Effects of the addition of Pd on the hydrogen absorption–desorption characteristics of Ti33V33Cr34 alloys

The hydrogen absorption–desorption performance of the body-centered-cubic (bcc) Ti–V–Cr–Pd alloys have been investigated. Ti₃₃V₃₃Cr₃₄ ingots with 0, 0.05, 0.5 at.% Pd were prepared by arc melting. X-ray diffraction (XRD) revealed that all of these alloys were homogeneous bcc solid solutions. Pd-containing (0.05, 0.5 at.% Pd) Ti–V–Cr alloys have better initial activation properties than those without Pd, and the desorption plateau pressure of the (Ti₃₃V₃₃Cr₃₄)_99.5Pd_0.5 alloy was substantially higher than that of the alloy without Pd. It is also found that the hysteresis difference is smaller in these alloys and degradation of hydrogen absorption capacity becomes steady after the 25th cycling test. (Ti₃₃V₃₃Cr₃₄)_99.5Pd_0.5 alloy exhibits large hydrogen absorption and desorption capacity of up to 3.42 and 2.07 mass% at 353 K, respectively.     

热处理对包含正二十面体准晶相Ti1.4V0.6Ni合金电极的电化学性能的影响（英文）

研究了热处理前后Ti1.4V0.6Ni合金的结构和电化学性能。采用X射线粉末衍射(XRD)方法分析合金的结构。电化学特性包括放电容量、循环稳定性和高倍率放电性能等。XRD衍射分析表明,在590°C热处理30min的合金,主要包含正二十面体准晶相、Ti2Ni(FCC)相、V基固溶相(BCC)和C14Laves相(Hex)。电化学测试显示,热处理后在30°C和放电电流密度为30mA/g的条件下,合金电极的最大放电容量可达330.9mA·h/g,并且循环稳定性和高倍率放电性能也得到改善。此外,通过电化学阻抗和合金内部氢的扩散系数研究了合金电极的动力学性能。     

Influence of the addition of vanadium on the hydrogenation properties of the compounds TiFe0.9Vx and TiFe0.8Mn0.1Vx (x = 0, 0.05 and 0.1)

TiFe_0.9 and TiFe_0.8Mn_0.1 hydrides have suitable equilibrium pressures at ambient conditions and are potential candidates for hydrogen storage applications. In this work, we study the influence of the addition of small amounts of vanadium on the hydrogenation properties of TiFe_0.9V_x and TiFe_0.8Mn_0.1V_x (x = 0, 0.05 and 0.1) alloys. The excess of Ti from TiFe in these materials results in the precipitation of Ti and Ti₂Fe-type phases. In the analysis of the chemical composition, vanadium was observed in small amount in all phases for each sample which contains vanadium. Vanadium tends to substitute Fe sites, which results in a decrease of the plateau pressures. The addition of vanadium as TiFe_0.8Mn_0.1V_x (x = 0.05 and 0.1) alloys has beneficial effects on the equilibrium plateaus of the hydrides: the plateaus become flatter and a significant reduction in the pressure hysteresis is observed.     

Ti2ZrNbV高熵合金的相稳定性和时效强化

采用真空电弧熔炼法制备了具有体心立方结构的Ti₂ZrNbV(at%)高熵合金。研究了固溶体相的稳定性,以及金属间化合物V₂Zr析出对拉伸性能的改善。结果表明：合金在900℃以上是稳定单一均质固溶体相,低于此温度时,Laves相V₂Zr容易在基体中析出。单一固溶相的不稳定性可用于强化Ti₂ZrNbV高熵合金。经过固溶和时效处理后,合金的拉伸屈服强度可达1145 MPa,塑性伸长率为8.3%。     

Pulverization mechanism of the multiphase Ti–V-based hydrogen storage electrode alloy during charge/discharge cycling

Pulverization is an important key factor for the electrochemical cycle stability of many hydrogen storage alloys. In this paper, the pulverization mechanism of the multiphase Ti–V-based hydrogen storage alloy which mainly consists of a V-based solid solution phase with the BCC structure and a C14 Laves phase is studied based on a sample material of the Ti_0.8Zr_0.2V_2.7Mn_0.5Cr_0.6Ni_1.25Fe_0.2 alloy. The microstructure of the alloy and the morphology change of the alloy electrode during the charge/discharge process were observed by transmission electron microscope, scanning electron microscope and atomic force microscope, etc. The effect of mechanical properties of the V-based phase and the C14 Laves phase on the pulverization behavior of the Ti–V-based alloy is discussed. The results show that microcracks initially occur at the phase boundary of the V-based phase and the C14 Laves phase and then extend to the C14 Laves phase in the charge/discharge process. The phase boundary is composed of a Ti segregated amorphous layer with a thickness of about 90 nm, mismatching with the crystallized V-base phase and C14 Laves phase. The toughness of the C14 Laves phase is much lower and the hardness is higher than that of the V-based phase. The weak bonding strength of the phase boundary, the lower toughness of the C14 Laves phase and the large volume expansion/contraction of the C14 Laves phase during charge/discharge cycling are the main factors that cause the pulverization of the Ti–V-based alloy.     

