Tuning hydrogen storage properties and reactivity: Investigation of the LiBH4-NaAlH4 system

Tuning the hydrogen storage properties of complex metal hydrides is of vast interest. Here, we investigate the hydrogen release and uptake pathways for a reactive hydride composite, LiBH₄−NaAlH₄ utilizing in situ synchrotron radiation powder X-ray diffraction experiments. Sodium alanate transforms to sodium borohydride via a metathesis reaction during ball milling or by heating at T∼95 °C. NaBH₄ decomposes at ∼340 °C in dynamic vacuum, apparently directly to solid amorphous boron and hydrogen and sodium gas and the latter two elements are lost from the sample. Under other conditions, T=400 °C and p(H₂)=∼1 bar, NaBH₄ only partly decomposes to B and NaH. On the other hand, formation of LiAl is facilitated by dynamic vacuum conditions, which gives access to the full hydrogen contents in the LiBH₄−NaAlH₄ system. Formation of AlB₂ is observed (T∼450 °C) and other phases, possibly AlB_x or Al_1−xLi_xB₂, were observed for the more Li-rich samples. This may open new routes to the stabilization of boron in the solid state in the dehydrogenated state, which is a challenging and important issue for hydrogen storage systems based on borohydrides.     

Investigation of thermodynamic properties of cerium dioxide by statistical moment method

The thermodynamic properties of the cerium dioxide (CeO₂) are studied using the statistical moment method, including the anharmonicity effects of thermal lattice vibrations. The free energy, linear thermal expansion coefficient, bulk modulus, specific heats at the constant volume and those at the constant pressure, C_V and C_P, are derived in closed analytic forms in terms of the power moments of the atomic displacements. The temperature dependence of the thermodynamic quantities of cerium dioxide is calculated using three different interatomic potentials. The influence of dipole polarization effects on the thermodynamic properties and thermodynamic stability of cerium dioxide have been studied in detail.     

Thermodynamics and defect structures of silver sulfide

Published measurements of sulfur vapor pressure and silver electromotive force were used to determine thermodynamic properties of silver sulfide above 379 K. They were Gibbs-Duhem integrated to estimate the formation properties of stoichiometric Ag₂S of fcc, bcc, and monoclinic crystal structures. Statistical thermodynamics was applied to estimate free energies and find possible atom arrangements in off-stoichiometric silver sulfide. Theoretical calculations show that silver vacancies and atoms may be in quasi-chemical equilibrium between tetrahedral and octahedral sites in the fcc structure and between two states of atoms within tetrahedral sites in the bcc structure and within octahedral sites in the monoclinic structure. A strong indication is that vacancy clusters should predominate, each containing four-atom vacancies in the fcc phase and three-atom vacancies in the bcc phase.     

A review of catalyst-enhanced magnesium hydride as a hydrogen storage material

Magnesium hydride remains an attractive hydrogen storage material due to the high hydrogen capacity and low cost of production. A high activation energy and poor kinetics at practical temperatures for the pure material have driven research into different additives to improve the sorption properties. This review details the development of catalytic additives and their effect on the activation energy, kinetics and thermodynamic properties of magnesium hydride.     

Electrical conductivity and structural stability of SrCo1−xFexO3−δ

Perovskite compounds in the system of SrCo_1−xFe_xO_3−δ (x=0.2, 0.4 and 0.6) were synthesized by solid state reaction. SrCo_1−xFe_xO_3−δ shows the p-type small polaron conduction behavior. Electrical conductivity and oxygen vacancy content decrease with increase in Fe content. The incorporation of Fe increases the structural stability of SrCo_1−xFe_xO_3−δ at low temperatures, while decreasing the structural stability at high temperatures. Oxygen partial pressure has a strong influence on electrical conductivity. At low oxygen partial pressure, SrCo_0.8Fe_0.2O_3−δ will transform from cubic to orthorhombic structure. This structure can remain in 5%H₂/Ar only for a short time and then dissociates into Sr₃Fe₂O_6.64 and Co due to the reduction of B-site elements.     

Preparation and characterization of lithium niobate as a novel photocatalyst in hydrogen generation

Several chemical compounds based lithium niobate have been tested in the reaction for the photocatalytic hydrogen generation. The photocatalysts have been prepared by impregnation of Nb₂O₅ in the aqueous solution of lithium hydroxide and then the calcination at the temperature range of 400-650 °C. In this report, we present the interesting study showing that the most active catalyst for the photocatalytic generation of hydrogen is the one containing two lithium niobate phases such as LiNbO₃ and LiNb₃O₈. It means that the lithium niobates based catalyst without any further modification or doping can be applied as a novel material for this process.     

