Ionic thermocurrents in sodium fluoride thin film

Ionic thermocurrent (ITC) in NaF thin film deposited between gold electrodes has been investigated in situ in the temperature region 300–500 K. The thermally stimulated polarization current (TSPC) and thermally stimulated depolarization current (TSDC) obtained under low electric field pf polarization (E_p) at a lower temperature of polarization (T_p) exhibited current-peak temperatures (T_M) about 420 K and 450 K. The activation energies associated with the first and the second current peaks were 1.15 + 0.05 eV and 0.65 + 0.02 eV, which are assigned to cation vacancy blocking at the grain boundary barrier and the electrode contact interface barrier respectively. Polarization under a strong electric field (E_p > MV m₋₁) at T_p > 480 K causes a quasi-stable shift of the ITC peak positions to higher temperature. The current peak positions and magnitudes then depend upon the polarity of the electrode metal during polarization, and activation energies associated with the first peak positions are 0.90 + 0.02 eV and 0.79 + 0.02 eV for positive and negative bias at the counter electrode respectively, which may be attributed to the clustering of the cation vacancies and the dislocation networks at the interfaces.     

Investigation of the diffusion of hydrogen in palladium by means of spin-lattice relaxation in the rotating frame

The diffusion of hydrogen in palladium $\text{(}\text{H}\text{Pd}\text{= 0.73)}$ has been investigated from 170 to 300K by measurements of the proton spin-lattice relaxation time in the rotating frame, T_1?. In contrast to previous T₁ measurements, a single activation energy of 0.225 eV is obtained, in agreement with the high-temperature T₁ data and with internal friction experiments at about 120K.     

Lithium motion in Li0.33 TiS2 and Li0.94 TiS2

We have studied the motion of lithium ions in Li_xTiS₂ (x = 0.33, 0.94) using pulsed NMR techniques. The temperature dependences of the spin lattice relaxation in the rotating frame (T_1?) suggest comparable activation energies for lithium ion diffusion for both samples, 3370 K, but an appreciably longer hopping time for the x = 0.94 sample. Low temperature values of T₂ agree with calculated and measured second moments for both materials.     

Étude par rmn de la localisation et des mouvements des protons dans les hydrures MgH2 et Mg2NiH4

Wide line and pulsed NMR studies are reported for MgH₂; and Mg₂NiH₄ hydrides at 79 and 30 MHz in the temperature range between 100 and 500 K. Line shape data confirm a rutile type structure for MgH₂, and lead to the evaluation that 97% of the hydrogen is present in this phase, the remainder being in solid solution MgH_x, (x<0.04).Mg₂NiH₄ shows a Gaussian line, whose peak-to-peak width decreases from 6.16 to 4.28 G in the range 320–365 K. From 365 to 480 K the spectrum shows a second, narrower, line (0.85 G), implying that approximately 7% of the protons have migrated from their initial position to energetically less stable sites. The thermal behaviour of the T₁ and T₂ relaxation times shows a dramatic variation in the 320–370 K temperature range in connection with the change of the proton localization. Relaxation mechanisms can be attributed mainly to conduction electron-nucleus interactions. With rising temperature, diffusion mechanisms are also involved. A diffusion activation energy of about 0.35 eV has been determined, with a diffusion coefficient 3.45 × 10^?8 < D < 4.6 × 10^?8 cm²/s.     

Superconductivity of hydrides Ti3SbHx

The effect of interstitially dissolved hydrogen on the transition temperature T_c of superconductivity has been investigated in cubic A-15 type (Cr₃Si type) hydrides Ti₃SbH_x, 0 ? x ? 2. The transition temperature T_c decreases with increasing hydrogen content x from 5.6 K in Ti₃Sb to 1.0 K in Ti₃SbH_1.0.     

Mobility of electrons in SnS2−xSex

The electrical resistivities and Hall constants of the semiconducting compounds SnS_2?xSe_x have been measured at temperatures ranging from 100 to 450 K and three donor ionization energies (0.013, 0.086 and 0.25 eV) have been identified. The Hall mobilities exhibit for T> 200K a temperature dependence of the form μ～ (T/T₀)^?n separating the SnS_2?xSe_x compounds into two groups one behaving like SnS₂ and the other like SnSe₂.     

Nuclear magnetic resonance study of HfV2Hx and ZrV2Hx (0 ⩽ x ⩽ 4.2) hydrides

A proton NMR spin echo study of the system HfV₂H_x and ZrV₂H_x (0 ? x ? 4.5) hydrides are reported. The T₁ spin lattice relaxation rate enables us to extract the activation energy for diffusion, E_a, as well as the attempt frequency v₀; both depend strongly on the hydrogen concentration. The existence of a correlation between E_a and v₀ in these and other hydride systems yield the temperature dependence of the activation energy.     

