Hydrogen Absorption Thermodynamic Properties of Rare Earth Based Hydrogen Storage Alloy in Benzene

The hydriding/dehydriding thermodynamic properties of the slurry system formed by suspending La rich mischmetal nickel hydrogen storage alloy (MlNi 5) in Benzene (C 6H 6) were investigated. The pressure composition isotherms for both the alloy powder and the slurry suspended with MlNi 5 were measured at several temperatures(10, 20, 30, 40 ℃). The standard enthalpy of formation Δ H ° and standard entropy of formation Δ S ° for the alloy powder with and without benzene were determined respectively. The experimental results show that the values of Δ H ° and Δ S ° for the hydriding reaction of hydrogen storage alloy (MlNi 5) of the slurry system and the gas solid system are all very close.

Kinetics of the hydrogen absorption and desorption processes of hydrogen storage alloys: A review

High hydrogen absorption and desorption rates are two significant index parameters for the applications of hydrogen storage tanks.The analysis of the hydrogen absorption and desorption behavior using the isothermal kinetic models is an efficient way to investigate the kinetic mechanism.Multitudinous kinetic models have been developed to describe the kinetic process.However,these kinetic models were de-duced based on some assumptions and only appropriate for specific kinetic measurement methods and rate-controlling steps(RCSs),which sometimes lead to confusion during application.The kinetic analysis procedures using these kinetic models,as well as the key kinetic parameters,are unclear for many researchers who are unfamiliar with this field.These problems will prevent the kinetic models and their analysis methods from revealing the kinetic mechanism of hydrogen storage alloys.Thus,this review mainly focuses on the summarization of kinetic models based on different kinetic measurement methods and RCSs for the chemisorption,surface penetration,diffusion of hydrogen,nucleation and growth,and chemical reaction processes.The analysis procedures of kinetic experimental data are expounded,as well as the effects of temperature,hydrogen pressure,and particle radius.The applications of the kinetic models for different hydrogen storage alloys are also introduced.

Structure of Liquid Aluminum and Hydrogen Absorption

The hydrogen content in aluminum melts at different temperature was detected. The structure in aluminum melts was investigated by molecular dynamics simulation. The first peak position of pair correlation function, atomic coordination number and viscosity of aluminum melts were calculated and they changed abnormally in the same temperature range. The mechanism of hydrogen absorption has been discussed. From molecular dynamics calculations, the interdependence between melt structural properties and hydrogen absorption were obtained.

Hydrogen absorption of NdDyFeCoNbCuB sintered magnets

Hydrogen absorption and desorption characteristics for high coercivity NdDyFeCoNbCuB sintered bulk magnets were studied, by differential scanning calorimetry （DSC） measurement and hydrogenation kinetics measurement. The DSC measurements showed that hydrogenation of Nd-rich phase occurred in the temperature range of 40-185 ℃, hydrogenation of the tetragonal （Ф） phase in the temperature range of 185-220 ℃, as well as the disproportionation of the Ф phase that occurred in a broad temperature range from around 500 to 800 ℃. The hydrogenation kinetics measurements indicated that hydrogen absorption of the bulk magnets at 50 ℃ absorbed more hydrogen than at 150 ℃, although this procedure was slower at 50 ℃ than at 150℃. This phenomenon was discussed by means of pressure-concentration-temperature （p-c-T） diagrams.

HYDROGEN ABSORPTION OF FeTi+x wt-% La ALLOYS WITH ALTERNATE LAYER STRUCTURE

Superior hydrogen absorbability of the alloys fo FeTi-La with alternate layer structure was found firstly.It would be available at 30℃ under 6 MPaH_2 without any prior treatment.