Sorption study of an anionic dye - benzopurpurine 4B - on calcined and uncalcined Mg-Al layered double hydroxides

In this paper, the elimination from aqueous solution of the pollutant benzopurpurine 4B by Mg-Al-CO₃ hydrotalcite and its modified form Mg-Al-500 has been studied. Mg-Al-CO₃²⁻ layered double hydroxide with an Mg/Al molar ratio of 2.0 was synthesized by the co-precipitation method, and its modification was carried out by calcination. The affinity of these materials with a mixture of benzopurpurine 4B was studied as a function of dye-adsorbent contact time, initial pH of the solution, initial dye concentration and temperature. The results indicate that HDLs were effective in removing benzopurpurine 4B anionic dye. Their saturated adsorption capacities are very high, particularly for the calcined material Mg-Al-500 compared to the standard one Mg-Al-CO₃²⁻.The characterisation of the solid Mg-Al-500, both fresh and after removal of the dye by X-ray diffraction and infrared spectroscopy, shows that the benzopurpurine 4B adsorption on this calcined phase is enhanced by reconstruction of a matrix hydrotalcite intercalated by the dye, with basal spacing of 23.77 Å, which is larger than that of Mg-Al-CO₃²⁻ LDHs (7.57 Å).     

Thermodynamic modeling of Fe–Ni pentlandite

Gibbs energy modeling of iron–nickel pentlandite has been performed using experimental data of ternary phase equilibria. A three-sublattice approach in the framework of the Compound Energy Formalism is developed to refine a two-sublattice model of pentlandite recently applied within a complete assessment of the Fe–Ni–S system. Experimental data about the iron site fraction on the octahedral sublattice at 523.15 K for the composition Fe₅Ni₄S₈ as well as the enthalpy of formation at 298.15 K for the composition Fe_4.5Ni_4.5S₈ are predicted satisfactorily by the novel model. New possibilities to interpret experimental phase equilibrium data on complex phase relations with pentlandite are discussed together on the basis of the recent extension of a second high-temperature heazlewoodite phase to a ternary solution phase.     

Ab initio calculations study of the electronic, optical and thermodynamic properties of NaMgH3, for hydrogen storage

The structural stability, electronic structure, optical and thermodynamic properties of NaMgH₃ have been investigated using the density functional theory. Good agreement is obtained for the bulk crystal structure using both the local density approximation (LDA) and the generalized gradient approximation (GGA) for the exchange-correlation energy. It is found from the electronic density of states (DOS) that the valence band is dominated by the hydrogen atoms while the conduction band is dominated by Na and Mg empty states. Also, the DOS reveals that NaMgH₃ is a large gap insulator with direct band gap 3.4 eV. We have investigated the optical response of NaMgH₃ in partial band to band contributions and the theoretical optical spectrum is presented and discussed in this study. Optical response calculation suggests that the imaginary part of dielectric function spectra is assigned to be the interband transition. The formation energy for NaMgH₃ is investigated along different reaction pathways. We compare and discuss our result with the measured and calculated enthalpies of formation found in the literature.     

Thermochemical studies on RE2O2CO3 (RE=Gd, Nd) decomposition

Thermochemistry in the decomposition of gadolinium di-oxycarbonate, Gd₂O₂CO₃(s) and neodymium di-oxycarbonate, Nd₂O₂CO₃(s) was studied over the temperature region of 774-952 K and 775-1105 K, respectively. The equilibrium properties of the decomposition reactions were obtained by tensimetric measurement of the CO₂(g) pressure over the biphasic mixture of RE₂O₂CO₃(s) and RE₂O₃(s) at different temperatures (RE=Gd, Nd) and also by thermogravimetric analysis of the decomposition temperature at different CO₂ pressures. The temperature dependence of the equilibrium pressure of CO₂ thus measured could be given by

ln p_CO2/Pa (±0.13)=−22599.1/T+35.21 (774≤T (K)≤952) for Gd₂O₂CO₃ decomposition and

ln p_CO2/Pa (±0.19)=−23824.7/T+33.14 (775≤T (K)≤1105) for Nd₂O₂CO₃ decomposition.

From the above vapor pressure expressions, the median enthalpy and entropy of the decomposition of the oxycarbonates were calculated by the second law analysis and their thermodynamic stabilities were derived. The results are discussed in the light of available thermochemical data of the compounds.     

