Study of surface-bulk mass transport and phase transformation in nano-TiO2 using hyperfine interaction technique

Phase transition from anatase to rutile for the 70 nm TiO₂ crystallite has been investigated by the time differential perturbed angular correlation (TDPAC) technique. The study involved the annealing of the TiO₂ nanocrystals, adsorbed with the nuclear probe (¹⁸¹Hf/¹⁸¹Ta) at trace level, at different temperatures for different durations. The TDPAC measurement was also supported by XRD measurement where the width of the peaks increases with the increase in annealing temperature indicating a crystal growth. The samples annealed up to 823 K for 4 h showed no phase transition, except for the growth of the crystallites. However, it showed phase transition at the same temperature (823 K), when annealed for longer duration, indicating the slower kinetics of the phase transition process. Further the sample, when annealed at 1123 K for 4 h, showed phase transition. It has also been observed that the ¹⁸¹Hf tracer, adsorbed on 70 nm anatase TiO₂, diffuses from surface to bulk during the phase transition process and the extent of diffusion in anatase differs from that in rutile phase. However, surface to bulk mass-transfer is found to play a significant role in the phase transition process.     

Structural stability,electronic structure and mechanical properties of 4d transition metal nitrides TMN (TM=Ru,Rh, Pd)

Ab initio calculations are performed to investigate the structural stability, electronic, structural and mechanical properties of 4d transition metal nitrides TMN (TM=Ru, Rh, Pd) for five different crystal structures, namely NaCl, CsCl, zinc blende, NiAs and wurtzite. Among the considered structures, zinc blende structure is found to be the most stable one among all three nitrides at normal pressure. A structural phase transition from ZB to NiAs phase is predicted at a pressure of 104 GPa, 50.5 GPa and 56 GPa for RuN, RhN and PdN respectively. The electronic structure reveals that these nitrides are metallic. The calculated elastic constants indicate that these nitrides are mechanically stable at ambient condition.     

Thermoelectric properties of Bi0.9Sb0.1 prepared by high pressure

The Bi_0.9Sb_0.1 powders were prepared by mechanical alloying and then pressed under 6 GPa at different pressing temperatures. X-ray diffraction spectra showed that the single phase was formed. The nanostructure of grain was observed by bright-field imaging. Electrical conductivity, Seebeck coefficient, and thermal conductivity had been investigated in the temperature range of 80-300 K. The absolute Seebeck coefficient value of 120.3 μV/K was measured at 130 K. The figure-of-merit reached a maximum value of 0.90×10⁻³ K⁻¹ at 140 K.     

Experimental constraints on the phase diagram of elemental zirconium

The phase diagram of zirconium metal has been studied using synchrotron X-ray diffraction and time-of-flight neutron scattering at temperatures and pressures up to 1273 K and 17 GPa. The equilibrium phase boundary of the α-ω transition has a dT/dP slope of 473 K/GPa, and the extrapolated transition pressure at ambient temperature is located at 3.4 GPa. For the ω-β transition, the phase boundary has a negative dT/dP slope of 15.5 K/GPa between 6.4 and 15.3 GPa, which is substantially smaller than a previously reported value of −39±5 K/GPa in the pressure range of 32-35 GPa. This difference indicates a significant curvature of the phase boundary between 15.3 and 35 GPa. The α-ω-β triple point was estimated to be at 4.9 GPa and 953 K, which is comparable to previous results obtained from a differential thermal analysis. Except for the three known crystalline forms, the β phase of zirconium metal was found to possess an extraordinary glass forming ability at pressures between 6.4 and 8.6 GPa. This transformation leads to a limited stability field for the β phase in the pressure range of 6-16 GPa and to complications of high-temperature portion of phase diagram for zirconium metal.     

Experimental constraints on the phase diagram of titanium metal

The phase transformations of titanium metal have been studied at temperatures and pressures up to 973 K and 8.7 GPa using synchrotron X-ray diffraction. The equilibrium phase boundary of the α-ω transition has a dT/dP slope of 345 K/GPa, and the transition pressure at room temperature is located at 5.7 GPa. The volume change across the α-ω transition is ΔV=0.197 cm³/mol, and the associated entropy change is ΔS=0.57 J/mol K. Except for ΔV, our results differ substantially from those of previous studies based on an equilibrium transition pressure of 2.0 GPa at room temperature. The α-ω-β triple point is estimated to be at 7.5 GPa and 913 K, which is comparable with previous results obtained from differential thermal analysis and resistometric measurements. An update, more accurate phase diagram is established for Ti metal based on the present observations and previous constraints on the α-β and ω-β phase boundaries.     

