Grazing-incidence synchrotron radiation diffraction studies on irradiated Ce-doped and pristine Y-stabilized ZrO2 at the Rossendorf beamline.

In this work, Ce-doped yttria-stabilized zirconia (YSZ) and pure YSZ phases were subjected to irradiation with 14 MeV Au ions. Irradiation studies were performed to simulate long-term structural and microstructural damage due to self-irradiation in YSZ phases hosting alpha-active radioactive species. It was found that both the Ce-doped YSZ and the YSZ phases had a reasonable tolerance to irradiation at high ion fluences and the bulk crystallinity was well preserved. Nevertheless, local microstrain increased in all compounds under study after irradiation, with the Ce-doped phases being less affected than pure YSZ. Doping with cerium ions increased the microstructural stability of YSZ phases through a possible reduction in the mobility of oxygen atoms, which limits the formation of structural defects. Doping of YSZ with tetravalent actinide elements is expected to have a similar effect. Thus, YSZ phases are promising for the safe long-term storage of radioactive elements. Using synchrotron radiation diffraction, measurements of the thin irradiated layers of the Ce-YSZ and YSZ samples were performed in grazing incidence (GI) mode. A corresponding module for measurements in GI mode was developed at the Rossendorf Beamline and relevant technical details for sample alignment and data collection are also presented.

Synthesis of Single Crystals of ε-Iron and Direct Measurements of Its Elastic Constants.

Seismology finds that Earth's solid inner core behaves anisotropically. Interpretation of this requires a knowledge of crystalline elastic anisotropy of its constituents-the major phase being most likely ε-Fe, stable only under high pressure. Here, single crystals of this phase are synthesized, and its full elasticity tensor is measured between 15 and 33 GPa at 300 K. It is calculated under the same conditions, using the combination of density functional theory and dynamical mean field theory, which describes explicitly electronic correlation effects. The predictive power of this scheme is checked by comparison with measurements; it is then used to evaluate the crystalline anisotropy in ε-Fe under higher density. This anisotropy remains of the same amplitude up to densities typical of Earth's inner core.

Deconvoluting Cr states in Cr-doped UO2 nuclear fuels via bulk and single crystal spectroscopic studies.

Cr-doped UO2 is a leading accident tolerant nuclear fuel where the complexity of Cr chemical states in the bulk material has prevented acquisition of an unequivocal understanding of the redox chemistry and mechanism for incorporation of Cr in the UO2 matrix. To resolve this, we have used electron paramagnetic resonance, high energy resolution fluorescence detection X-ray absorption near energy structure and extended X-ray absorption fine structure spectroscopic measurements to examine Cr-doped UO2 single crystal grains and bulk material. Ambient condition measurements of the single crystal grains, which have been mechanically extracted from bulk material, indicated Cr is incorporated substitutionally for U+4 in the fluorite lattice as Cr+3 with formation of additional oxygen vacancies. Bulk material measurements reveal the complexity of Cr states, where metallic Cr (Cr0) and oxide related Cr+2 and Cr+32O3 were identified and attributed to grain boundary species and precipitates, with concurrent (Cr+3xU+41-x)O2-0.5x lattice matrix incorporation. The deconvolution of chemical states via crystal vs. powder measurements enables the understanding of discrepancies in literature whilst providing valuable direction for safe continued use of Cr-doped UO2 fuels for nuclear energy generation.

High-Pressure and High-Temperature Chemistry of Phosphorus and Nitrogen: Synthesis and Characterization of α- and γ-P3N5.

The direct chemical reactivity between phosphorus and nitrogen was induced under high-pressure and high-temperature conditions (9.1 GPa and 2000-2500 K), generated by a laser-heated diamond anvil cell and studied by synchrotron X-ray diffraction, Raman spectroscopy, and DFT calculations. α-P3N5 and γ-P3N5 were identified as reaction products. The structural parameters and vibrational frequencies of γ-P3N5 were characterized as a function of pressure during room-temperature compression and decompression to ambient conditions, determining the equation of state of the material up to 32.6 GPa and providing insight about the lattice dynamics of the unit cell during compression, which essentially proceeds through the rotation of the PN5 square pyramids and the distortion of the PN4 tetrahedra. Although the identification of α-P3N5 demonstrates for the first time the direct synthesis of this compound from the elements, its detection in the outer regions of the laser-heated area suggests α-P3N5 as an intermediate step in the progressive nitridation of phosphorus toward the formation of γ-P3N5 with increasing coordination number of P by N from 4 to 5. No evidence of a higher-pressure phase transition was observed, excluding the existence of predicted structures containing octahedrally hexacoordinated P atoms in the investigated pressure range.