Hydrogen absorption of LaFe_(11.5)Si_(1.5) compound under low hydrogen gas pressure

Hydrogen absorptions of LaFe11.sSi1.5 compound in 1-atm hydrogen gas at different temperatures are investigated. The hydrogen content in the hydrogenated sample does not increase with the increase of temperature of hydrogen absorption but changes complicatedly. The characteristic of first-order transition in LaFe11.sSil.5 compound is weakened after hydrogen absorption. It leads the peaks of magnetic entropy to become wider and the hysteresis loss to reduce significantly, but relative cooling power （RCP） is not changed considerably.

THIN FILM PREPARATION OF AMORPHOUS Ti-Ni ALLOY AND THEIR HYDROGEN ABSORPTION PROPERTIES

Amorphous Ti_(0.88)Ni_(1.00) and Ti_(1.69)Ni_(1.00) alloy films are prepared by means of ion beam sputtering using TiNi and Ti_2Ni alloy targets, respectively. Their hydrogen absorption properties are investigated by a galvanostatic method. The results show th the discharge capacity of the Ti_(1.69)Ni_(1.00) sample is higher than that of the Ti_(0.88)Ni_(1.00) sample. And the film electrodes have high durability and long cycle life.

ELECTROCHEMICAL PROPERTIES OF THE HYDROGEN ABSORPTION OF AMORPHOUS Ml－Ni ALLOY FILMS

The amorphous Ml-Ni films were prepared by means of ion beam sputtering the electrochemical hydrogen storage,discharge ability and durability of amorphous film electrodes are investigated,The results show that the maximum capacities of the amorphous MlNi_(1.79),MlNi_(2.52),and MlNi_(3.44) samples are 90,100 and 142 mAh/g,respectively,and the MlNi_(3.44) amorphous film does not off and disintegrate into fine particles a fier more than 580 cycles.

Microstructure and Hydrogen Absorption/Desorption Behavior of Mg23-xLaxNi10 Alloy

Induction melting was used as a routine method to synthesize Mg_（23）Ni_（10）, Mg_（22）LaNi_（10） and Mg_（21）La_2Ni_（10） alloys, and followed by a detailed microstructural characterization which included X-ray diffraction（XRD）, scanning electron microscopy（SEM） with energy dispersive spectrometer（EDS）, high resolution transmission electron microscope（HRTEM） and hydrogen absorption/desorption measurements. XRD analysis results showed that Mg_2Ni and Mg phases were detected in the XRD pattern of the Mg_（23）Ni_（10） alloy, however, the La addition results in conversion from Mg to LaMg_3 and La_2Mg_（17） phases and appearance of crystal defects included dislocations, twin grain boundary and vacancy in the Mg_（22）LaNi_（10） and Mg_（21）La_2Ni_（10） alloy textures. The total maximum hydrogen absorption capacity was 4.45 wt% for the Mg_（23）Ni_（10） alloy, however, the Mg_（22）LaNi_（10） and Mg_（21）La_2Ni_（10） alloys with vacancy, dislocations and twin grain boundary, absorbed 3.66 wt% and 3.60 wt%, respectively, indicating that the La addition led to decreasing of the maximum hydrogen absorption capacity. Besides, hydrogen absorption/desorption of 90% of saturated state expended for about 456 and 990 s for pristine Mg_（23）Ni_（10） alloy, by contrast, the time decreased owing to improvement of hydrogen absorption and desorption kinetics in the alloy with La element, with which the uptake time for hydrogen content to 90% of saturated state was 150 and 78 s, and 90% hydrogen can be released in 930 and 804 s for Mg_（22）LaNi_（10） and Mg_（21）La_2Ni_（10） alloys in the experimental condition.

Study on Hydrogen Storage Properties,Anti-Oxide Ability and Rate Limiting Step of ZrCr-Based Alloy after Introducing Cobalt as Additive

In this work,the microstructure,hydrogen storage properties,anti-oxide ability and rate limiting step of Zr(Cr_(1−x)Co_(x))_(2)(x=0,0.2,0.4 and 0.6)alloys have been investigated.After studying the crystal structure,we found that all alloy samples could show C14-type phase but the alloy sample x=0 could also show a small amount of Cr phase.Rietveld fitting showed that lattice parameter and unit cell volume of C14-type phase decreased with increasing x.After further research,it was clear that the first hydrogen absorption capacity decreased with increasing x.But introducing more Co content had a positive influence on the effective hydrogen storage capacity and cyclic hydrogen absorption and desorption properties of the alloy sample.We also found that adding Co to ZrCr_(2)alloy could improve its anti-oxide ability.In addition to this,the rate limiting step model was also studied.

