moderate temperatures. This also shows the importance of the availability of reaction cells for single-crystal neutron diffraction to explore the phase diagram and associated structural changes of non-stoichiometric oxygen ion conductors and respective diffusion mechanisms.

La2CoO4+δ is a strongly correlated oxide with exciting physical and electronic properties originating from the subtle interplay of the lattice, orbital, charge, and spin degrees of freedom. In particular, oxygen-rich La2CoO4.25 is a key compound for studying oxygen and electronic ordering phenomena and their correlation. Single-crystal growth of these phases has been plagued by difficulties related to their incongruent melting. In this work, we report on the growth and characterization of high-quality, centimeter-sized La2CoO4.25 single crystals, suitable for neutron scattering experiments. La2CoO4+δ single crystals were grown by the traveling solvent floating zone without the addition of a solvent but continuously stabilizing the growth conditions. Postsynthesis annealing at 500 °C in oxygen flux yielded phase-pure La2CoO4.25, which was further characterized by single-crystal neutron and X-ray diffraction, as well as by scanning electron microscopy with energy-dispersive X-ray spectroscopy, revealing its quality in terms of composition, homogeneity, and crystalline quality. For La2CoO4.25, a complex structure with a two-dimensional modulation vector related to oxygen ordering was revealed by single-crystal X-ray and neutron powder diffraction studies. In addition, magnetic measurements coupled with preliminary single-crystal elastic neutron scattering experiments exhibited antiferromagnetic ordering with a Néel temperature (TN) of 36 K with a complex magnetic structure involving the doubling of all orthorhombic axes.

High resolution and high intensity neutron powder diffraction are used to determine the temperature dependence of the crystallographic and magnetic structure of the orthoferrite CeFeO3. The high temperature G x -type magnetic coupling of the Fe-sublattice described by the Γ4 (G x A y F z ) irreducible representation changes at the spin reorientation temperature T SR = 228 K to a G y -type coupling of Γ1 (A x G y C z ). The spin reorientation is of first order and sees a hysteresis of about 2.5 K at T SR. Below 35 K faint magnetic peaks reflecting C z type magnetic coupling appear and are argued to be related to the Ce-sublattice. Magnetic moments at 2 K amount to μ Fe = 4.15 μ B and μ Ce = 0.11 μ B. CeFeO3 is only the second RFeO3 compound after DyFeO3 showing this ground state magnetic structure of the Fe-sublattice. The orthorhombic structure Pbnm is kept over the whole temperature range.

Hole doping in Nd${}_{2}$NiO${}_{4.00}$ can be either achieved by substituting the trivalent Nd atoms by bivalent alkaline earth metals or by oxygen doping, yielding Nd${}_{2}$NiO${}_{4+\delta}$. In this study, we investigated the interplay between oxygen and spin ordering for a low oxygen doping concentration i.e. Nd${}_{2}$NiO${}_{4.10}$. Although the extra oxygen doping level remains rather modest with only one out of 20 possible interstitial tetrahedral lattice sites occupied, we observed by single crystal neutron diffraction the presence of a complex 3D modulated structure related to oxygen ordering already at ambient, the modulation vectors being $\pm$2/13\textit{\textbf{a*}}$\pm$3/13\textit{\textbf{b*}}, $\pm$3/13\textit{\textbf{b*}}$\pm$2/13\textit{\textbf{b*}} and $\pm$1/5\textit{\textbf{a*}}$\pm$1/2\textit{\textbf{c*}} and satellite reflections up to fourth order. Temperature dependent neutron diffraction studies indicate the coexistence of oxygen and magnetic ordering below T${}_{N}$ $\simeq$ 48 K, the wave vector of the Ni sublattice being \textbf{\textit{k}}=(100). In addition, magnetic satellite reflections adapt exactly the same modulation vectors as found for the oxygen ordering, evidencing a unique coexistence of 3D modulated ordering for spin and oxygen ordering in Nd${}_{2}$NiO${}_{4.10}$. Temperature dependent measurements of magnetic intensities suggest two magnetic phase transitions below 48 K and 20 K, indicating two distinct onsets of magnetic ordering for the Ni and Nd sublattice, respectively.