Investigation of hydrogen absorption/desorption properties of ZrMn0.85−xFe1+x alloys

The crystal structures and hydrogen absorption/desorption properties of the ZrMn_0.85−xFe_1+x alloys (x = 0, 0.2, 0.4) were investigated systematically. The pressure–composition (PC) isotherms and absorption kinetics were measured at 273–333 K by the volumetric method. Besides the crystal structure, the plateau pressure and the hydrogen intake capacity, this article also discussed the absorption kinetics, the pulverization resistance and the thermodynamic properties. XRD patterns revealed that ZrMn_0.85Fe and ZrMn_0.65Fe_1.2 were formed as hexagonal C14 laves phase structure while ZrMn_0.45Fe_1.4 possessed cubic C15 laves phase structure. With the increase of Fe and decrease of Mn, the plateau pressure increased while the hydrogen intake capacity lowered and the hydrogen absorption kinetics degraded. On the other hand, the hysteresis alleviated, the pulverization resistance improved and the stability of the hydrides decreased. The decomposition pressure was increased to more than 160 times for ZrMn_0.85Fe and more than 2500 times for ZrMn_0.65Fe_1.2 compared with that of the ZrMn₂ alloy.     

Effect of rapid solidification on the structural and electrochemical properties of the Ti–V-based hydrogen storage electrode alloy

The structural and electrochemical properties of the as-cast and rapidly solidified Ti_0.8Zr_0.2V_2.4Mn_0.48Cr_0.72Ni_0.9 alloys were studied. Both the as-cast and the rapidly solidified alloys were mainly composed of a C14 Laves phase matrix with hexagonal structure and a V-based solid solution phase with body centered cubic (BCC) structure. The V-based solid solution phase showed very fine dendrites in the rapidly solidified alloy instead of the large dendrites as observed in the as-cast alloy. In addition, the content of the C14 Laves phase in the alloy decreased greatly after rapid solidification. Electrochemical measurements indicated that the rapidly solidified alloy had a lower discharge capacity, a slower activation rate, a worse high rate dischargeability, a smaller exchange current density and limiting current density, but an improved cycle life compared with that of the as-cast alloy.     

Structural and hyperfine properties of Ti48Zr7Fe18 nano-compounds and its hydrides

It is well established that Ti-based nano-alloys are able to absorb hydrogen with relatively high hydrogen to metal ratio of 4/3. In this study the Ti₄₈Zr₇Fe₁₈ nano-compound, prepared by mechanical alloying (MA), has been investigated. In its initial state the compound is amorphous, however upon thermal treatment it transforms to the quasicrystalline icosahedral structure (i-phase), which is based on the Mackay cluster type. Structural characterization of the sample was made by means of XRD measurements. Thermodynamic properties were studied by differential scanning calorimetry (DSC) and thermal desorption spectroscopy (TDS). To find the influence of hydrogen and structure type on hyperfine interactions the Mössbauer spectroscopy (MS) experiment was performed, as well. The amorphous sample after MA was hydrogenated in order to unveil hydrogen influence on crystal properties of the sample. Upon hydrogenation of the amorphous sample a decomposition into simple hydrides took place.     

加工对吸氢La0.6Pr0.4Fe11.4Si1.6B0.2合金磁热稳定性的影响研究

采用工业原料和感应熔炼法制备出La0.6Pr0.4Fe11.4Si1.6B0.2板锭,通过高温短时退火获得NaZn13型主相合金,进行氢化处理并研究了合金颗粒尺寸对吸氢处理后La0.6Pr0.4Fe11.4Si1.6B0.2氢化物磁热性能的影响。外形尺寸3-5 cm的大尺寸样品在吸氢后出现严重粉化,呈层片状剥离的破碎状态,但心部仍保持完整块状。外形尺寸小于1 cm的小尺寸样品吸氢后形状保持完好。La0.6Pr0.4Fe11.4Si1.6B0.2合金存在吸氢粉化临界尺寸。采用外形尺寸小于1 cm的样品吸氢能够防止合金氢化粉化现象发生,有利于铸造样品直接吸氢获得一定尺寸和几何形状的块状La0.6Pr0.4Fe11.4Si1.6B0.2Hx样品。     