Heat capacity of paramagnetic nickelocene: Comparison with diamagnetic ferrocene

Nickelocene [bis(η⁵-cyclopentadienyl)nickel: Ni(C₅H₅)₂, electron spin S=1, the ground state configuration ³A_2g] is paramagnetic and belongs to a typical molecule-based magnet. Heat capacities of nickelocene have been measured at temperatures in the 3−320 K range by adiabatic calorimetry. By comparing with those of diamagnetic ferrocene crystal, a small heat capacity peak centered at around 15 K and a sluggish hump centered at around 135 K were successfully separated. The low-temperature peak at 15 K caused by the spin is well reproduced by the Schottky anomaly due to the uniaxial zero-field splitting of the spin S=1 with the uniaxial zero-field splitting parameter D/k=45 K (k: the Boltzmann constant). The magnetic entropy 9.7 J K⁻¹ mol⁻¹ is substantially the same as the contribution from the spin-manifold R ln 3=9.13 J K⁻¹ mol⁻¹ (R: the gas constant). The sluggish hump centered at around 135 K arises from rotational disordering of the cyclopentadienyl rings of nickelocene molecule. The enthalpy and entropy gains due to this anomaly are 890 J mol⁻¹ and 6.9 J K⁻¹ mol⁻¹, respectively. As the hump spreads over a wide temperature region, separation of the hump from the observed heat capacity curve involves a little bit ambiguity. Therefore, these values should be regarded as being reasonable but tentative. The present entropy gain is comparable with 5.5 J K⁻¹ mol⁻¹ for the sharp phase transition at 163.9 K of ferrocene crystal. This fact implies that although the disordering of the rings likewise takes place in both nickelocene and ferrocene, it proceeds gradually in nickelocene and by way of a cooperative phase transition in ferrocene. A reason for this originates in loose molecular packing in nickelocene crystal. Molar heat capacity and the standard molar entropy of nickelocene are larger than those of ferrocene beyond the mass effect over the whole temperature region investigated. This fact provides with definite evidences for the loose molecular packing in nickelocene crystal.     

Structural and magnetic ordering in the two-dimensional coordination polymer Co(ox)(bpy-d8), (ox=C2O4, bpy-d8=4,4′-bipyridine-d8)

Neutron diffraction and magnetic susceptibility studies of the two-dimensional coordination polymer Co(ox)(bpy-d8) are presented, where ox=C₂O₄²⁻ and bpy-d8=4,4′-bipyridine-d8 (fully deuterated). The neutron powder diffraction data reveal a second-order crystallographic phase transition at 290 K. Above 290 K, a disordered structure, space group Immm, is observed that is closely related to the ordered structure previously proposed on the basis of single crystal X-ray diffraction. At low temperatures, the structure is an ordered variant of the high-temperature phase with space group I222. In both phases, the Co ions are linked by the oxalate forming infinite chains that are crosslinked by the bpy ligands.The magnetic susceptibility follows qualitatively a quasi one-dimensional chain behavior. It exhibits a broad maximum around 35 K, corresponding to a strong antiferromagnetic coupling through the oxalate bridges. A kink at 9 K marks the onset of long-range antiferromagnetic ordering due to much weaker interchain magnetic interactions.The magnetically ordered structure determined from the low-temperature neutron diffraction data can be described with the propagation vector (1/2, 1/2, 1/2), i.e. a doubling of the unit cell in each principal direction. It is concluded that a significant antiferromagnetic interaction is mediated through the bpy ligands, although the Co-Co distance along these bridges is 11.4 Å.     

Heat capacities of the electron acceptor 7,7,8,8-tetracyano- quinodimethane (TCNQ) and its radical-ion salt NH4(TCNQ) showing spin-Peierls transition