High resolution and high intensity neutron powder diffraction are used to determine the temperature dependence of the crystallographic and magnetic structure of the orthoferrite CeFeO

Depending on the synthesis route, the oxygen ion electrolyte Sr

Depending on the synthesis route, the oxygen ion electrolyte Sr2ScGaO5 shows two polymorphs, a brownmillerite and a cubic perovskite framework. In order to better explore oxygen diffusion pathways ...

We investigated the influence of oxygen over-stoichiometry on apical oxygen disorder and magnetic correlations in Nd2NiO4+d (d~0.11) in the temperature range of 2-300 K by means of synchrotron x-ray powder diffraction, neutron single crystal and powder diffraction studies, combined with macroscopic magnetic measurements. In the investigated temperature range, the compound crystalizes in a tetragonal commensurate structure with the P42/ncm space group with excess oxygen atoms occupy the 4b (3/4 1/4 1/4) interstitial sites, coordinated by four apical oxygen atoms. Large and anisotropic thermal displacement parameters are found for equatorial and apical oxygen atoms, which are strongly reduced on an absolute scale compared to the Nd2NiO4.23 phase. Maximum Entropy analysis of the neutron single crystal diffraction data uncovered anharmonic contributions to the displacement parameters of the apical oxygen atoms, toward the nearest vacant 4b interstitial site, related to the phonon assisted oxygen diffusion mechanism. Macroscopic magnetization measurements and neutron powder diffraction studies reveal long-range antiferromagnetic ordering of the Ni-sublattice at TN ~ 53 K with a weak ferromagnetic component along the c-axis, while the long-range magnetic ordering of the Nd-sublattice occurs below 10 K. Temperature dependent neutron diffraction patterns show the appearance of a commensurate magnetic order at TN with the propagation vector k = (100) and the emergence of an additional incommensurate phase below 30 K, while both phases coexist at 2 K. The commensurate magnetic structure is best described by the P42/nc`m` Shubnikov space group. Refined magnetic moments of the Ni and Nd-sites at 2 K are 1.144(76) muB and 1.632(52) muB respectively. A possible origin of the incommensurate phase is discussed and a tentative magnetic phase diagram is proposed.

LaAlO3 perovskites, as such and with 25% molar Al substitution by Cu, Co, or Ga, have been prepared by sol-gel methods and tested as heterogeneous catalysts in the gas-phase conversion of ethanol. LaAlO3 presented a significant acidic character, with high formation of ethylene by ethanol dehydration. B-site substitutions increased the basicity of the catalysts, favoring the dehydrogenation of ethanol to acetaldehyde. The most reducible Cu- and Co-substituted materials, characterized by easier formation of surface oxygen vacancies, promoted the self-condensation of acetaldehyde by the Tishchenko mechanism, with formation of acetone and odd-carbon number products. Aldol coupling of acetaldehyde, favored on pure and Ga-substituted LaAlO3, led to the formation of butadiene and hexadiene. The role of Ga insertion, favoring both dehydrogenation of ethylene and dehydration of higher alcohols, corresponds to an amphoteric character. The formation of olefins and diolefins on all catalysts suggests that LaAl-based materials present the most acidic character among La-perovskites.

International audience; The results of the synthesis and characterization of the optimally doped La1.85Ca0.15(Cu1−xNix)O4-δ solid solution with x = 0, 0.1, 0.2 and 0.3 are reported. The versatility of these La1.85Ca0.15(Cu1−xNix)O4−δ materials is explained on the basis of structural features and the ability to accommodate oxygen nonstoichiometry. According to powder X-ray and neutron diffraction data, La1.85Ca0.15(Cu1−xNix)O4−δ adopts the tetragonal structure with oxygen vacancies occurring preferentially at the Oap sites within the {(La/Ca)O} layers of the perovskite blocks and the oxygen deviation from stoichiometry δ was found to be δ=0.0905(6). The bulk conductivity indicated an Arrhenius-type thermally activated process and oxygen vacancies are the possible ionic charge carriers at T=270 °C. An increase of the conductivity was detected when Ni was introduced. With nickel ratio variation, a strong correlation was observed between the Cu(Ni)-Oap apical bond length variation and the conductivity variation through controlling the O2− ion migration.