Single-Bonded Cubic AsN from High-Pressure and High-Temperature Chemical Reactivity of Arsenic and Nitrogen.

Chemical reactivity between As and N2 , leading to the synthesis of crystalline arsenic nitride, is here reported under high pressure and high temperature conditions generated by laser heating in a diamond anvil cell. Single-crystal synchrotron X-ray diffraction at different pressures between 30 and 40 GPa provides evidence for the synthesis of a covalent compound of AsN stoichiometry, crystallizing in a cubic P21 3 space group, in which each of the two elements is single-bonded to three atoms of the other and hosts an electron lone pair, in a tetrahedral anisotropic coordination. The identification of characteristic structural motifs highlights the key role played by the directional repulsive interactions between non-bonding electron lone pairs in the formation of the AsN structure. Additional data indicate the existence of AsN at room temperature from 9.8 up to 50 GPa. Implications concern fundamental aspects of pnictogens chemistry and the synthesis of innovative advanced materials.

Crystal Structure and Non-Hydrostatic Stress-Induced Phase Transition of Urotropine Under High Pressure.

High-pressure behavior of hexamethylenetetramine (urotropine) was studied in situ using angle-dispersive single-crystal synchrotron X-ray diffraction (XRD) and Fourier-transform infrared absorption (FTIR) spectroscopy. Experiments were conducted in various pressure-transmitting media to study the effect of deviatoric stress on phase transformations. Up to 4 GPa significant damping of molecular librations and atomic thermal motion was observed. A first-order phase transition to a tetragonal structure was observed with an onset at approximately 12.5 GPa and characterized by sluggish kinetics and considerable hysteresis upon decompression. However, it occurs only in non-hydrostatic conditions, induced by deviatoric or uniaxial stress in the sample. This behavior finds analogies in similar cubic crystals built of highly symmetric cage-like molecules and may be considered a common feature of such systems. DFT computations were performed to model urotropine equation of state and pressure dependence of vibrational modes. The first successful Hirshfeld atom refinements carried out for high-pressure diffraction data are reported. The refinements yielded more realistic C-H bond lengths than the independent atom model even though the high-pressure diffraction data are incomplete.

Incommensurate crystal structure of PbHfO3.

Controversy in the description/identification of so-called intermediate phase(s) in PbHfO3, stable in the range ∼420-480 K, has existed for a few decades. A synchrotron diffraction experiment on a partially detwinned crystal allowed the structure to be solved in the superspace group Imma(00γ)s00 (No. 74.2). In contrast to some previously published reports, in the pure compound only one distinct phase was observed between Pbam PbZrO3-like antiferroelectric and Pm3m paraelectric phases. The modulation vector depends only slightly on temperature. The major structure modulation is associated with the displacement of lead ions, which is accompanied by a smaller amplitude modulation for the surrounding O atoms and tilting of HfO6 octahedra. Tilting of the octahedra results in a doubling of the unit cell compared with the parent structure.

Anisotropic thermal expansion of black phosphorus from nanoscale dynamics of phosphorene layers.

Black phosphorus (bP) is a crystalline material which can be seen as an ordered stacking of two-dimensional layers, referred to as phosphorene. The knowledge of the linear thermal expansion coefficients (LTECs) of bP is of great interest in the field of 2D materials for a better understanding of the anisotropic thermal properties and exfoliation mechanism of this material. Despite several theoretical and experimental studies, important uncertainties remain in the determination of the LTECs of bP. Here, we report accurate thermal expansion measurements along the three crystallographic axes using in situ high temperature X-ray diffraction. From the progressive reduction of the diffracted intensities with temperature, we monitored the loss of the crystal structure of bP across the investigated temperature range, evidencing two thermal expansion regimes at temperature below and above 706 K. Below 706 K, a strong out-of-plane anisotropy can be observed, while at temperatures above 706 K a larger thermal expansion occurs along the a crystallographic direction. From our data and by taking advantage of ab initio optimization, we propose a detailed anisotropic thermal expansion mechanism of bP, which leads to an inter- and intra-layer destabilization. An interpretation of it, based on the high T perturbation of the stabilizing sp orbital mixing effect, is provided, consistent with the high pressure data.

High Pressure Investigation of the S-N2 System up to the Megabar Range: Synthesis and Characterization of the SN2 Solid.