Magnetic entropy change and magnetic properties of LaFe_(11.5)Si_(1.5) after controlling the Curie temperature by partial substitution of Mn and hydrogenation

Magnetic properties and magnetic entropy changes of La（Fe_（1-x）Mn_x）_（11.5）Si_（1.5）H_y compounds are investigated. Their Curie temperatures are adjusted to room temperature by partial Mn substitution for Fe and hydrogen absorption in 1-atm（1 atm = 1.01325×10~5Pa） hydrogen gas. Under a field change from 0 T to 2 T, the maximum magnetic entropy change for La（Fe_（0.99）Mn_（0.01））_（11.5）Si_（1.5）H_（1.61）is-11.5 J/kg. The suitable Curie temperature and large value of ？S_m make it an attractive potential candidate for the room temperature magnetic refrigeration application.

Boundary Element Method (BEM) Analysis for Galvanic Corrosion of Hot Dip Galvanized Steel Immersed in Seawater

A numerical analysis of galvanic corrosion of hot-dip galvanized steel immersed in seawater was presented. The analysis was based on the boundary element methods （BEMs） coupled with Newton-Raphson iterative technique to treat the nonlinear boundary conditions, which were determined by the experimental polarization curves. Results showed that galvanic current density concentrates on the boundary of steel substrate and zinc coating, and the sacrificial protection of zinc coating to steel substrate results in overprotection of steel cathode. Not only oxygen reduction but also hydrogen reduction could occur as cathode reactions, which probably led up to the adsorption and absorption of hydrogen atoms. Flat galvanized steel tensile sample shows a brittle behavior similar to hydrogen embrittlement according to the SSRT （show strain rate test） in seawater.

Hydrogen Absorption and Desorption during Heat Treatment of AISI 4140 Steel

Hydrogen plays an important role in the formation of quench cracks of structural steels. To clarify hydrogen ab- sorption and desorption during heat treatment of AISI 4140 steel, thermal desorption spectrometry （TDS） analysis was carried out for the specimens in the as-rolled, as quenched, and quenched and tempered conditions. Results show that hydrogen content increased from 0. 127 ×10 6 in the as-rolled specimen to 0. 316 × 10-6 in the as-oil-quenched specimen. After tempering at 200 ℃, the hydrogen content in the oil-quenched specimen decreased to 0. 155 × 10-6 , and the peak temperature of hydrogen desorption increased from 200 to 360 ℃. From the dependence of hydrogen content in the as-quenched specimens on austenitizing time, it can be deduced that hydrogen absorption occurs during austenitizing. The simulation of hydrogen absorption contributes to a better understanding on the distribution of hy- drogen during the heat treatment in structural steels.

Thermodynamics of hydrogen absorption and desorption in TC21 alloy

In this paper,it was addressed a hydrogen absorbing and desorbing thermodynamics inα+βtype TC21 titanium alloy with high strength and toughness based on thermodynamic experiments and calculation.The relationship between concentration(C),temperature(T),and pressure(P)of TC21 alloy is shown by P-C-T curves during hydrogen absorption and desorption process,which were measured by multistep hydrogenation/dehydrogenation methods from 625 to 750℃.The P-C-T isotherms at a given temperature were separated into three regions.The partial thermodynamic functions of hydrogen reaction were evaluated by a modified form of Sievert’s law and P-CoTrelation of different regions was expressed by the modified Sievert’s law.The results show that the enthalpy of hydrogen reaction in the first and third region relies on hydrogen content.According to Vant’s Hoff law,enthalpy and entropy of hydrogenation platform in TC21 alloys are-53.58 kJ·mol^(-1)and-127.41 J·K·mol^(-1),respectively.Compared with P-C-T curves of hydrogen absorption,that of hydrogen desorption exists hysteresis.