Heat capacities of the electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its radical-ion salt NH₄-TCNQ have been measured at temperatures in the 12-350 K range by adiabatic calorimetry. A λ-type heat capacity anomaly arising from a spin-Peierls (SP) transition was found at 301.3 K in NH₄-TCNQ. The enthalpy and entropy of transition are Δ_trsH=(667±7) J mol⁻¹ and Δ_trsS=(2.19±0.02) J K⁻¹ mol⁻¹, respectively. The SP transition is characterized by a cooperative coupling between the spin and the phonon systems. By assuming a uniform one-dimensional antiferromagnetic (AF) Heisenberg chains consisting of quantum spin (S=1/2) in the high-temperature phase and an alternating AF nonuniform chains in the low-temperature phase, we estimated the magnetic contribution to the entropy as Δ_trsS_mag=0.61 J K⁻¹ mol⁻¹ and the lattice contribution as Δ_trsS_lat=1.58 J K⁻¹ mol⁻¹. Although the total magnetic entropy expected for the present compound is R ln 2 (=5.76 J K⁻¹ mol⁻¹), a majority of the magnetic entropy (∼4.6 J K⁻¹ mol⁻¹) persists in the high-temperature phase as a short-range-order effect. The present thermodynamic investigation quantitatively revealed the roles played by the spin and the phonon at the SP transition. Standard thermodynamic functions of both compounds have also been determined.     

Structural characterization,thermal, vibrational properties and molecular motions in perovskite-type diaminopropanetetrachlorocadmate NH3(CH2)3NH3CdCl4 crystal

The work presents a detailed analysis of the sequencing of the structural phase transitions in NH₃(CH₂)₃NH₃CdCl₄ crystal by differential scanning calorimetry (DSC), X-ray, infrared, far infrared and Raman spectroscopy. DSC studies have shown that in analyzed crystal occurring one reversible continuous phase transition at 375/374 K (on heating/cooling). Observed in Nujol and Fluorolube mulls in the wide temperature range between 296 K and 413 K spectral changes through the structural phase transition can be attributed to an onset of motion of cations. An assignment of some bands due to internal modes has been also proposed.     

Phase transitions in CsHSO4 up to 2.5 GPa: Impedance spectroscopy under pressure

Phase transitions in CsHSO₄ at pressures up to 2.5 GPa have been studied with the help of electrical impedance measurements. The phase boundaries have been identified with the help of calculated activation energies of electrical conductivity and dielectric relaxation time. The derived temperatures of phase transition from the low conductive phase II into super ionic phase I at pressure less than 1 GPa confirm the previous results of Ponyatovski? et al. (1985) [4] and Friesel et al. (1989) [27]. The phase diagram derived in this study for pressure larger than 1 GPa differs from the data of Ponyatovski? et al. (1985) [4]. The phase transitions IV-VI and VI-I occur at higher temperatures having significantly larger Clapeyron slope. The phase VII was not identified from heating cycle and appears only under cooling between phases I and VI. The phase VIII was detected at 2.5 GPa at T<350 K and only during heating.     

Oxygen guest molecules in the nanopores of nanographite-network

Magnetic properties of nanographite-network-based nanoporous carbon having high surface area are investigated in the presence of magnetic oxygen guest molecules. The nanographite domains (stacked nanographene sheets) of 2-3 nm average in-plane size have localized spins of non-bonding π-electron state (edge-state) in the zigzag-shaped periphery of individual nanographene sheets. The electron paramagnetic resonance signal of edge-state spins is found to be highly sensitive to the presence of magnetic oxygen molecules. The line-width variation in the limit of lower oxygen pressure (1-20 Pa) shows that the magnetic interaction of oxygen can be divided into two temperature regimes, viz., the regime below 100 K, where chemisorption of oxygen is effective and the regime above 100 K, where only physisorption of oxygen takes place. Here, 100 K marks the energy of physisorption of oxygen molecules on nanographene, which is higher than the condensation energy of oxygen molecules represented by the boiling point of oxygen, 90 K, owing to the capillary effect. Above 100 K, magnetically active physisorbed oxygen molecules work to increase the line-width, which is governed by the dipolar field with oxygen molecules. The presence of a maximum in the line-width around 150 K, which is higher than 100 K, suggests the diffusion motion of oxygen molecules reduces the strength of exchange interaction between the edge-state spins and the oxygen spins as the temperature is elevated.     

High sensitivity of magnetism of the “114” ferrimagnet CaBaCo4O7 to stoichiometry deviation

The effect of oxygen/cobalt off-stoichiometry upon magnetism in CaBaCo₄O₇ has been investigated. It is shown that the oxides CaBaCo₄O_7+δ and CaBaCo_4−xO_7−δ (0≤x≤0.20) synthesized below 1100 °C in air exhibit phase separation, where ferrimagnetic regions with T_C~56 K to 64 K coexist with regions of magnetic clusters. The latter are detected from ac-susceptibility measurements, which show various frequency dependent peaks at ~14–20 K, 37 K, and 45 K, depending on the stoichiometry. The origin of this phenomenon is attributed to the great sensitivity of the material to oxidation as the synthesis of temperature is lowered, leading to the introduction of additional Co³⁺ cations, with respect to the ideal formula CaBaCo₂²⁺Co₂³⁺O_7. This excess Co³⁺ tends to destroy the ferromagnetic zig-zag chains of the ferrimagnetic structure and creates various cobalt spin clusters, leading to the inherent phase separation in the samples.     