International audience; In the framework of nowadays challenges in the automotive catalysis, directed to the mitigation of pollution caused by the emissions of internal combustion engines, a series of LaAl1-xCoxO3 perovskites were investigated with the purpose of enhancing the oxidation of soot in the presence of NOx. Perovskite oxides LaAl1-xCoxO3 (x=0; 0.25; 0.5; 0.75 and 1) were synthesized by a solgel route and characterized by different methods: X-Ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR), N2-sorption, O2/NOx-temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). The perovskite oxides were tested as catalysts for NO oxidation in isothermal mode and for NOx-assisted soot oxidation in temperature programmed reaction. Structural results reveal that Co is well incorporated in the perovskite structure expanding the unit cell, and doping Co may result in the distortion of the BO6 octahedra of the general ABO3 perovskite structure. An increase in Co substitution with x up to 0.75 remarkably promotes the oxidation activity, whereas total replacement of Al by Co degrades the catalytic performance. Among the prepared solids, LaAl0.25Co0.75O3 is the most active for NO oxidation, with a conversion of 78% at 320 °C, and it also exhibits the highest activity for NOxassisted soot oxidation, with a T10% of 377 °C while maintaining high NO2 production (71%). The outstanding performance of LaAl0.25Co0.75O3 is associated with the high mobility of lattice oxygen species and the role of surface adsorbed oxygen seems not to be prominent. The strong correlation of catalytic activity with NOx-TPD profiles suggests that NOx adsorption on catalyst surface is an essential step in soot oxidation. It is also shown that higher calcination temperature promotes the crystallinity of perovskite phase and leads to the improvement in the catalytic activity. The present work indicates that the prepared perovskite catalysts are competitive with noble-metal rivals for NOx-assisted soot oxidation and outperform them in NO2 production for further NOx abatement.

Supplementary files http://www.rsc.org/suppdata/c8/cy/c8cy00806j/c8cy00806j1.pdf; International audience; Two sets of copper oxide–brownmillerite Ca2Fe2O5 catalysts are prepared and studied for CO oxidation. The first set of catalysts is prepared by classical wet impregnation of the Ca2Fe2O5 support. The second set is prepared by Ca2Fe2O5 B-site doping. The active catalyst species are generated during hydrogen treatment. The two sets of catalysts behave very differently in CO oxidation. The performance of the impregnated catalysts is independent of the Cu content, while the performance of the doped catalysts can be tuned by the copper content. The best performing catalyst is a doped-reduced catalyst with 40 mol% Cu. Detailed characterization of the catalysts is carried out using nitrogen physisorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and in situ X-ray absorption fluorescence spectroscopy (XAFS).

Oxygen intercalation/deintercalation in Pr

We investigated moderate-temperature oxygen diffusion mechanisms in Sr2ScGaO5 with Brownmillerite structure type. From oxygen isotope 18O−16O exchange experiments we determined that oxygen mobility sets in above 550 °C. Temperature-dependent neutron and X-ray (synchrotron) diffraction experiments allowed us to correlate the oxygen mobility with a subtle phase transition of the orthorhombic room-temperature structure with I2mb space group toward Imma, going along with a disorder of the (GaO4)∞-tetrahedral chains. From lattice dynamical simulations we could clearly evidence that dynamic switching of the (GaO4)∞-tetrahedral chains from its R to L configuration sets in at 600 °C, thus correlating oxygen diffusion with the dynamic disorder. Oxygen ion diffusion pathways are thus constrained along the onedimensional oxygen vacancy channels, which is a different diffusion mechanism compared to that of the isostructural CaFeO2.5, where diffusion of the apical oxygen atoms into the vacant lattice sites are equally involved in the diffusion pathway. The proposed ordered room-temperature structure in I2mb is strongly supported by 17O, 45Sc, and 71Ga NMR measurements, which indicate the presence of crystallographically unique sites and the absence of local disordering effects below the phase transition. The electric field gradient tensor components measured at the nuclear sites are found to be in excellent agreement with calculated values using the WIEN2k program. The oxygen site assignment has been independently confirmed by 17O{45Sc} transfer of adiabatic populations double-resonance experiments.

The purpose of this paper is to present the reaction of a cuprate La 1.8 Pr 0.2 CuO 4 with CaH 2 which yields La 1.8 Pr 0.2 CuO 3.5 , a new oxygen-vacancy-ordered arrangement of cooperatively-distorted Cu 2 O 3 planes containing 4-coordinate Cu + sites. This new compound has been characterized by X-ray diffraction, electron paramagnetic resonance (EPR) and DSC. The X-ray powder diffraction data have revealed that this cuprate is crystallized with the so-called “pseudo-S” type structure, showing a monoclinic symmetry and space group A2/m . Concerning the EPR measurements, they have shown the presence of Cu 2+ cation and a hyperfine structure suggesting a pronounced hybridization of the copper–oxygen bond. Finally, X-ray diffraction has demonstrated that the obtained La 1.8 Pr 0.2 CuO 3.5 , heated in oxygen at 420 °C, turns topotactically into La 1.8 Pr 0.2 CuO 4 with a T′-type structure (I4/mmm).

