High pressure X-ray diffraction study of ReS2

The high-pressure behavior of rhenium disulfide (ReS₂) has been investigated to 51.0 GPa by in situ synchrotron X-ray diffraction in a diamond anvil cell at room temperature. The results demonstrate that the ReS₂ triclinic phase is stable up to 11.3 GPa, at which pressure the ReS₂ transforms to a new high-pressure phase, which is tentatively identified with a hexagonal lattice in space group P6?m2. The high-pressure phase is stable up to the highest pressure in this study (51.0 GPa) and not quenchable upon decompression to ambient pressure. The compressibility of the triclinic phase exhibits anisotropy, meaning that it is more compressive along interlayer directions than intralayer directions, which demonstrates the properties of the weak interlayer van der Waals interactions and the strong intralayer covalent bonds. The largest change in the unit cell angles with increasing pressures is the increase of β, which indicates a rotation of the sulfur atoms around the rhenium atoms during the compression. Fitting the experimental data of the triclinic phase to the third-order Birch-Murnaghan EOS yields a bulk modulus of K_OT=23±4 GPa with its pressure derivative K_OT′= 29±8, and the second-order yields K_OT=49±3 GPa.     

Successive phase transitions in tetra(isopropylamine)decachlorotricadmate (II) [(CH3)2CH NH3]4Cd3Cl10] crystal - Dielectric and dilatometric studies

Single crystal of a new [(CH₃)₂CHNH₃]₄Cd₃Cl₁₀ compound was grown and its properties have been characterized by dielectric and dilatometric investigations. Dielectric measurement evidenced the phase transitions at T₁ = 352.8 K, T₂ = 293.5 K and T₃ = 261.5 K on cooling run. Dilatometric measurement of thermal expansion showed clearly two successive phase transitions at T₁ and at T₂. No temperature hysteresis was observed for phase transitions at T₁ and T₂. Large temperature hysteresis was observed at T₃ in dielectric studies. Transitions at T₁ and T₃ are classified as a first order and at T₂ as a continuous one. Anomalies of electric permittivity and expansion connected with the transitions are observed at practically the same temperatures and close to those observed earlier in DSC (Differential Scanning Calorimetry) studies. Results of dilatometric studies were applied to estimate critical coefficient β for continuous phase transition at T₁ which is equal to 0.40 ± 0.01.     

A first-principles study of vibrational modes in Cu2O and Ag2O crystals

A first-principles investigation of cuprite crystals (Cu₂O and Ag₂O) has been performed. For Cu₂O, the calculated frequencies at the Γ point of the Brillouin zone are in very good agreement with the experimental frequencies. For Ag₂O, the presence of E_u and F_2u vibrational modes with negative frequencies indicates a low temperature phase transition, in agreement with recent high resolution X-ray and neutron diffraction measurements. The energy scanning along these two modes shows a double-well potential, within which only the Ag atoms vibrate. As a result, the origin of the phase transition can be attributed to displacive disorder of the Ag atoms.     

High-temperature B2 ordering in Fe50Co50 alloy

High-temperature (above 1200 °C) B2 ordering was experimentally found in the Fe₅₀Co₅₀ alloy with the help of the electron diffraction. Using the X-ray photoelectron spectroscopy method the “ordering-phase separation” transition was shown to lead to changes both in the 3d-electron spectra of the valence band (3d-valence electron localization on Fe atoms increases at phase separation and it decreases at ordering). The investigation of multiplet splitting of the 3s-electron spectra of core-level electrons reveals that magnetic moments on Fe and Co atoms in the Fe₅₀Co₅₀ alloy are larger, when there is the tendency toward ordering, and they are smaller in the case of the tendency toward phase separation. A number of examples are presented, which are indicative of the fact that chemical ordering can influence magnetic ordering by the formation of the respective microstructures and magnetic ordering has no influence on chemical ordering. It can be concluded that the phase transition “ordering-phase separation” takes place both at 730 °C and at the temperature somewhat higher that 1200 °C.     

Intermediate-temperature polymorphic phase transition in KH2PO4: A synchrotron X-ray diffraction study

We have used synchrotron X-ray diffraction to investigate the structural and chemical changes undergone by polycrystalline KH₂PO₄ (KDP) upon heating within the 30-250 °C temperature interval. Our data show evidence of a polymorphic transition at T∼190 °C from the room-temperature tetragonal KDP phase to a new intermediate-temperature monoclinic KDP modification (spacegroup P2₁/m and lattice parameters a=7.590, b=6.209, c=4.530 Å, and β=107.36°). The monoclinic RDP polymorph remains stable upon further heating to 235 °C, and is isomorphic to its RbH₂PO₄ and CsH₂PO₄ counterparts.     