Thermodynamics of ice at high pressures and low temperatures

A new equation of state of ice Ih recently proposed by Feistel and Wagner [J. Phys. Chem. Ref. Data 35 (2006) 1021-1047] is used to study the phenomena related to the equilibrium isentropic compression of an ice-water mixture and dynamic loading of solid ice. New results are presented concerning the properties of the new equation of state, equilibrium solid-liquid phase transitions and Hugoniots of low-temperature (100 K) and temperate (263 K) shock-compressed ice.     

Electron hopping mechanism in hematite (α-Fe2O3)

The frequency dependence of the real (?′) and imaginary (?″) parts of the dielectric constant of polycrystalline hematite (α-Fe₂O₃) has been investigated in the frequency range 0-100 kHz and the temperature range 190-350 K, in order to reveal experimentally the electron hopping mechanism that takes place during the Morin transition of spin-flip process. The dielectric behaviour is described well by the Debye-type relaxation (α-dispersion) in the temperature regions T<233 K and T>338 K. In the intermediate temperature range 233 K<T<338 K a charge carrier mechanism takes place (electron jump from the O²⁻ ion into one of the magnetic ions Fe³⁺) which gives rise to the low frequency conductivity and to the Ω-dispersion. The temperature dependence of relaxation time (τ) in the −ln τ vs 10³/T plot shows two linear regions. In the first, T<238 K, τ increases with increasing T implying a negative activation energy −0.01 eV, and in the second region T>318 K τ decreases as the temperature increases implying a positive activation energy 0.12 eV. The total reorganization energy (0.12-0.01) 0.11 eV is in agreement with the adiabatic activation energy 0.11 eV given by an ab initio model in the literature. The temperature dependence of the phase shift in the frequencies 1, 5, 10 kHz applied shows clearly an average Morin temperature T_Mo=284±1 K that is higher than the value of 263 K corresponding to a single crystal due to the size and shape of material grains.     

An origin of light induced centers in the visible range in ferroelectric oxides: possible role of the states of charge transfer vibronic excitons

A light induced absorption peculiarity connected with an absorption peak in the visible range for SBN/Ce was detected. The analysis of these data together with investigation results for a visible range center (VIS-center) absorption study in SBN/Ce and Cr, in nominally pure strontium barium niobate (SBN) as well as in Ba_0.77Ca_0.23TiO₃ crystals give support to charge transfer vibronic excitons (CTVEs) as origin of the phenomenon. While the fast (with relaxation time ∼1 ns at T∼300 K) response can be connected with transitions between excited branches of the adiabatic potential of the CTVE phase, the slow (with relaxation time ∼50 s at T∼230 K for SBN/Cr) response is connected with transitions between ground and first excited CTVE phase branches. The additional contribution to the latter effect due to the absorption of recharged oxygen ions which are in the framework of charge transfer induced by the CTVE cannot be disregarded. The explanation of the main results of the experiments shows that the VIS-center phenomena can be induced by the CTVE-states.     

Growth of crystalline quartz films with AT-cut plane by means of catalyst-enhanced vapor-phase epitaxy under atmospheric pressure

Crystalline quartz films with an AT-cut plane have been grown by catalyst-enhanced vapor-phase epitaxy, at atmospheric pressure, using two quartz buffer layers on a sapphire (110) substrate. In this method, the first quartz buffer layer was deposited on the sapphire (110) substrate at 773 K. After annealing at 823 K, the second buffer layer was deposited at 723 K. The crystal quartz epitaxial layer was then grown at 843 K. The X-ray full-width-at-half-maximum (FWHM) value of the crystalline quartz film obtained was smaller than that of crystalline quartz prepared using a hydrothermal process. The crystalline quality of the quartz films was dependent on the thickness of the buffer layers. Furthermore, it was found that angle control of the cut plane depended on the film thickness of the second buffer layer. The quartz films grown by vapor phase epitaxy show good oscillation characteristics at room temperature.     