Solution calorimetric investigation of AgCl-AgI ionic conductor composites at 298 K: observation of metastable AgI modifications

The enthalpies of solution of pure silver halides AgCl and AgI and a composite material with molar composition 0.5 AgCl-0.5 AgI were measured at 298 K in a mixture of Na₂S₂O₃ (1 M) and NH₄OH (1 M). X-ray diffraction patterns showed that the composite material contained the metastable γ-AgI phase; different mechanisms for its stabilization were discussed. The phase transition enthalpies of AgI modifications and the enthalpy of formation of the composite material were deduced from the measurements. The latter could be related to a change of interfacial enthalpies.     

Study of the structural, dielectric and magnetic properties of Bi2O3 and PbO addition on BiFeO3 ceramic matrix

In this paper we studied the effects of Bi₂O₃ and PbO addition on BiFeO₃ (BFO) ceramic matrix. The structural, dielectric and magnetic properties of fifteen BFO samples were discussed in view of possible applications in RF and microwave devices. The present work also reports the preparation of the samples. Polyvinyl alcohol (PVA) and tetraethyl orthosilicate (TEOS) were also added as a binder in the fabrication procedure. The samples have been studied by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and magnetic hysteresis measurements. Further, a study based on impedance spectroscopy also has been done. Dielectric permittivity (ε′) and dielectric loss (tan δ) were measured at room temperature in the frequency range 100 Hz-10 MHz, as well as a.c. conductivity. The -Im[Z(f)] versus Re[Z(f)] plot has been obtained. The samples were investigated in view of possible applications like miniaturized filters, diplexers and dielectric resonator antennas (DRA). In the RF and MW frequency region, the application of magneto-dielectric and multiferroic perovskite composite materials is desirable for the miniaturization of components.     

YB48 the metal rich boundary of YB66; crystal growth and thermoelectric properties

It was discovered that the well-known higher boride YB₆₆, one of the first reported phonon glass electron crystals (PGEC), could be obtained in a much more metal-rich composition than previously thought possible. Using the floating zone growth method, YB₄₈ single crystals with YB₆₆ crystal structure could be obtained, and their thermoelectric properties measured. This expansion of the homogeneity range of the well-known YB₆₆ compound is surprising and a new Y atomic site was discovered. YB₄₈ exhibits much higher power factors than YB₆₆ which increase rapidly with increasing temperature. The obtained dimensionless figure of merit of this compound at 990 K is approximately 30 times higher than that of previously reported YB₆₆ samples, and higher than any other pristine higher boride. This discovery reveals YB₄₈ as a promising high temperature thermoelectric material.     

Magnetic properties for the Cu2MnSnSe4 and Cu2FeSnSe4 compounds

Magnetic susceptibility χ measurements in the range from 2 to 300 K were carried out on samples of the Cu₂FeSnSe₄ and Cu₂MnSnSe₄ compounds. It was found that Cu₂FeSnSe₄ was antiferromagnetic showing ideal Curie-Weiss behavior with a Néel temperature T_N of about 19 K and Curie-Weiss temperature θ=−200 K, while for Cu₂MnSnSe₄ the behavior was spin-glass with a freezing temperature T_f of about 22 K and Curie-Weiss temperature θ=−25 K. The spin-glass order parameter q(T), determined from the susceptibility data, was found to be in agreement with the prediction of conventional spin-glass theory.     

Effect of magnetic field in the microhardness studies on calcium hydrogen phosphate crystals

Calcium hydrogen phosphate dihydrate (CaHPO₄·2H₂O, brushite) crystals are grown in gel medium at physiological pH by single diffusion method in the presence of different magnetic field strengths, namely 0, 0.1 and 0.2 Tesla. The results indicate that in the presence of magnetic field, the number of brushite crystals formed at the gel-solution interface reduces and the average size of the crystals increases. This shows that the growth of brushite crystal was favored by magnetism. Vickers and Knoop microhardness studies were carried out on the crystals grown at various magnetic fields. The Vickers (H_V) and Knoop (H_K) microhardness numbers were found to increase with increasing load. The values of Meyer’s index number (n) decrease while the magnetic field strength increases. Nevertheless the n values are greater than 1.6, which shows that the brushite crystals grown under magnetic fields still fall in the soft material category. The brittle index (Bi), yield strength (σ_y) and elastic stiffness constant (c₁₁) were calculated. The Young’s Modulus was calculated using the Knoop hardness value and found to decrease in higher magnetic field strengths.     