Sulfur and nitrogen represent one of the most studied inorganic binary systems at ambient pressure on account of their large wealth of metastable exotic ring-like compounds. Under high pressure conditions, however, their behavior is unknown. Here, sulfur and nitrogen were compressed in a diamond anvil cell up to about 120 GPa and laser-heated at regular pressure intervals in an attempt to stabilize novel sulfur-nitrogen compounds. Above 64 GPa, an orthorhombic (space group Pnnm) SN2 compound was synthesized and characterized by single-crystal and powder X-ray diffraction as well as Raman spectroscopy. It is shown to adopt a CaCl2-type structure-hence it is isostructural, isomassic, and isoelectronic to CaCl2-type SiO2-comprised of SN6 octahedra. Complementary theoretical calculations were performed to provide further insight into the physicochemical properties of SN2, notably its equation of state, the bonding type between its constitutive elements, and its electronic density of states. This new solid is shown to be metastable down to about 20 GPa, after which it spontaneously decomposes into S and N2. This investigation shows that despite the many metastable S-N compounds existing at ambient conditions, none of them are formed by pressure.

Pressure-induced transformation of CH3NH3PbI3: the role of the noble-gas pressure transmitting media.

The photovoltaic perovskite, methylammonium lead triiodide [CH3NH3PbI3 (MAPbI3)], is one of the most efficient materials for solar energy conversion. Various kinds of chemical and physical modifications have been applied to MAPbI3 towards better understanding of the relation between composition, structure, electronic properties and energy conversion efficiency of this material. Pressure is a particularly useful tool, as it can substantially reduce the interatomic spacing in this relatively soft material and cause significant modifications to the electronic structure. Application of high pressure induces changes in the crystal symmetry up to a threshold level above which it leads to amorphization. Here, a detailed structural study of MAPbI3 at high hydrostatic pressures using Ne and Ar as pressure transmitting media is reported. Single-crystal X-ray diffraction experiments with synchrotron radiation at room temperature in the 0-20 GPa pressure range show that atoms of both gaseous media, Ne and Ar, are gradually incorporated into MAPbI3, thus leading to marked structural changes of the material. Specifically, Ne stabilizes the high-pressure phase of NexMAPbI3 and prevents amorphization up to 20 GPa. After releasing the pressure, the crystal has the composition of Ne0.97MAPbI3, which remains stable under ambient conditions. In contrast, above 2.4 GPa, Ar accelerates an irreversible amorphization. The distinct impacts of Ne and Ar are attributed to differences in their chemical reactivity under pressure inside the restricted space between the PbI6 octahedra.

The updated Zn-Sb phase diagram. How to make pure Zn13Sb10 ("Zn4Sb3").

The Zn-Sb system contains two well-known thermoelectric materials, Zn1-δSb and Zn13-δSb10 ("Zn4Sb3"), and two other phases, Zn9-δSb7 and Zn3-δSb2, stable only at high temperatures. The current work presents the updated phases diagram constructed using the high-temperature diffraction studies and elemental analysis. All phases are slightly Zn deficient with respect to their stoichiometric compositions, which is consistent with their p-type charge transport properties. Either at room or elevated temperatures, Zn1-δSb and Zn13-δSb10 display deficiencies of the main Zn sites and partial Zn occupancy of the other interstitial sites. A phase pure Zn13-δSb10 sample can be obtained from the Zn13Sb10 loading composition, and there is no need to use a Zn-richer composition such as Zn4Sb3. While the Zn13-δSb10 phase is stable till its decomposition temperature of 515 °C, it may incorporate some additional Zn around 412 °C, if elemental Zn is present.

The High-Pressure Oxide Tb3 O5 and its Non-Centrosymmetric Low-Temperature Polymorph-A Comprehensive Study.

In this article, the first thoroughly characterized mixed-valent binary rare earth oxide synthesized under high-pressure/high-temperature conditions, and its low-temperature polymorph are reported. Crystalline HT-HP-Tb3 O5 has been prepared from an equimolar mixture of Tb4 O7 and Tb2 O3 under reaction conditions of 8 GPa and 1323 K. Single-crystal X-ray structure determination showed that HT-HP-Tb3 O5 crystallizes in the orthorhombic space group Pnma, isopointal to the ß-Yb5 Sb3 -type structure. Temperature-dependent measurements of the magnetic susceptibility showed that HT-HP-Tb3 O5 is a Curie-Weiss paramagnet. The observed effective magnetic moment of µeff =9.21(2) µB per formula unit fits well to the calculated moment of µcalc =9.17 µB . Low-field measurements revealed antiferromagnetic ordering at TN =3.6(1) K. Heat capacity measurements indicated an intrinsic structural phase transition of HT-HP-Tb3 O5 at low temperature, which was confirmed by synchrotron X-ray powder diffraction data recorded at 2 K. The metastable high-pressure modification HT-HP-Tb3 O5 undergoes a translationengleiche transition from space group Pnma to Pn21 a (non-standard setting of Pna21 ), leading to the low-temperature polymorph LT-HP-Tb3 O5 by loss of a mirror plane (displacive phase transition).