Calorimetric investigation of the magnetic transition in quasi-one-dimensional molecule-based ferrimagnets: [Mn(OC14H29)4TPP][TCNE]·MeOH and [MnF4TPP][TCNE]·0.5MeOH

Heat capacity study was performed, for the first time, for [MnF₄TPP][TCNE]·0.5MeOH and [Mn(OC₁₄H₂₉)₄TPP][TCNE]·MeOH complexes in the 1.8-100 K temperature range under the 0-9 T magnetic field and disclosed new aspects inherent in such strongly coupled charge-transfer Mn-porphyrin-TCNE linear chain systems, where TPP=5,10,15,20-tetraphenylporphyrinato, TCNE=tetracyanoethylene and MeOH=methanol. Any heat capacity anomaly due to the onset of the magnetic long-range-order was not detected, whereas the magnetic phase transition has clearly been observed around 20 K by previous magnetic studies. As these materials are well approximated by quasi-one-dimensional ferrimagnetic Heisenberg chains with very large intrachain spin-spin interactions, the most part of the magnetic entropy is retained above the phase transition temperature as the dominant short-range order. This is the reason why no magnetic phase transition was detected by calorimetry. On the other hand, the big effect observed in the magnetic susceptibility is well accounted for if the formation of magnetic domains is assumed in the crystal.     

Structure and low-temperature properties of Ba8Ni6Ge40

Structural, magnetic, heat capacity, electrical and thermal transport properties are reported on polycrystalline Ba₈Ni₆Ge₄₀. Ba₈Ni₆Ge₄₀ crystallizes in a cubic type I clathrate structure with unit cell a=10.5179 (4) Å. It is diamagnetic with susceptibility χ_dia=−1.71×10^-6 emu/g Oe. An Einstein temperature 75 K and a Debye temperature 307 K are estimated from heat capacity data. It exhibits n-type conducting behavior below 300 K. It shows high Seebeck coefficients (−111×10^-6 V/K), low thermal conductivity (2.25 W/K m), and low electrical resistivity (8.8 mΩ cm) at 300 K.     

Detailed infrared spectroscopic study of thermal transitions in new hybrid [(CH3)2CHNH3]4Cd3Cl10 crystal

Phase transitions of tetra(isopropylammonium)decachlorotricadmate(II) [(CH₃)₂CHNH₃]₄Cd₃Cl₁₀ crystal have been studied by infrared, far infrared and Raman measurements in wide temperature range, between 11 K and 388 K. The temperature changes of wavenumber, center of gravity, width and intensity of the bands were analyzed to clarify cationic and anionic contributions to the phase transitions mechanism. The results of investigation showed earlier by differential scanning calorimetry (DSC), thermal expansion and dielectric measurements clearly confirmed the sequence of phase transitions at T₁=353 K, T₂=294 K and T₃=260 K. The current results derived from DSC and infrared measurements revealed additional phase transition at T₄=120 K.     

Effects of lattice and local dynamics in EPR spectra and electron spin relaxation of vibronic Cu(imidazole)6 complexes in Zn(imidazole)6Cl2·4H2O crystals

Cu(im)₆ complexes in Zn(im)₆Cl₂·4H₂O exhibit a strong Jahn-Teller effect which is static below 100 K and the complex in localized in the two low-energy potential wells. We have reinvestigated electron paramagnetic resonance (EPR) spectra in the temperature range 4.2-300 K and determined the deformation directions produced by the Jahn-Teller effect, energy difference 11 cm⁻¹ between the wells and energy 300 cm⁻¹ of the third potential well. The electron spin relaxation was measured by electron spin echo (ESE) method in the temperature range of 4.2-45 K for single crystal and powder samples. The spin-lattice relaxation is dominated by a local mode of vibration with energy 11 cm⁻¹ at low temperatures. We suppose that this mode is due to reorientations (jumps) of the Cu(im)₆ complex between the two lowest energy potential wells. At intermediate temperatures (15-35 K), the T₁ relaxation is determined by the two-phonon Raman processes in acoustic phonon spectrum with Debye temperature Θ_D=167 K, whereas at higher temperatures the relaxation is governed by the optical phonon of energy 266 cm⁻¹. The ESE dephasing is produced by an instantaneous diffusion below 15 K with the temperature-independent phase memory time , then it grows exponentially with temperature with an activation energy of 97 cm⁻¹. This is the energy of the first excited vibronic level. The thermal population of this level leads to a transition from anisotropic to isotropic EPR spectrum observed around 90 K. FT-ESE gives ESEEM spectrum dominated by quadrupole peaks from non-coordinating ¹⁴N atom of the imidazole rings and the peak from double quantum transition ν_dq. We show that the amplitude of the ν_dq transition can be used to determine the number of non-coordinating nitrogen atoms.