International audience; Oxygen-deficient Sr$_2$ScGaO$_5$ single crystals with a cubic perovskite structure were grown by the floating-zone technique. The transparent crystals of this pure 3D oxygen electrolyte are metastable at ambient temperature, showing one-sixth of all oxygen positions vacant. While neutron single-crystal diffraction, followed by maximum entropy analysis, revealed a strong anharmonic displacements for the oxygen atoms, a predominant formation of ScO$_6$ octahedra and GaO$_4$ tetrahedra is indicated by Raman spectroscopic studies, resulting in a complex oxygen defect structure with short-range order. Temperature-dependent X-ray powder diffraction (XPD) and neutron powder diffraction (NPD) studies reveal the cubic Sr$_2$ScGaO$_5$ to be thermodynamically stable only above 1400 °C, while the stable modification below this temperature shows the brownmillerite framework with orthorhombic symmetry. Cubic Sr$_2$ScGaO$_5$ remains surprisingly kinetically stable upon heating from ambient temperature to 1300 °C, indicating a huge inertia for the retransformation toward the thermodynamically stable brownmillerite phase. Ionic conductivity investigated by impedance spectroscopy was found to be 10$^{–4}$ S/cm at 600 °C, while oxygen 18O/16O isotope exchange indicates a free oxygen mobility to set in at around 500 °C.

Oxygen-deficient Sr

32nd European Crystallography Meeting, ECM 32, Vienna, Austria, 18 Aug 2019 - 23 Aug 2019; Acta crystallographica / A Foundations and advances 75(a2), MS27-04 (2019). doi:10.1107/S2053273319091289 special issue: "August 2019 issue Abstracts of the 32nd European Crystallography Meeting Vienna, Austria, 18-23 August 2019", Published by Blackwell, Oxford [u.a.]

We investigated the formation of extended defects in CaFeO2.5, predominantly appearing as antiphase boundaries (APBs), as a function of the synthesis method and temperature. While CaFeO2.5 is known to adopt an ordered oxygen defect structure showing long range order of the (FeO4)∞ chains in its bulk form, interestingly, we demonstrated that the length of these (FeO4)∞ chains can be considerably scaled down to few nanometers by adopting a modified sol–gel method (low temperature synthesis) while the grain size of the resulting nano-phase CaFeO2.5 is around 50 nm. We discuss the synthesis dependent modulation of the length of APBs, characterized by X-ray diffraction and high resolution TEM, to be at the origin of an amplified switching dynamics of the (FeO4)∞ chains. This can accordingly explain the reduction of the onset temperature for oxygen diffusion to set in from 450 °C for bulk-CaFeO2.5 to 320 °C for nano-CaFeO2.5, as determined by 18O/16O oxygen isotope exchange reactions.

International audience; We investigated the first charge cycle of LaNi3.6Co0.7Al0.4Mn0.3 (LaMM) during electrochemical reduction in a 6N KOD (potassium deuteroxide) electrolyte, corresponding to conditions of commercially used batteries by means of in situ neutron powder diffraction. Our measurement allowed to directly analyze the phase range of the α and β phases and the related volume change as a function of the charge transfer. The intercalation of hydrogen was followed in a home-made electrochemical cell, installed on the high intensity neutron powder diffractometer (DMC) at the Swiss continuous spallation neutron source. Compared to previous investigations following mostly in situ charging under pressure (following pressure-composition-temperature isotherms, PCT), our experimental conditions reflect closely the process as used in technical battery applications

International audience; The existing controversy about the symmetry of the crystal structure of the ground state of the critical doped La1.95Sr0.05CuO4 has been resolved by analyzing the single crystalneutron diffraction data collected between 5 and 730 K. We observed small but significant intensities for “forbidden” reflections given by extinction rules of the orthorhombic Bmab space group at low temperatures. A careful investigation of neutron diffraction data reveals that the crystal structure of La1.95Sr0.05CuO4 at 5 K is monoclinic with B2/m (2/m 1 1) space group. The monoclinic structure emerges from the orthorhombic structure in a continuous way; however, the structure is stable below ∼120 K which agrees with other observed phenomena. Our results on symmetry changes are crucial for the interpretation of physical properties also in other high temperature superconductors with similar structures