Structural stability and mechanism of compression of stoichiometric B13C2 up to 68GPa.

Boron carbide is a ceramic material with unique properties widely used in numerous, including armor, applications. Its mechanical properties, mechanism of compression, and limits of stability are of both scientific and practical value. Here, we report the behavior of the stoichiometric boron carbide B13C2 studied on single crystals up to 68 GPa. As revealed by synchrotron X-ray diffraction, B13C2 maintains its crystal structure and does not undergo phase transitions. Accurate measurements of the unit cell and B12 icosahedra volumes as a function of pressure led to conclusion that they reduce similarly upon compression that is typical for covalently bonded solids. A comparison of the compressional behavior of B13C2 with that of α-B, γ-B, and B4C showed that it is determined by the types of bonding involved in the course of compression. Neither 'molecular-like' nor 'inversed molecular-like' solid behavior upon compression was detected that closes a long-standing scientific dispute.

Stability of iron-bearing carbonates in the deep Earth's interior.

The presence of carbonates in inclusions in diamonds coming from depths exceeding 670 km are obvious evidence that carbonates exist in the Earth's lower mantle. However, their range of stability, crystal structures and the thermodynamic conditions of the decarbonation processes remain poorly constrained. Here we investigate the behaviour of pure iron carbonate at pressures over 100 GPa and temperatures over 2,500 K using single-crystal X-ray diffraction and Mössbauer spectroscopy in laser-heated diamond anvil cells. On heating to temperatures of the Earth's geotherm at pressures to ∼50 GPa FeCO3 partially dissociates to form various iron oxides. At higher pressures FeCO3 forms two new structures-tetrairon(III) orthocarbonate Fe43+C3O12, and diiron(II) diiron(III) tetracarbonate Fe22+Fe23+C4O13, both phases containing CO4 tetrahedra. Fe4C4O13 is stable at conditions along the entire geotherm to depths of at least 2,500 km, thus demonstrating that self-oxidation-reduction reactions can preserve carbonates in the Earth's lower mantle.

Synthetic Approach for (Mn,Fe)2(Si,P) Magnetocaloric Materials: Purity, Structural, Magnetic, and Magnetocaloric Properties.

A conventional solid-state approach has been developed for the synthesis of phase-pure magnetocaloric Mn2-xFexSi0.5P0.5 materials (x = 0.6, 0.7, 0.8, 0.9). Annealing at high temperatures followed by dwelling at lower temperatures is essential to obtain pure samples with x = 0.7, 0.8, and 0.9. Structural features of the samples with x = 0.6 and 0.9 were analyzed as a function of temperature via synchrotron powder diffraction. The Curie temperature, temperature hysteresis, and magnetic entropy change were established from the magnetic measurements. According to the diffraction and magnetization data, all samples undergo a first-order magnetostructural transition, but the first-order nature becomes less pronounced for samples that are more Mn rich.

Stability of Fe,Al-bearing bridgmanite in the lower mantle and synthesis of pure Fe-bridgmanite.

The physical and chemical properties of Earth's mantle, as well as its dynamics and evolution, heavily depend on the phase composition of the region. On the basis of experiments in laser-heated diamond anvil cells, we demonstrate that Fe,Al-bearing bridgmanite (magnesium silicate perovskite) is stable to pressures over 120 GPa and temperatures above 3000 K. Ferric iron stabilizes Fe-rich bridgmanite such that we were able to synthesize pure iron bridgmanite at pressures between ~45 and 110 GPa. The compressibility of ferric iron-bearing bridgmanite is significantly different from any known bridgmanite, which has direct implications for the interpretation of seismic tomography data.

Identification, structural characterization and transformations of the high-temperature Zn9-δSb7 phase in the Zn-Sb system.

The Zn9-δSb7 phase has been identified via high-temperature powder diffraction studies. Zn9-δSb7 adopts two modifications: an α form stable between 514 °C and 539 °C and a Zn-poorer ß form stable from 539 °C till its melting temperature of 581 °C. The Zn9-δSb7 structure was solved from the powder data using the simulated annealing approach. Both modifications adopt the same hexagonal structure (P6/mmm) but with slightly different lattice parameters. The α-to-ß transformation is abrupt and first-order in nature. The Zn atoms occupy the tetrahedral holes created by Sb atoms. The ideal Zn9Sb7 composition can be explained by its tendency to adopt a charge balance configuration. Out of 7 Sb atoms, 3 Sb atoms form dimers (Sb(2-) ions) and 4 Sb atoms are isolated (Sb(3-) ions), which require 9 Zn(2+) cations for charge neutrality.