Ionic lithium conductivity in sulphur base glasses. 7Li NMR study of xLi2S−(1−x)GeS2 system

The lithium mobility in glasses of composition xLi₂S?(1?x)GeS₂ has been followed by c.w. (for x = 0.3; 0.4 and 0.5) and pulsed NMR (for x = 0.3 and 0.5) between ? 150 and + 280°C.The second moment of the resonance line of ⁷Li(0.89–1.51 G²) is proportional to the molar fraction of Li₂S, which may be correlated to an homogeneous Li nuclei distribution.The resonance line profiles and their thermal evolution seem to show that some Li⁺ ions do not participate in the conduction.Thermal variation of the spin-lattice relaxation time T₁, shows a strongly asymmetrical shape, if one considers In $\text{T}{}^{\mathrm{?1}}{}_1\text{= ?(T}{}^{\mathrm{?1}}\text{)}$ on both sides of the observed maxima. This behaviour may be explained by a distribution of the Li correlation times τ corresponding to different jump distances between various possible sites. The Cole-Davidson model allows the best agreement between experimental and theoretical values of the correlation times.The activation energies deduced from this model are close to those obtained from conductivity measurements (0.43 eV by NMR, 0.56 eV by conductivity determinations for x = 0.50), they may be correlated to the longer Li⁺ jumps in the vitreous matrix.     

Magnetic properties of titanium vanadium hydrides

Measurements have been made of the magnetic susceptibility X in ternary titanium-vanadium hydrides Ti_1?yV_yH_x in the range 0<y< 0.5 and with a hydrogen to metal ratio from 1.6 to 1.92; they cover the temperature interval from 80 to 440 K. The x^?T curves of some of the ternary hydrides possess a maximum similar to that seen in binary hydrides. Its occurrence depends upon both hydrogen and vanadium concentration. Comparison with the lattice constants shows that this dependence is related to the transition from the cubic γ-phase to the tetragonal δ-phase. The x^?T curves of those samples showing the phase transition were extrapolated from the cubic phase down to lower temperatures. Conclusions were drawn from the measured and extrapolated susceptibility values, as to the influence of both hydrogen and vanadium concentrations on the electronic structure of these hydrides. The dependence of the magnetic susceptibility on the vanadium concentration shows that, in the cubic phase, the fermi energy lies on the increasing side of a maximum in the density of states curve. The degree of occupation of the conduction band does not depend on the hydrogen concentration. The rigid band model cannot be used in the hydrides studied here to account for the effects of varying their hydrogen concentration.     

Etude par RMN de la structure dynamique de l'alanate Na3AlH6

A low temperature wide-line NMR study has allowed a determination of the AI-H bond lengths in cryolite-type Na₃AlH₆. It was found from the thermal behavior of the proton lines that the |AIH₆|^3? octahedra reorient around a C₄ axis. Starting below 170 K, this rotation can be hindered by lattice defects. Above room temperature it becomes isotropic, and a quick protonic exchange appears.The thermal narrowing of the linewidth and the T₁ and T_1ρ relaxation times lead to activation energies of about 0.38 eV for axial rotation and 0.51 eV for protonic exchange. The minimum in T₁ is in good agreement with the exchange model. Absorption phenomena, as well as partial decomposition of Na₃AlH₆ during the heat treatments, explain the presence of small amounts of mobil hydrogen.     

Self-diffusion of oxygen in superstoichiomertric uranium dioxide in the range of the superion phase transition

The self-diffusion of oxygen in the superion transition range (1300–3000 K) of superstoichiometric uranium dioxide UO_{2 + x} is studied by the method of molecular dynamics using the pair interaction potential recovered from data for the thermal expansion of the UO₂ lattice. It is shown that three portions can be distinguished in the temperature dependence of the coefficient of oxygen self-diffusion in UO_{2 + x} , lnD = f(1/T), for all the compositions studied (x = 0, 0.008, and 0.030). These portions, each being described by the Arrhenius relationship, correspond to the crystalline, transition, and superion states of UO_{2 + x} . At low temperatures (1300–1820 K), the activation energies of oxygen diffusion for the above compositions are, respectively, 2.66 ± 0.44, 1.33 ± 0.10, and 1.00 ± 0.09 eV. At the beginning of the transition region, these activation energies rise to 3.40 ± 0.11, 2.24 ± 0.10, and 1.66 ± 0.60 eV. In the superion state, the activation energy of oxygen diffusion for all the compositions is the same, 1.25 ± 0.15 eV, within the error limit. As the oxygen content in UO_{2 + x} grows, the phase transition temperature decreases considerably and may reach 1600 K at x = 0.2. Comparison with experimental data for the low-temperature oxygen diffusion coefficient and with the data of UO₂ simulation using graphic processors shows good agreement of the results. By comparing the concentration dependences of the oxygen diffusion coefficient that are obtained by magnetic dynamics simulation with experimental data, it is shown that quantitative calculation of these dependences in the case of UO_{2 + x} can be carried out only for compositions with x < 0.03 if the given type of potential is used.     