Flow hydrogen absorption of LaFe_(10.9)Co_(0.8)Si_(1.3) compound under constant low hydrogen gas pressure

The hydrogen absorption of the LaFe（10.9）-Co（0.8）Si（1.3） compound under constant 1.01 × 10-5 Pa H2 gas in a flow hydrogen atmosphere was studied. The effects of hydrogen absorption on structure, Curie temperature, phase transition and magnetic property were investigated by X-ray diffraction（XRD）, differential scanning calorimeter（DSC） and superconducting quantum interference device,respectively. The hydrides of LaFe（10.9）Co（0.8）Si（1.3） crystallize into NaZn（13）-type structural phase after hydrogen absorption at temperature from 548 to 623 K. Lower hydrogen absorption temperature is of no advantage for pure 1：13 phase formation in a flow H2 atmosphere. The Curie temperature（TC） of LaFe（10.9）Co（0.8）Si（1.3） compound increases by70 K or more after hydrogen absorption. For LaFe（10.9）-Co（0.8）Si（1.3）H（1.8） compound, the maximum magnetic entropy change and the relative cooling power under a magnetic field change of 0-2 T are 6.1 J·kg^-1·K^-1 and 170 J·kg^-1,respectively. Large refrigerant capacity, low hysteresis loss and wide temperature span of magnetic entropy change peak make it a competitive practical candidate for magnetic refrigerant.

Polymeric Iodoplumbate Incorporating Copper Iodide Complex Cation Layer:Structure and Theoretical Study of a New Semi-conductive Hybrid:{[Cu(Ⅱ)(bipy)_2I][PbI_3](H_2O)_2}_n

A new iodoplumbate polymer incorporating copper iodide complex cation {[Cu（Ⅱ）（bipy）2I][PbI3]（H2O）2}n 1（bipy = 2,2＇-bipyridine） has been synthesized and structurally determined.It crystallizes in the triclinic system,space group P1 with a = 7.979（4）,b = 14.538（11）,c = 15.853（8）,α = 110.77（2）,β = 97.955（18）,γ = 104.88（2）°,V = 1607.3（17）3,Z = 2,C20H16CuI4N4O2Pb,Mr = 1122.72,Dc = 2.320 g/cm3,F（000） = 1006,μ（MoKα） = 9.753,the final R = 0.0627 and wR = 0.1741 for 4846 observed reflections with Ⅰ 〉 2σ（Ⅰ）.Structural analysis indicates that 1 consists of 2-D {[Cu（Ⅱ）（bipy）2I]}nn＋ cation layers（based on π-π interaction and hydrogen bonds） and [PbI3]nn-polyanions.The C-H···I hydrogen bonds between {[Cu（Ⅱ）（bipy）2I]}nn＋ cation layers and [PbI3]nn-polyanions lead to the formation of an interesting 3-D network.Optical absorp-tion spectrum indicates that 1 is a semiconductor,which is further validated by DFT calculation.Its electronic structure is also discussed.

Impact of severe plastic deformation on kinetics and thermodynamics of hydrogen storage in magnesium and its alloys