High substitution of Fe for Zr in ZrV1.6P0.4O7 with small amount of FeV0.8P0.2O4 for low thermal expansion

Fe³⁺-doped ZrV_1.6P_0.4O₇ with Fe:Zr molar ratios of 1:9, 2:8, 3:7 and 4:6 was synthesized to reduce phase transition and obtain low thermal expansion. It is shown that the phase transition temperature of Fe-doped ZrV_1.6P_0.4O₇ is reduced obviously with increasing the content of Fe. Fe³⁺ ion with lower valence and smaller radius than that of Zr⁴⁺ favors to extend the bond angle of V–O–V(P) close to 180° in ZrV_1.6P_0.4O₇, which is considered responsible for the normal structure at room temperature and low thermal expansion. The thermal expansion coefficients of Fe-doped ZrV_1.6P_0.4O₇ for Fe:Zr molar ratios from 1:9 to 4:6 are calculated to be from −4.33×10⁻⁶$-4.33\times {10}^{-6}$ to 5.2×10⁻⁷ K⁻¹$5.2\times {10}^{-7}{\text{K}}^{-1}$ by linear thermal expansion measurement. The effect of small amount of FeV_0.8P_0.2O₄ formation with higher content of Fe³⁺ on thermal expansion coefficients of the samples is discussed.     

Electrical and thermal studies in the commensurate incommensurate phase region of (NH4)2ZnCl4 single crystal

DC electrical conductivity for a virgin and poled annealed (NH₄)₂ZnCl₄b-axis single crystal shows a defect controlled property. A Schottky mechanism is a probable mechanism of conduction in regions of strong structural transitions. The rise of conductivity in the incommensurate and paraelectric phases is linked to an increase in discommensurations density. The activation energies (ΔE) in the three phases region were calculated. DTA measurements shows that the crystal is stable up to 200 °C and the phase transition temperatures were observed at 42, 94.8 and 137 °C. The effective activation energy (E_e) was obtained using Kissinger and Mahadevan equations. It was found to be equal to 0.49 eV. This correlates with the value obtained through DC conductivity.     

X-ray study of c-axis parameters in disordered stage II Agχ TiS2

X-ray measurements have been performed on disordered Stage II Ag_χ TiS₂ crystals with χ = 0.18 and 0.19. The c-axis structure was determined using the 00.l reflections for 4 ?l? 29. A principal result is that the intercalation of Ag⁺ between S layers produces unequal TiS distances in the adjacent TiS₂. The charge transfer to the Ti layer produces an expanded TiS distance adjacent to the Ag layer. The TiS distance away from the Ag ions is accordingly contracted. This effective (indirect) repulsive interaction between Ag⁺ and Ti may provide a mechanism for staging in these materials by keeping the Ag layers as far apart as possible.     

In situ observations of temperature- and pressure-induced phase transitions in TiH2: Angle-dispersive and synchrotron energy-dispersive X-ray diffraction studies

We investigated the behavior of the structure of titanium hydride (TiH₂), an important compound in hydrogen storage research, at elevated temperatures (0-120 °C) and high pressures (1 bar-34 GPa). Temperature-induced changes of TiH₂ as indicated in the alteration of the ambient X-ray demonstrated a cubic to tetragonal phase transition occurring at about 17 °C. The main focus of this study was to identify any pressure-induced structural transformations, including possible phase transitions, in TiH₂. Synchrotron X-ray diffraction studies were carried out in situ (diamond anvil cell) in a compression sequence up to 34 GPa and in subsequent decompression to ambient pressure. The pressure evolution of the diffraction patterns revealed a cubic (Fm-3m) to tetragonal (I4/mmm) phase transition at 2.2 GPa. The high-pressure phase persisted up to 34 GPa. After decompression to ambient conditions the observed phase transition was completely reversible. A Birch-Murnaghan fit of the unit cell volume as a function of pressure yielded a zero-pressure bulk modulus K₀=146(14) GPa, and its pressure derivative K′₀=6(1) for the high-pressure tetragonal phase of TiH₂.     

Effects of annealing temperature on structure and magnetic properties of amorphous Fe61Co27P12 nanowire arrays

Arrays of Fe₆₁Co₂₇P₁₂ nanowire with an aspect ratio about 70 were prepared in anodic aluminum oxide templates by electrodeposition. The influences of annealing temperature on structure and magnetic properties of Fe₆₁Co₂₇P₁₂ nanowires were studied. When the specimens were annealed below 400 °C, there are no obvious changes in structure except relaxation. With the annealing temperature increasing from 400 to 600 °C, the Fe-Co phase is detected by X-ray diffraction and Mössbauer spectra. The crystalline fraction and hyperfine field can be derived from Mössbauer spectra. The room temperature magnetic hysteresis loops show that the coercivity and squareness of the nanowire arrays in parallel to the wire axis increase with the increasing of annealing temperature, which mainly attributes to the strengthening of anisotropy.     