Proton magnetic resonance studies of TiCuH

The TiCuH structure can be described as alternating layers of TiH₂ and Cu atoms and, thus, corresponds to a two-dimensional analog of metal hydrides with CaF₂- type structures. Measurements of the proton relaxation times for TiCuH yield an activation energy of 0.79 eV for hydrogen diffusion. This result strongly suggests the H-atoms in TiCuH jump directly between the tetrahedral sites rather than through the vacant octahedral sites as proposed for H-atom jumps in f.c.c. TiH_x. In addition, the Korringa constant and hydrogen diffusion rate for TiCuH are compared with similar parameters for TiH_x and several ternary titanium hydrides.     

PAC study of nuclear relaxation in solids:181Ta in hafnium hydrides

The electric quadrupole interaction (QI) at the site of¹⁸¹Ta in different hafnium hydrides HfH_x has been investigated as a function of temperature by TDPAC measurements. Below 300 K the QI is static within a 300 nsec time window. Above 300 K a dynamic QI related to the diffusion of hydrogen atoms leads to relaxation effects in the TDPAC spectra. The average residence time between hydrogen jumps, evaluated on the basis of the theory of stochastic perturbations, ranges from 100 nsec at 400 K in the ɛ-phase to 1 nsec at 700 K in the α-phase of the hafnium-hydrogen system. The activation energy for hydrogen jumps was found to be independent of the hydrogen concentration: E_a=0.53(12) eV.     

NMR spectral densities and two dimensional diffusion in TiS2(NH3)1.0 and TaS2(NH3)x

NMR measurements of proton spin-lattice relaxation times T₁ and T_1? in the layered intercalation compounds TiS₂(NH₃)_1.0 and TaS₂(NH₃)_x (x = 0.8, 0.9, 1.0) are reported as functions of frequency and temperature (100 K – 300 K). These observations probe the spectral density of magnetic fluctuations due to motions of the intercalated molecules at frequencies accessible to the T₁ (4–90 MHz) and T_1? (1–100 kHz) measurements. Since the average molecular hopping time (τ) can be changed by varying temperature, different regions of the spectral density can be examined. For T > 200 K, both T^?1₁ and T^?1_1? vary logarithmically with frequency, reflecting the two dimensional character of the molecular diffusion. The temperature dependence of T₁ suggests that a more accurate picture of the short time dynamics is required. No dependence of relaxation rate on vacancy concentration is found.     

Effect of carbon doping on thermodynamic behavior of MgB2

The thermodynamic behavior of carbon doped MgB₂ has been studied using a rigid ion model (RIM). The model potential consists of the long-range Coulomb, the short-range repulsive and the van der Waals interactions. This model has successfully explained the cohesive and thermodynamic properties of Mg(B_1−xC_x)₂ (x=0.0, 0.02, 0.05, 0.075, 0.1, 0.2). The properties studied are the cohesive energy, molecular force constant, Restrahlen frequency, compressibility, Debye temperature and Gruneisen parameter. Our results on Restrahlen frequency and Debye temperature are in reasonably good agreement with the available experimental data. In addition, we have computed the specific heat C_p for Mg(B_1−xC_x)₂ (x=0.2) as a function of temperature T in the range 16 K?T?1000 K. We have also shown the variation of specific heat C_p with doping concentration at room temperature (300 K). The calculated specific heat C_p for Mg(B_1−xC_x)₂ (x=0.2) in the temperature range 16 K?T?22 K for which experimental results are available, agrees pretty well with the experimental data.     

Thermodynamic study of compounds of the Nd-Ba-Cu-O system

Standard enthalpies of formation for solid solutions of composition Nd_{1 + x} Ba_{2 ? x} Cu₃O _y (x = 0–0.8, y = 6.65–7.24) from oxides were determined by solution calorimetry. The heat capacity of NdBa₂Cu₃O_6.87 phase was measured in the range 5–320 K by low-temperature adiabatic calorimetry. The absolute entropy S ^o(T), the difference of enthalpies H ^o(T)-H ^o(0 K), and the reduced Gibbs energy Φ^o(T) = S ^o(T)–[H ^o(T)–H ^o(0)]/T were calculated on the basis of smoothed dependence C _p (T) in the 0–320 K range. An assessment was made for the heat capacities and the absolute entropies of solid solutions Nd_1+x Ba_2?x Cu₃O _y . The obtained set of thermodynamic parameters can be used for the calculation of phase equilibria in the Nd-Ba-Cu-O system.     