Investigation of the Y2Te3–Cu2Te–PbTe system at 870 K and crystal structures of the Y7Cu3Te12 and YCu0.264Te2 compounds

The structural and magnetic properties of doubly substituted Nd₂Fe_17−x−yTi_xGa_y (0 ≤ x ≤ 1.0, 0 ≤ y ≤ 3) compounds have been investigated by a combined technique of X-ray diffraction, neutron diffraction and magnetic measurements. Rietveld refinements of the diffraction data indicate that all the samples crystallize in the rhombohedral Th₂Zn₁₇-type structure. For a given Ti content (x), the lattice parameters a and c, and unit cell volume V of Nd₂Fe_17−x−yTi_xGa_y all increase linearly with increasing Ga content. The addition of Ti initially has a considerably positive effect on the increasing rates of a, c, and unit cell volume V, but later the effect becomes very slight and even negative with the further increase of Ti content. The site occupancies of Ti and Ga in the crystallographic sites change a little compared to what is observed in the corresponding singly substituted compounds. The effects of Ti and Ga on the bond lengths of the doubly substituted compounds are quite different from that of the singly substituted compounds. Magnetic measurements show the T_C of Nd₂Fe_17−x−yTi_xGa_y increases with increasing Ti content for a low Ga content while it behaves conversely for a higher Ga content. The T_C of Nd₂Fe_17−x−yTi_xGa_y increases with increasing Ga content for a particular Ti content, while the addition of Ti results in a slower increase of T_C on the Ga content (y ≤ 3). For a given Ti content, the M_s of Nd₂Fe_17−x−yTi_xGa_y first increases a little and then decreases with the increase of Ga content, while for a given Ga content the M_s of Nd₂Fe_17−x−yTi_xGa_y decreases with the increase of Ti content.     

Improvement of the hydrogen storage properties and electrochemical characteristics of Ti0.85VFe0.15 alloy by Ce substitution

The effect of Ce substitution for Ti on the microstructure, hydrogen absorption characteristics and electrochemical properties of Ti_0.85−xCe_xVFe_0.15 (x = 0, 0.02 and 0.05) is studied in detail. In the Ti-V-Fe series, the composition Ti_0.85VFe_0.15 which crystallizes in single phase BCC structure shows the highest hydrogen storage capacity of 3.7 wt%. In the present study, the effect of Ce addition (2 and 5 at%) on the hydrogen absorption properties of Ti_0.85VFe_0.15 has been investigated by X-ray diffraction, electron probe microanalysis (EPMA) and pressure-composition isotherm studies. The hydrogen absorption capacity is found to be higher for the Ce substituted alloys. The alloys Ti_0.85VFe_0.15, Ti_0.83Ce_0.02VFe_0.15 and Ti_0.80Ce_0.05VFe_0.15 show maximum hydrogen storage capacities of 3.7, 4.02 and 3.92 wt%, respectively. Kinetic studies show that the hydrogen absorption is quite fast for all the three alloys and they reach near saturation value in about 120 s. Electrochemical studies of the Ce (2 at%) substituted alloy, Ti_0.83Ce_0.02VFe_0.15 show higher electrocatalytic activity for the hydrogen electrode reactions as compared to Ce-free parent compound, Ti_0.85VFe_0.15.     

Hydrophilicity and photocatalysis of Ti1−xVxO2 films prepared by sol-gel method

Ti_1−xV_xO₂ films were prepared by sol-gel dip-coating method. To study the effects of vanadium incorporation on the self-cleaning properties of TiO₂ film, the crystallization behavior and surface morphology of Ti_1−xV_xO₂ films were investigated by an X-ray diffraction (XRD) analysis and an Atomic force microscope (AFM) respectively. The band-gap E_g of Ti_1−xV_xO₂ was determined by optical transmission spectra. Hydrophilicity and photocatalysis of Ti_1−xV_xO₂ films were characterized. The results showed that Ti_1−xV_xO₂ films had super-hydrophilicity and greater photocatalysis under day light illumination when x = 0.1-0.2. An optimal photocatalytic activity was obtained when x = 0.15. Moreover, Ti_0.85V_0.15O₂ films were proven to have excellent photocatalysis and hydrophilicity in visible region simultaneously, which made the application of Ti_0.85V_0.15O₂ film as self-cleaning and anti-fogging material practical under everyday condition.     