Magnetic field induced changes in linear and nonlinear optical properties of Ti incorporated Cr2O3 nanostructured thin film

We report the magnetic field effect on the linear and nonlinear optical properties of pulse laser ablated Ti-incorporated Cr₂O₃ nanostructured thin film. Optical properties have been experimentally analyzed under Voigt geometry by performing ultraviolet-visible spectroscopy and closed aperture Z-scan technique using a continuous wave He–Ne laser source. Nonlinear optical response reveals a single peak-valley feature in the far field diffraction pattern in absence of magnetic field ($\mathrm{B}=0$) confirming self-defocussing effect. This feature switches to a valley-peak configuration for $\mathrm{B}=5000\text{G}$, suggesting self-focusing effect. For $\mathrm{B}\le 750\text{G}$, oscillations were observed revealing the occurrence of higher order nonlinearity. Origin of nonlinearity is attributed to the near resonant d-d transitions observed from the broad peak occurring around 2 eV. These transitions are of magnetic origin and get modified under the application of external magnetic field. Our results suggest that magnetic field can be used as an effective tool to monitor the sign of optical nonlinearity and hence the thermal expansion in Ti-incorporated Cr₂O₃ nanostructured thin film.     

Role of the TiO6 octahedra on the ferroelectric and piezoelectric behaviour of the poled PbMg1/3Nb2/3O3-xPbTiO3 (PMN-PT) single crystal and textured ceramic

Field cooling (FC) poled/unpoled PMN-29%PT single crystal and room temperature (RT) poled/unpoled PMN-34.5%PT textured ceramic were investigated between ∼0 and 300 °C by thermal expansion, dielectric and Raman spectroscopy. New phase transitions are evidenced at 40, 91 and 180 °C in the case of FC PMN-29%PT as well as at 70 and 200 °C for RT PMN-34.5%PT and their order is discussed. The physical properties of the textured ceramics are rather similar to the ones observed for the single crystals that make them low-cost alternative for a wide range of applications. However, the temperatures and character of the phase transitions strongly depend on the kind of the poling conditions. Temperature dependences of the Raman line parameters show that the NbO₆ octahedra remain stable during temperature increase, while TiO₆ ones evolve quasi-continuously. The step transitions of the Pb²⁺ ion sublattice are evidenced. This suggests that the TiO₆ and Pb²⁺ sublattices are especially coupled. The role of the TiO₆ clusters on the structural phase transitions and dielectric properties of the PbMg_1/3Nb_2/3O₃-xPbTiO₃ (PMN-PT) system is discussed. The presence of the Raman modes above the maximum dielectric permittivity reveals that the local symmetry is lower than the cubic one (Pm3m). The decrease of the Raman line intensities vs. temperature indicates precisely the continuous evolution of the local symmetry towards the cubic one. The temperature evolution of the Rayleigh wing parameters appears sensitive to the phase transitions’ presence.     

X-ray diffraction, Cs and H NMR and thermal studies of CdZrCs1.5(H3O)0.5(C2O4)4·xH2O displaying Cs and water dynamic behavior

A novel mixed cadmium zirconium cesium oxalate with an open architecture has been synthesized from precipitation methods at room pressure. It crystallizes with an hexagonal symmetry, space group P3₁12 (no. 151), a=9.105(5) Å, c=23.656(5) Å, V=1698(1) Å³ and Z=3. The structure displays a [CdZr(C₂O₄)₄]²⁻ helicoidal framework built from CdO₈ and ZrO₈ square-based antiprisms connected through bichelating oxalates, which generates channels along different directions. Cesium cations, hydronium ions and water molecules are located inside the voids of the anionic framework. They exhibit a dynamic disorder which has been further investigated by ¹H and ¹³³Cs solid-state NMR. Moreover a phase transition depending both upon ambient temperature and water vapor pressure was evidenced for the title compound. The thermal decomposition has been studied in situ by temperature-dependent X-ray diffraction and thermogravimetry. The final product is a mixture of cadmium oxide, zirconium oxide and cesium carbonate.     

The Ag M5N45N45 Auger photoelectron coincidence spectra of disordered Ag0.5Pd0.5 alloy

An effect of disorder broadening (DB) on the Ag M₅N₄₅N₄₅ Auger spectra in the random substituted Ag_0.5Pd_0.5 has been investigated by Auger photoelectron coincidence spectroscopy (APECS). Data were collected for the Ag M₅N₄₅N₄₅ Auger line coincident with the Ag 3d_5/2 photoelectron line (and its higher and lower binding energy sides). It is shown that the broadening of the Ag M₅N₄₅N₄₅ line is directly associated with the presence of disorder broadening of the Ag 3d_5/2 photoelectron line. The APECS experiment is used to demonstrate the broadening in a novel way.     