Gd4Ge(3-x)Pn(x) (Pn = P, Sb, Bi, x = 0.5-3): stabilizing the nonexisting Gd4Ge3 binary through valence electron concentration. Electronic and magnetic properties of Gd4Ge(3-x)Pn(x).

Gd(4)Ge(3-x)Pn(x) (Pn = P, Sb, Bi; x = 0.5-3) phases have been prepared and characterized using X-ray diffraction, wavelength-dispersive spectroscopy, and magnetization measurements. All Gd(4)Ge(3-x)Pn(x) phases adopt a cubic anti-Th(3)P(4) structure, and no deficiency on the Gd or p-element site could be detected. Only one P-containing phase with the Gd(4)Ge(2.51(5))P(0.49(5)) composition could be obtained, as larger substitution levels did not yield the phase. Existence of Gd(4)Ge(2.51(5))P(0.49(5)) and Gd(4)Ge(2.49(3))Bi(0.51(3)) suggests that the hypothetical Gd(4)Ge(3) binary can be easily stabilized by a small increase in the valence electron count and that the size of the p element is not a key factor. Electronic structure calculations reveal that large substitution levels with more electron-rich Sb and Bi are possible for charge-balanced (Gd(3+))(4)(Ge(4-))(3) as extra electrons occupy the bonding Gd-Gd and Gd-Ge states. This analysis also supports the stability of Gd(4)Sb(3) and Gd(4)Bi(3). All Gd(4)Ge(3-x)Pn(x) phases order ferromagnetically with relatively high Curie temperatures of 234-356 K. The variation in the Curie temperatures of the Gd(4)Ge(3-x)Sb(x) and Gd(4)Ge(3-x)Bi(x) series can be explained through the changes in the numbers of conduction electrons associated with Ge/Sb(Bi) substitution.

Mono and dinuclear arene ruthenium(II) triazoles by 1,3-dipolar cycloadditions to a coordinated azide in ruthenium(II) compounds.

The dimeric η(6)-hexamethylbenzene ruthenium(II) triazole compounds of formulation [{(η(6)-C(6)Me(6))Ru(N(3)C(2)(CO(2)R)(2))}(2)(µC(2)O(4))] have been synthesized by 1,3-diploar cycloadditions of coordinated azido compound [{(η(6)-C(6)Me(6))Ru(L(1))N(3)}] (1) with substituted acetylene, RO(2)CC(2)CO(2)R via unexpected oxidation of the coordinated ligand to oxalate (where; L(1) = 5-hydroxy-2-(hydroxymethyl)-4-pyrone; R = Me, 3 or Et, 4). In contrast, a similar 1,3-dipolar cycloaddition reaction of [{(η(6)-C(6)Me(6))Ru(L(2))N(3)}] (2) (where; L(2) = tropolone) with acetylene yielded the monomeric triazole compound [(η(6)-C(6)Me(6))Ru(L(2)){N(3)C(2)(CO(2)R)(2)}] (where; R = Me, 5; Et, 6). The compounds were characterized by spectroscopy and the structures of representative compounds 4 and 6 have been determined by single crystal X-ray diffraction. The two ruthenium centres in the compound 4, are linked by a tetra-dentate oxalate group. Both compounds, 4 and 6, crystallized in a triclinic space group P-1.

Gd(5)Si(4-x)Bi(x) structures: novel slab sequences achieved by turning off the directionality of nearest-slab interactions.

Substitution of Bi for Si leads to the complete cleavage of the interslab dimers T-T in the Gd(5)Si(4-x)Bi(x) system with x = 1.58 - 2.42 (T is a mixture of Si and Bi). Equivalence of the interslab T...T contacts, achieved through combination of the electronic and geometrical parameters, removes directionality of nearest-slab interactions and allows for a novel slab stacking. Two new slab sequences, ABCDABCD (x = 2.07, I4(1)/acd space group) and ABADABAD (x = 2.42, P4(2)bc), have been discovered in Gd(5)Si(4-x)Bi(x) in addition to the known one, ABAB, that is dominant among the RE(5)X(4) phases (RE is a rare-earth element, X is a p-element). The slab stacking for x = 2.07 and x = 2.42 is dictated by the second-nearest slab interactions which promote an origin shift either for the entire slab sequence as in ABCDABCD or for every other second-nearest slab pair as in ABADABAD. The loss of the directionality of the nearest-slab bonding allows for extensive stacking faults and leads to diffuse scattering.