Synthesis of Ti3SiC2 bulks by infiltration method

T₃SiC₂ bulks have been synthesized by infiltrating Si liquid into porous precursor pellets composed of solid TiC and Ti powders. Silicon pellets were placed at the bottom of the precursor pellets as the liquid source. The starting compositions can be represented by the formula 2TiC + Ti + xSi, where x = 1.0, 1.2, 1.5 and 1.8, respectively. The phase formation and microstructure of the bulks were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with energy-dispersive spectroscopy (EDS) system. The results demonstrated that the TiC/Ti precursor pellet could only react with Si completely when the x value is 1.8. Impurities SiC, Ti-Si binary compounds and Ti₈C₅ appeared along the silicon diffusion direction. It is found that the compositions of impurities strongly depended on the Si-concentration. Reaction mechanism of this Ti₃SiC₂ infiltration synthesis has also been discussed based on the Si-concentration changes on the diffusion path.     

Combustion synthesis of Ti3Si1−xAlxC2 solid solutions from TiC-, SiC-, and Al4C3-containing powder compacts

Preparation of the Ti₃Si_1−xAl_xC₂ solid solution with x = 0.2-0.8 was investigated by self-propagating high-temperature synthesis (SHS) using TiC-, SiC-, and Al₄C₃-containing powder compacts. Due to the variation of reaction exothermicity with sample stoichiometry, the combustion temperature and reaction front velocity decreased with increasing Al content of Ti₃Si_1−xAl_xC₂ for the TiC- and Al₄C₃-added samples, but increased for the samples with SiC. In contrast to the formation of Ti₃(Si,Al)C₂ as the dominant phase for the TiC- and SiC-added samples, TiC was identified as the major constituent in the final products of samples adopting Al₄C₃. In addition, the evolution of Ti₃(Si,Al)C₂ was improved by increasing the Al content of the TiC- and SiC-added powder compacts, but deteriorated considerably upon the increase of Al₄C₃ in the Al₄C₃-containing sample.     

Effects of TiC and Al4C3 addition on combustion synthesis of Ti2AlC

Preparation of the ternary carbide Ti₂AlC was conducted by combustion synthesis in the mode of self-propagating high-temperature synthesis (SHS) from the elemental powder compacts of Ti:Al:C = 2:1:1, TiC-containing samples with TiC of 6.67–14.3 mol%, and Al₄C₃-containing samples with Al₄C₃ of 1.96–10 mol%. Effects of TiC and Al₄C₃ addition were studied on combustion characteristics and the degree of phase conversion. Due to the growth of laminated Ti₂AlC grains, the reactant compact was subjected to an axial elongation during the SHS process. Because the addition of TiC and Al₄C₃ led to a decrease in the reaction temperature, the flame-front propagation velocity was correspondingly reduced for the TiC- and Al₄C₃-containing samples when compared with the elemental reactants. Based upon the XRD analysis, formation of Ti₂AlC along with a secondary phase TiC was identified in the synthesized products. The grains of Ti₂AlC are typically plate-like with a size of 10–20 μm and several laminated Ti₂AlC grains form a layered structure. The content of Ti₂AlC yielded from the elemental powder compacts is about 85 wt%. The addition of TiC was found to facilitate the formation mechanism and therefore to enhance the extent of Ti₂AlC conversion approaching 90 wt%. As a result of the reduced exothermicity of the reaction, however, the content of Ti₂AlC decreased slightly in the products synthesized from the Al₄C₃-added samples.     

Dissociation of Ti2O3 from titania slag under mechanical activation

In this present study, the effects of mechanical activation on the characterization of titania slag were systematically investigated. The crystal structures, surface chemical functional groups, and microstructure of the samples were characterized before and after mechanical activation using XRD, FT-IR, and Raman spectroscopy techniques, respectively. It was found that untreated titania slag under mechanical activation was mainly composed of Fe₃Ti₃O₁₀ and rutile TiO₂, but that of being treated by mechanical activation was mainly composed of Fe₃Ti₃O₁₀, Ti₂O₃ and rutile TiO₂. Ti₂O₃ is transformed partially from Fe₃Ti₃O₁₀ under moderate mechanical activation conditions for 12 h. The demonstration of mechanical activation techniques can be applied effectively and efficiently to the treatment processing of titania slag.     