Magnesium and its alloys are the most investigated materials for solid-state hydrogen storage in the form of metal hydrides,but there are still unresolved problems with the kinetics and thermodynamics of hydrogenation and dehydrogenation of this group of materials.Severe plastic deformation(SPD)methods,such as equal-channel angular pressing(ECAP),high-pressure torsion(HPT),intensive rolling,and fast forging,have been widely used to enhance the activation,air resistance,and hydrogenation/dehydrogenation kinetics of Mg-based hydrogen storage materials by introducing ultrafine/nanoscale grains and crystal lattice defects.These severely deformed materials,particularly in the presence of alloying additives or second-phase nanoparticles,can show not only fast hydrogen absorption/desorption kinetics but also good cycling stability.It was shown that some materials that are apparently inert to hydrogen can absorb hydrogen after SPD processing.Moreover,the SPD methods were effectively used for hydrogen binding-energy engineering and synthesizing new magnesium alloys with low thermodynamic stability for reversible low/room-temperature hydrogen storage,such as nanoglasses,high-entropy alloys,and metastable phases including the high-pressureγ-MgH2 polymorph.This work reviews recent advances in the development of Mg-based hydrogen storage materials by SPD processing and discusses their potential in future applications.

mproved Hydrogen Storage Properties of Ti_(23)V_(40)Mn_(37)Alloy Doped with Zr_(7)Ni_(10) by Rapid Solidification

As-cast and rapidly solidified Ti_(23)V_(40)Mn_(37)alloy doped with Zr_(7)Ni_(10) was synthesized by arc melting and melt-spinning.The microstructure,activation property,hydrogen absorption kinetics,and hydrogen absorption/desorption thermodynamics were investigated to evaluate a comprehensive hydrogen storage property of the alloys.Both preparation methods had a negligible effect on the lattice parameter of BCC and C14 Laves phases in the alloys.The alloy prepared by melt-spinning showed an increased proportion of BCC phase,larger hydrogen absorption capacity,faster hydrogen absorption rate,and higher hydrogen absorption/desorption platform pressure.The dehydriding enthalpy and endothermic peak temperature of the rapidly solidified alloy were 33.55±2.14 KJ/mol H_(2)and 526.2 K,respectively,which are smaller than those of the as-cast alloy.It indicates the decreased hydride stability and improved hydrogen desorption property.By contrast with the as-cast alloy,the rapidly solidified alloy showed a preferable comprehensive hydrogen storage property.

Hydrogenation behaviors and characteristics of bulk Ti-6Al-4V alloy at different isothermal temperatures

The bulk Ti-6Al-4V alloy was hydrogenated at the temperature range of 723-973 K,and the hydrogen absorption characteristics and hydrogen absorption kinetics were investigated.The results show that there are two types of hydrogen absorption characteristics at different temperatures.The hydrogen content decreases,and the time reaching reaction equilibrium is shorten with the isothermal hydrogenation temperature increasing.Meanwhile,the mechanism of the hydrogen absorption kinetics is different at different temperatures.The incubation period exists at the initial hydrogen absorption stage below 823 K,and K(a2)(the reaction rate constant of Stage 2)>>K(a1)(the reaction rate constant of Stage 1).And there is no incubation period over 823 K,K(a1)>>K(a2).

Effect of Preparation Technique on Microstructure and Hydrogen Storage Properties of LaNi(3.8)Al(1.0)Mn(0.2) Alloys

La Ni3.8Al1.0Mn0.2 alloy was prepared by vacuum induction melting and melt-spinning.The effects of different preparation techniques of the as-cast,cast then annealed,as-spun and spun then annealed alloys on the microstructure and hydrogen storage properties were investigated.The results indicated that the non-Ca Cu5 phases in the alloy became tinier and more dispersive after annealing or melt-spinning compared to those of the as-cast one.But in the spun then annealed alloy,the non-Ca Cu5 phases disappeared and only a single-phase with Ca Cu5 type structure was found.For all the alloys,the cell volume was increased in an order of as-cast 〈 spun then annealed 〈 cast then annealed 〈 as-spun,and the change of plateau pressure showed the opposite trend with that of the cell volume.The plateau could be flattened after melt-spinning or annealing,and the spun then annealed alloy showed the minimum plateau slope.The absorption kinetics of the alloy was promoted after melt-spinning or annealing.It is suggested that the change in cell volume and compositional homogeneity resulting from different preparation techniques contribute to the difference of the hydrogen storage properties of the investigated alloys.