Evaluation of Gibbs free energies of formation of Ce–Cd intermetallic compounds using electrochemical techniques

Gibbs free energies of formation of six Ce–Cd intermetallic compounds, CeCd, CeCd₂, CeCd₃, CeCd_58/13, CeCd₆ and CeCd₁₁, were evaluated systematically using electrochemical techniques in the temperature range of 673–923 K in the LiCl–KCl–CeCl₃–CdCl₂ molten salt bath. The linear dependence of the Gibbs free energies of formation on temperature yields to the enthalpies and entropies of formation of these intermetallic compounds. By extrapolating the Gibbs free energy of Ce–Cd intermetallic compounds to the Cd distillation temperature, it was clear that the Gibbs free energy of Ce–Cd intermetallic compounds decreases gradually from CeCd₆ to CeCd₂ and attains minimum value at CeCd₂. This suggests on the Cd distillation from the U–Pu–Ce–Cd alloy that the dissolution of U or Pu into CeCd₂ should be mostly taken into consideration.     

Biasing effects on thallium and silver chlorides with dc/ac voltage

Comparison was made between crystals of thallium chloride and silver chloride on their biasing effects with dc/ac voltage. Previous reports say that, although their electrical conductivities are similar, the dominant charge carriers in the former are the Cl⁻ ions while the Ag⁺ ions in the latter. The present dc/ac study demonstrates the following: for thallium chloride, although Cl⁻ conduction may be dominant under low bias field, Tl⁺ conduction supercedes Cl⁻ conduction when the bias field is enhanced. For silver chloride, Ag⁺ conduction is overwhelming within wide temperature range, to cause easy dielectric breakdown on dc biasing. Concerning the extrinsic conductivity seen at temperatures below 60 °C (thallium chloride) or below 150 °C (silver chloride), it is ascribed to grain-boundary related electron conduction, not to grain-boundary related Tl⁺ or Ag⁺ conduction as reported earlier.     

Effect of varying mixture ratio of raw material powders on the thermoelectric properties of AlMgB14-based materials prepared by spark plasma sintering

Thermoelectric properties of AlMgB₁₄-based materials prepared by spark plasma sintering were investigated. Al, Mg, and B powders were used as raw material powders. The raw powders were mixed using a V-shaped mixer, and then the mixture was sintered at 1673 K or 1773 K. The mixture ratio of raw powders was varied around stoichiometric ratio of AlMgB₁₄. X-ray diffraction patterns of samples showed that all samples consist of AlMgB₁₄ and MgAl₂O₄. The Seebeck coefficient of the samples exhibited significant change depending on the varying mixture ratio and sintering temperature. One sample exhibited a large negative value for the Seebeck coefficient (approximately −500 μV/K) in the temperature range from 573 K to 1073 K, while others showed positive value (250–450 μV/K). Thus n-type AlMgB₁₄-based material has been realized by varying raw material ratio and sintering temperature.     

Influence of the active layer thickness on the electrical properties of ZnO thin film transistors fabricated by radio frequency magnetron sputtering

We report on the electrical properties of bottom-gate ZnO thin film transistors (TFTs) with different active layer thicknesses. The ZnO active layer films with thickness varied from 20 to 100 nm were deposited by radio frequency (rf) magnetron sputtering on SiO₂/p-Si substrate and annealed at a high temperature of 950 °C. The transistor with 40 nm thick ZnO exhibited the best performance, with a field effect mobility of 27.5 cm²/V s, a threshold voltage of −2.4 V and an on/off ratio of 7×10³.     

Equivalent electric circuit analyses of ionic thermocurrent in sodium-doped CaF2 crystals

The characteristics of high-temperature ionic thermocurrent (HT ITC) in CaF₂ doped with different sodium concentrations were studied by the Teflon-insulated electrode ITC method. It was shown that, with increasing sodium concentration, the HT ITC band moved toward a Na⁺-F_V dipole band with a peak at 162 K. The results of analyses of the HT ITC spectra using an equivalent electric circuit proved that the activation energy of space charge migration related to HT ITC was also strongly dependent on the doped sodium concentrations if varied from 0.94 to 0.46 eV with increasing sodium concentration in our ITC study. In addition, the broadening of the Na⁺-F_V dipole band was observed in 3 nominal mole% NaF-doped CaF₂, which was accompanied by a considerable decrease of the activation energy from 0.46 to 0.29 eV without showing marked temperature shifts of the peak ITC bands.