SrFeO(2.5) and SrCoO(2.5) are able to intercalate oxygen in a reversible topotactic redox reaction already at room temperature to form the cubic perovskites Sr(Fe,Co)O(3), while CaFeO(2.5) can only be oxidized under extreme conditions. To explain this significant difference in low temperature oxygen mobility, we investigated the homologous SrFeO(2.5) and CaFeO(2.5) by temperature dependent oxygen isotope exchange as well as by inelastic neutron scattering (INS) studies, combined with ab initio (DFT) molecular dynamical calculations. From (18)O/(16)O isotope exchange experiments we proved free oxygen mobility to be realized in SrFeO(x) already below 600 K. We have also evidence that low temperature oxygen mobility relies on the existence of specific, low energy lattice modes, which trigger and amplify oxygen mobility in solids. We interpret the INS data together with the DFT-based molecular dynamical simulation results on SrFeO(2.5) and CaFeO(2.5) in terms of an enhanced, phonon-assisted, low temperature oxygen diffusion for SrFeO(3-x) as a result of the strongly reduced Fe-O-Fe bond strength of the apical oxygen atoms in the FeO(6) octahedra along the stacking axis. This dynamically triggered phenomenon leads to an easy migration of the oxide ions into the open vacancy channels and vice versa. The decisive impact of lattice dynamics, giving rise to structural instabilities in oxygen deficient perovskites, especially with brownmillerite-type structure, is demonstrated, opening new concepts for the design and tailoring of low temperature oxygen ion conductors.

Conventional high-temperature reactions limit the control of coordination polyhedra in transition-metal oxides to those obtainable within the bounds of known coordination geometries for a given transition metal. For example, iron atoms are almost exclusively coordinated by three-dimensional polyhedra such as tetrahedra and octahedra. However, recent works have shown that binary metal hydrides act as reducing agents at low temperatures, allowing access to unprecedented structures. Here we show the reaction of a perovskite SrFeO3 with CaH2 to yield SrFeO2, a new compound bearing a square-planar oxygen coordination around Fe2+. SrFeO2 is isostructural with 'infinite layer' cupric oxides, and exhibits a magnetic order far above room temperature in spite of the two-dimensional structure, indicating strong in-layer magnetic interactions due to strong Fe d to O p hybridization. Surprisingly, SrFeO2 remains free from the structural instability that might well be expected at low temperatures owing to twofold orbital degeneracy in the Fe2+ ground state with D4h point symmetry. The reduction and the oxidation between SrFeO2 and SrFeO3 proceed via the brownmillerite-type intermediate SrFeO2.5, and start at the relatively low temperature of 400 K, making the material appealing for a variety of applications, including oxygen ion conduction, oxygen gas absorption and catalysis., 簡便な手法により、化学の常識を覆す鉄酸化物を発見. 京都大学プレスリリース. 2007-12-13.

An investigation of the quaternary Ln 2 O 3 –SrO–NiO–CuO system has shown that compounds of the formula Ln 2− x Sr x Ni 0.8 Cu 0.2 O 4− δ (0 x 2 NiF 4 -type structure, but a new phase of stoichiometric composition is formed only at x = 1.67 (LnSr 5 Ni 2.4 Cu 0.6 O 11 ) with the smaller lanthanides cations Dy, Ho and Er. All the samples have been prepared at 1150 °C in 1 atm of O 2 gas flow using conventional solid state methods. Rietveld refinement of their crystal structures from powder X-ray diffraction data confirms that they adopt the tetragonal structure (space group I 4/ mmm , Z = 2). Magnetic susceptibility data for Ln 2− x Sr x Ni 0.8 Cu 0.2 O 4− δ (0 x 3+ cation.