X-ray diffraction study of cholesterol-cholesteryl oleate binary mixtures

Summary The phase transitions for binary mixtures of cholesteryl oleate (CO) and cholesterol (CH) have been investigated by X-ray diffraction, differential scanning calorimetry and optical microscopy. The phase diagrams on heating, involving the solid-solid and solid-isotropic liquid transitions, and on cooling, involving the cholesteric and smectic mesophases, have been derived. In particular, a strong supercooling effect of liquid cholesterol and a progressive decrease of the isotropic liquid-cholesteric and cholesteric-smectic transition temperatures were observed. Moreover, some structural modifications induced in the smecticA and in the cholesteric phase by the presence of CH in CO were detected. Finally the dependence of intermolecular distance in the isotropic liquid phase was studied as a function of temperature and mixture composition.

---

Riassunto Mediante diffrazione dei raggi X, calorimetria differenziale e microscopia ottica sono state studiate le transizioni di fase per miscele binarie di colesteril oleato (CO) e colesterolo (CH). Sono stati ricavati in riscaldamento il diagramma di fase per le transizioni solido-solido e solido-liquido isotropo ed in raffreddamento un diagramma di fase comprendente le mesofasi colesterica e smettica. In particolare sono stati osservati un marcato effetto di sovraraffreddamento del liquido del colesterolo ed una progressiva diminuzione delle temperature di transizione delle fasi liquido-isotropo colesterico e colestericosmettico. Inoltre sono state trovate alcune modificazioni strutturali indotte nella fase smetticaA ed in quella colesterica dalla presenza del CH nel CO. Infine è stata studiata la dipendenza della distanza intermolecolare nella fase liquido isotropo in funzione della temperatura e della composizione della miscela.

---

Резюме Исследуются фазовые переходы в бинарных смесях олеата холестерила (CO) и холестерола (CH) с помощью дифракции рентгеновских лучей, дифференциальной сканирующей калориметрии и оптической микроскопии. Получаются при нагревании фазовые диаграммы, вклюьающие переходы твердое тело-твердое тело и твердое тело-изотропная жидкость, а при охлаждении фазовая диаграмма, включающая холестерическую и смектическую мезофазы. В частности, наблюдается сильные эффект сверхохлаждения дия жидкого холестерола и постепенное уменьшение температур фазовых переходов изотропная жидкость-холестерик и холестерик-смектик. Кроме того, определяются структурные модификации, индуцированные в фазе смектикаА и в фазе холестерика наличием CH и CO. В эаключение, исследуется эависимость расстояния между молекулами в фазе изотропной жидкости, как функция температуры и состава смеси.

     

Thermal expansion property of anomalous magnetic alloy Fe70Al30

D0₃-type Fe₇₀Al₃₀ shows a transition from ferromagnetism to spin glass with anomalous slow spin dynamics below 170 K. Furthermore, it shows a structural transition from D0₃ to body-centered cubic (BCC) at 823 K. In this article, the relationship between the magnetic properties, thermal expansion coefficient (TEC), and crystal structure transition of D0₃-type Fe₇₀Al₃₀ is discussed. Below 170 K, TEC decreases with temperature, accompanied by a decrease in the Fe moments. In the ferromagnetic state between 170 K and the Curie temperature (T_C), TEC increases gradually with temperature. Above T_C, TEC increases rapidly. These temperature variations of TEC could be connected to the high-spin/low-spin transition and thermal spin fluctuations. During transition from D0₃ to disordered BCC at 823 K, TEC shows discontinuous behavior, similar to a first-order transformation. With further increase in temperature, TEC becomes constant. This implies that the phase transition from D0₃ to disordered BCC is accompanied by a change in spin fluctuation.     

Structural,thermal and electrical properties of the semiconductor system Ag(1−x)CuxInSe2

This paper presents a study of bulk samples synthesized of the Ag_1−xCu_xInSe₂ semiconductor system. Structural, thermal and electrical properties, as a function of the nominal composition (Cu content) x=0.0, 0.2, 0.4, 0.6, 0.8, and 1.0 were studied. The influence of x on parameters such as melting temperature, solid phase transition temperature, lattice parameters, bond lengths, crystallite size t (coherent domain), electrical resistivity, electrical mobility and majority carrier concentration was analyzed. The electrical parameters are analyzed at room temperature. In general, it is observed that the properties of the Ag_1−xCu_xInSe₂ system for x≤0.4 are dominated by n-AgInSe₂, while for x>0.4, these are in the domain of p-CuInSe₂. The crystallite size t in the whole composition range (x) is of the order of the nanoparticles. Secondary phases (CuSe, Ag₂Se and InSe) in small proportion were identified by XRD and DTA.