Application of tritium radioluminography to the detection of hydrogen diffusion in Ti-Cr alloy

Tritium radioluminography has been applied to determine the hydrogen (H) diffusion coefficients in Ti₅₀Cr₅₀ and Ti₄₀Cr₆₀ alloys, both with two-phase structures of a body-centered cubic (bcc) phase and a Laves phase. Using radioluminography, H distributions in those phases have been observed, and H penetration profiles have been measured. The tritium diffusion coefficients in the Ti₅₀Cr₅₀ and Ti₄₀Cr₆₀ alloys have been successfully determined by analyzing the tritium penetration profiles to be 3.3±0.3 × 10^?12 and 1.4±0.1×10^?12 m²/s, respectively. These values suggest that the H diffusion in the Laves phase is slower than that in the bcc phase. It is also suggested that H diffuses by short-circuiting diffusion through the interface between the bcc phase and the Laves phase.     

Effect of Ca on the microstructure and magnetocaloric effects in the La1−xCaxFe11.5Si1.5 compounds

The effect of Ca on the microstructure and magnetocaloric effects has been investigated in the La_1−xCa_xFe_11.5Si_1.5 (x = 0, 0.1, 0.2 and 0.3) compounds. The introduction of Ca leads to the appearance of minor α-Fe and Ca-rich phases, which affects the actual compositions of the main phases for the Ca containing samples. With increasing the Ca concentration, the Curie temperature T_C increases from 183 to 208 K, and the maximum magnetic entropy changes |ΔS| at the respective T_C with a magnetic field change from 0 to 5 T are 21.3, 19.5, 16.9, and 11.2 J/kg K for x = 0, 0.1, 0.2, and 0.3, respectively. The nature of the magnetic transition changes from first-order to second-order with an increase in Ca concentration, which leads to a reduction of the hysteresis and a decrease of the magnetic entropy change. However, the relative cooling power for La_1−xCa_xFe_11.5Si_1.5 compounds remains comparable with or even larger than that of other magnetocaloric materials over a wide temperature range. The higher T_C and the smaller hysteresis in comparison with those of the parent compound suggest that the La_1−xCa_xFe_11.5Si_1.5 compounds could be suitable candidates for magnetic refrigerants in the corresponding temperature range.     

Effect of microstructural orientation on in situ electrical resistance monitoring during S-HDDR processing of a Nd16Fe76B8 alloy

In situ electrical resistance monitoring during solid hydrogenation, disproportionation, desorption, and recombination (S-HDDR) processing of a Nd₁₆Fe₇₆B₈ alloy was carried out with the use of both longitudinal and transverse samples, with the as-cast columnar structure parallel and perpendicular to the current direction. Significant difference in the behaviour has been observed between these two kinds of samples in the first cycle of S-HDDR processing, especially during hydrogenation and disproportionation. These results have been interpreted in terms of the contribution of (1) the individual resistances of the constituent phases; (2) the particular distribution of the Nd-rich phase; (3) the factors related to hydrogen diffusion and hence to the reaction kinetics; (4) the formation of S-HDDR induced cavitation. During the second cycle of S-HDDR cycling, on the other hand, the behaviours of both samples were closely similar and this can be attributed to the formation of a non-oriented, more homogeneous, submicron microstructure and to the general re-distribution of the original Nd-rich phase after the first cycle of S-HDDR processing.     

Electromagnetic wave absorption properties of mechanically mixed Nd2Fe14B/C microparticles

Nd₂Fe₁₄B/C microparticles were prepared by a mechanical mixing technique using a weight ratio of 2:1. Paraffin-bonded Nd₂Fe₁₄B/C composites were fabricated using 40 wt% microparticles, and their electromagnetic wave absorption properties were studied and compared with those of the paraffin-bonded Nd₂Fe₁₄B composites in the 2-18 GHz frequency range and for 1-5 mm thickness. The Nd₂Fe₁₄B/C-paraffin composites exhibit dual dielectric resonance in complex relative permittivity (?_r) and essentially flat response in complex relative permeability (μ_r) rather than showing an abrupt change in both ?_r and μ_r as in the Nd₂Fe₁₄B-paraffin composites. The results are ascribed to the increased electrical resistivity in the Nd₂Fe₁₄B/C-paraffin composites and the protection on the magnetic properties of the Nd₂Fe₁₄B microparticles at 2-18 GHz by the presence of the C phase. Large reflection loss (RL) exceeding −10 dB and an optimal RL of −13.2 dB are achieved in the Nd₂Fe₁₄B/C-paraffin composites from 9.6 to 18 GHz at a thickness of 1.4-2.6 mm and at 18 GHz at a thickness of 1.4 mm, respectively.