International audience; Large size and high quality single crystals of Nd$_{2−x}$Sr$_x$NiO$_{4+δ}$ and Pr$_{2−x}$SrxNiO$_{4+δ}$, with selected composition (x = 0.0, 0.1 and 0.5), were grown by a floating-zone technique using an image furnace. We found that even small deviations from the ideal cation stoichiometry led to either NiO segregation or formation of Ni-poor Pr$_4$Ni$_3$O$_{10−x}$, or RE$_x$O$_y$ intergrowth phases, rendering the title compounds unstable even under ambient conditions. Related to potential applications as membranes in SOFC, we importantly found Nd$_{2−x}$Sr$_x$NiO$_{4+δ}$ and Pr$_{2−x}$SrxNiO$_{4+δ}$ powders, obtained from ground stoichiometric single crystals, to be stable in air at high temperature (1000 °C), contrary to the partial decomposition observed when synthesized as polycrystalline powders by classical solid state synthesis. The presence of NiO/Pr$_4$Ni$_3$O$_{10−x}$ or RE$_x$O$_y$ intergrowth phases are discussed as a drawback limiting high temperature stability for Pr$_2$NiO$_{4+δ}$. Grown single crystals were characterised by neutron and X-ray diffraction as well as by electron microscopy (SEM/EDS), revealing their excellent quality in terms of composition, homogeneity and crystallinity. For each crystal, the oxygen content was determined by thermogravimetric analysis in a reductive atmosphere. Transmission electron microscopy highlighted a complex incommensurate structure for Pr$_2$NiO$_{4.25}$ and Nd$_2$NiO$_{4.25}$ with a 2D modulation vector related to oxygen ordering.

International audience; Periodic DFT calculations allow an understanding of the strong orientation-dependent Ramanspectra of oriented CaFeO2.5 single crystals. Modes involving the oscillation of the apical oxygen(Oap) atoms perturb the induced electric dipoles. These are formed by anisotropy in the chargedistribution and are found to be strongly enhanced when the electric field of the linearly polarizedlaser line is parallel to the b axis. For the CaFeO2.5 ordered system, strong polarizability of thesemodes corresponds to strong Raman intensities. Conversely, the apical oxygen disorder observedin low-temperature oxygen-conducting SrFeO2.5 destroys the long-range coherence of therespective Raman modes, which consequently show a strongly reduced intensity. This studyprovides a vibrational tool to discriminate between ordered and disordered isomorporphousABO2.5 Brownmillerite frameworks. Furthermore, in combination with DFT calculations, we havefound that the weakening of the interlayer interactions is responsible for the loss of ordering inBrownmillerite compounds

International audience; We investigated the structure of Nd2NiO4+δ and Pr2NiO4+δ by single crystal neutron diffraction studies. While the real structure of both compounds is incommensurate, the scattering density of the respective average structures was explored using the Maximum Entropy Method. Unusually high displacement factors were found for the equatorial and apical oxygen atoms showing respectively large displacement amplitudes towards [001] and [110] with respect to the F-symmetry cell. The shifts of the apical oxygen atoms reach up to 1 Å from their average position, corresponding to a 25° tilt of the NiO6 octahedra. At 400 °C, i.e. slightly above the orthorhombic-tetragonal phase transition, the anharmonic apical oxygen displacements towards [110] in the commensurate tetragonal parent structure are strongly enhanced, showing a double-well potential and pointing towards the interstitial vacancy sites, creating a quasi continuous shallow energy diffusion pathway between apical and interstitial oxygen sites. These large displacement amplitudes are considered to be – at least partially – of dynamical origin, which is consistent with a phonon assisted diffusion mechanism, already activated at very moderate temperatures.

International audience; In this study we demonstrate the feasibility of following up a chemical reaction by single crystal x-ray (synchrotron) diffraction under operando conditions, carried out in a specially designed electrochemical cell mounted on the BM01A at the European Synchrotron Radiation Facility (ESRF). We investigated in detail the electrochemical oxidation of SrFeO 2.5 to SrFeO 3 on a spherical single crystal of 70 µ m diameter by in situ diffraction at an ambient temperature. Complete data sets were obtained by scanning the whole reciprocal space using a 2M Pilatus detector, resulting in 3600 frames with a resolution of 0.1° per data set, each obtained in 18 min. The crystal was mounted in a specially designed electrochemical cell with 1N KOH used as the electrolyte. During the electrochemical oxidation, the reaction proceeds following the phase sequence SrFeO 2.5 /SrFeO 2.75 /SrFeO 2.875 /SrFeO 3 , structurally accompanied by establishing a complex series of long-range oxygen vacancy ordering, which gets instantly organized at ambient temperature. The topotactic reaction pathway is discussed in terms of the evolution of the twin domain structure. The formation of SrFeO 2.875 is accompanied by the formation of diffuse streaks along the [1 0 0]-direction of the perovskite cell, reaching high d -spacings. The diffuse streaks are discussed and are thought to originate from a modified twin structure induced by the SrFeO 2.75 to SrFeO 2.875 transition, and the associated changes in the domain structure, developed during the oxygen intercalation. We equally analysed and discussed in detail the twin structure of all the title compounds. We confirm the ground state of SrFeO 2.5 is able to adopt the Imma space group symmetry, showing stacking faults of the tetrahedral layers along the stacking axis of the brownmillerite unit cell, indicated by the 1D diffuse rods. We showed that in situ single crystal diffraction has huge potential in the study of non-stoichiometric compounds under operando conditions, in order to obtain structural information i.e. about diffuse scattering, and microstructural information related to domain effects such as twinning—information far beyond that which powder diffraction methods allow us to obtain