A.C. electrical conductivity of potassium perchlorate

A.C. electrical conductivity of pottasium perchlorate (KP) has been measured in the temperature range 25–325°C at frequencies ranging from 50–500 Hz using an automated technique. Three regions with activation energies. 1.08 ± 0.02, 0.66 ± 0.01 and 0.39 ± 0.04eV are observed in ln(σT) vs 1/T plots at frequencies < - 50 Hz. Dielectric loss measurements on KP samples doped with CrO₄^2? and SO₄^2? ions show the presence of impurity-vacancy complexes with reorientation energies of 0.99 ±0.02 and 1.07 ± 0.01 eV respectively. The results are interpreted in terms of a defect model which highlights the role of various conduction and relaxation mechanisms in the a.c. electrical properties of the material.     

Structural and magnetic studies of the alloy system GdInxAg1-x

The structural and magnetic studies below room temperature of the alloy system GdIn_xAg_1-x(0?x?1) are reported. It has been found that alloys with x?0.5 crystallize in CsCl type cubic structure, but the distortion of the unit cell starts for alloys with x#62;0.5 and for these alloys the unit cell becomes tetragonal. No phase change is evident from the low temperature (295-8 K) structural studies. However, a break appears in the X^-1_m vs. T linear plot of each alloy of this system at a specific temperature (designated as break temperature T_B). The variation of T_B with x is similar to the variation of phase transition temperature with x reported for LaIn_xAg_1-x. Close agreement has been found in the values of effective magneton number (p), magnetic ordering [Néel (T_N) or Curie (T_C)] and paramagnetic Curie (θ_p) temperature for materials studied by us and earlier workers. The variation of magnetization with applied field strength (2.5-65)×10⁵ Am^-1) at 4.2 K has also been reported for ferromagnetic of this system. It has been concluded that alloys with 0.4?x?0.6 are simple ferromagnets with parallel alignment of magnetic moment in the ground state. The angular arrangement of the magnetic moment starts appearing in the ground state for alloys with x?0.4 for x#62;0.6 and continues till x becomes closure to 0.17 or 0.84. The alloys with x=0.17 or x=0.84 have θ_p and T_C equal to zero and appear paramagnetic. Angular arrangement in spins again appear for alloys with x?0.17 or x#62;0.84, however all materials with 0?x?0.17 or 0.84?x?1 remain antiferromagnetic.     

Electrical conductivity,absorption and luminescence measurements in cubic boron nitride

Electrical and optical measurements were carried out on tiny crystals of cubic boron nitride. The dark current i_D was found to change exponentially with T, with activation energies in the range 0·2–0·4 eV. A red electroluminescence, of intensity i_EL. proportional to i_D was observed. Upon illumination at low temperatures a photocurrent i_p proportional to the square root of the excitation intensity appeared. It varied exponentially with T, with an activation energy of 0.05 ± 0.01 eV. The crystals exhibited a red thermoluminescence with several unresolved peaks covering the temperature range 100–400K, and having activation energies in the range 0·15–0·40 eV.     

Transient and steady electron currents limited by ionic space charge in electrolytically coloured potassium halides

Transient electrical currents have been measured when potassium halides are electrolytically coloured under constant temperature and applied voltage. An analysis of the characteristics of these currents leads to the conclusion that they are electron currents limited by ionic space charge. A very detailed study of the transient current as function of temperature (T ? 825°K) and applied voltage (V ? 10³V) has been accomplished in KBr, KI and KC1 single crystals. A quadratic law of the type J_sαV², has been observed to be obeyed in the stationary level of the current, J_s. From the dependence of the steady value (J_s) on temperature we have obtained activation energies (W) for the process responsible for the propagation of the colour (F-centre) cloud from the cathode to the anode. The experimental values are W = 1.6, 1.6 and 1.8 eV for KBr, KI and KC1, respectively. According to these results and others obtained by other authors, it is proposed that the F-centre diffusion takes place by movement of the F-electron from the centre to the nearest anion vacancy under the action of the electric field and without passing through the conduction band. The propagation process appears to be controlled by the anion vacancy density and mobility. From the above values of W, we have obtained activation energies for the diffusion of anion vacancies of 0.8, 0.8 and 0.7 eV for KBr, KI and KC1, respectively.