Results are presented from neutron diffraction measurement of the strains in each phase, matrix and reinforcement, of a metal matrix composite bar before and after deformation beyond the elastic limit by four-point bending. The strains in each phase have been converted to stress. A stress separation technique was then applied, and the contributing mechanisms separated and identified. In this way the changes in the different contributions owing to plastic deformation have been determined. It is found that, initially, the average phase stresses can be explained in terms of a combination of essentially hydrostatic phase average thermal misfit stresses in the matrix (tension) and particles (compression) combined with a parabolic macrostress from quenching. After plastic bending the change in axial macrostress is as expected for that for a monolithic bar, but unexpectedly the misfit stresses had relaxed to approximately zero in both the tensile and compressive plastically strained regions of the bar.

International audience; Nonstoichiometric Nd2NiO4+δ shows oxygen ion mobility already at roomtemperature and as such is a promising material in the field of solid state ionic conductors.The present work aims to understand the impact of oxygen overstoichiometry on the lattice dynamics of the Nd2NiO4 framework and to correlate dynamic instabilities to the anionic mobility at room temperature. We performed neutron time-of-flight spectroscopy experiments coupled with DFT-based molecular dynamics calculations on the phases Nd2NiO4.0, Nd2NiO4.10, and Nd2NiO4.25. Specific signatures in the phonon density of states gave evidence that excess oxygen on interstitial lattice sites activates large displacements of the apical oxygen atoms along the [110] direction, thus favoring their diffusion toward interstitial sites within the rock salt-type layer already at ambient temperature. We implemented a position recurrence method to analyze apical oxygen displacements during the 40 ps time scale of molecular dynamics simulations. The resultshighlighted that dynamical delocalization of apical oxygen atoms along [110] is necessary to observe diffusion at room temperature, and thus ionic mobility at room temperature is activated by lattice dynamics

The residual stress field in shrink-fit disc-ring systems was investigated in the framework of a general research, the final goal of which is to establish optimisation criteria for the joining procedure in the AA6082 aluminium alloy. In particular, two different procedures were considered: the traditional thermoelastic and an innovative thermoelastoplastic coupling. The two processes were simulated by finite element calculations, which were optimised by comparison with existing analytic models. Neutron diffraction experiments were carried out on samples obtained by the two procedures. The comparison between the theoretical and experimental results showed a satisfactory agreement. Small differences found were ascribed to already existing residual stresses, which were actually measured in uncoupled samples.

In situ neutron diffraction experiments on polycrystalline shape memory alloys/SMA/transforming in thermomechanical cycles were carried out with the aim to learn how to determine stress—strain—temperature responses of SMAs from the in situ neutron diffraction data. Results of a single experiment on NiTi polycrystal deformed in compression at constant temperature are reported. It is found that the macroscopic stress—strain response of the polycrystal can be evaluated from diffraction measured lattice strains (peak position) and integral intensities of a particular well chosen austenite hkl-reflection. The neutron diffraction technique may thus be possibly used to evaluate in situ stress-strain-temperature responses of otherwise inaccessible SMA elements embedded in the smart SMA-composites.

The residual elastic strains determination by neutron diffraction has been performed on quartzite samples from a former texture study. The measured complete residual strain tensor has been considered as representative of the “natural” finite plastic deformation. Such tensors fitted to plastic tensors have been introduced in texture modelings. The results demonstrate the potential of complete and meaningful strain tensor determinations in rocks.