Hydrogen storage behavior of nanocrystalline and amorphous La-Mg-Ni-based LaMg_(12)-type alloys synthesized by mechanical milling

Nanocrystalline and amorphous LaMg11Ni+x%Ni(x=100,200,mass fraction)alloys were synthesized by mechanicalmilling.The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system.The gaseous hydrogen absorption and desorption properties were investigated by Sievert’s apparatus and differential scanningcalorimeter(DSC)connected with a H2detector.The results indicated that increasing Ni content significantly improves the gaseousand electrochemical hydrogen storage performances of the as-milled alloys.The gaseous hydrogen absorption capacities andabsorption rates of the as-milled alloys have the maximum values with the variation of the milling time.But the hydrogen desorptionkinetics of the alloys always increases with the extending of milling time.In addition,the electrochemical discharge capacity andhigh rate discharge(HRD)ability of the as-milled alloys both increase first and then decrease with milling time prolonging.

Mechanical and wear properties of Al-Al_3Mg_2 nanocomposites prepared by mechanical milling and hot pressing

β-A13Mg2 intermetallic was used as a reinforcing agent to improve the mechanical properties of an aluminum matrix. Different amounts of A13Mg2 nanoparticles （ranging from 0wt% to 20wt%） were milled with aluminum powders in a planetary ball mill for 10 h. Consolidation was conducted by uniaxial pressing at 400β under a pressure of 600 MPa for 2 h. Microstructural characterization confirms the uniform distribution of A13Mg2 nanoparticles within the matrix. The effects of nano-sized A13Mg2 content on the wear and mechanical properties of the composites were also investigated. The results show that as the A13Mg2 content increases to higher levels, the hardness, compressive strength, and wear resistance of the nanocomposites increase significantly, whereas the relative density and ductility decrease. Scanning electron microscopy （SEM） analysis of worn surfaces reveals that a transition in wear mechanisms occurs from delamination to abrasive wear by the addition of A13Mg2 nanoparticles to the matrix.

Influence of chloride salts on hydrogen generation via hydrolysis of MgH_2 prepared by hydriding combustion synthesis and mechanical milling

The effects of chloride salts(NaCl,MgCl2and NH4Cl)on the hydrolysis kinetics of MgH2prepared by hydridingcombustion synthesis and mechanical milling(HCS+MM)were discussed.X-ray diffraction(XRD)analyses show that high-purityMgH2was successfully prepared by HCS.Hydrolysis performance test results indicate that the chloride salt added during the millingprocess is favorable to the initial reaction rate and hydrogen generation yield within60min.A MgH2?10%NH4Cl composite exhibitsthe best performance with the hydrogen generation yield of1311mL/g and a conversion rate of85.69%in60min at roomtemperature.It is suggested that the chloride salts not only play as grinding aids in the milling process,but also create fresh surface ofreactive materials,favoring the hydrolysis reaction.

Electrochemical Hydrogen Storage Performance of the Nanocrystalline and Amorphous Pr-Mg-Ni-based Alloys Synthesized by Mechanical Milling

The PrMg12-type composite alloy of PrMg_(11)Ni + x wt% Ni (x=100,200) with an amorphous and nanocrystalline microstructure were synthesized through the mechanical milling.Effects of milling duration and Ni content on the microstructures and electrochemical hydrogen storage performances of the ball-milled alloys were methodically studied.The ball-milled alloys obtain the optimum discharge capacities at the first cycle.Increasing Ni content dramatically enhances the electrochemical property of alloys.Milling time varying may obviously impact the electrochemical performance of these alloys.The discharge capacities show a significant upward trend with milling duration prolonging,but milling for a longer time more than 40 h induces a slight decrease in the discharge capacity of the x=200 alloy.As milling duration increases,the cycle stability clearly lowers,while it first declines and then augments under the same condition for the x=200 alloy.The high-rate discharge abilities of the ball-milled alloys show the optimum values with milling time varying.

Microstructure and Mechanical Property of 2024 Aluminium Alloy Prepared by Rapid Solidification and Mechanical Milling

Rapidly solidified 2024 aluminium alloy powders were mechanically milled, then consolidated to bulk form. The microstructural changes of the powders in mechanical milling (MM) and consolidation process were characterized by X-ray diffraction analyses and transmission electron microscopy observations. The results showed that mechanical milling reduced the grain size to nanometer, dissolved the Al2Cu intermetallic compound into the aluminium matrix and produced an aluminium supersaturated solid solution. During consolidation process. the grain size increased to submicrometer, and the Al2Cu and Al2(Cu, Mg, Si, Fe, Mn) compounds precipitated owing to heating. Increasing consolidation temperature and time results in obvious grain growth and coarsening of second phase particles. The tensile yield strength of the consolidated alloy with submicrometer size grains increases with decreasing grain size, and it follows the famous HallPetch relation

Characterization of MCrAlY/nano-Al_(2)O_(3) nanocomposite powder produced by high-energy mechanical milling as feedstock for high-velocity oxygen fuel spraying deposition

Al_(2)O_(3) nanoparticles and MCrAlY/nano-Al_(2)O_(3) nanocomposite powder(M=Ni,Co,or NiCo)were produced using high-energy ball milling.The MCrAlY/nano-Al_(2)O_(3) coating was deposited by selecting an optimum nanocomposite powder as feedstock for high-velocity oxy-gen fuel thermal spraying.The morphological and microstructural examinations of the Al_(2)O_(3) nanoparticles and the commercial MCrAlY and MCrAlY/nano-Al_(2)O_(3) nanocomposite powders were investigated using X-ray diffraction analysis,field-emission scanning electron microscopy coupled with electron dispersed spectroscopy,and transmission electron microscopy.The structural investigations and Williamson-Hall res-ults demonstrated that the ball-milled Al_(2)O_(3) powder after 48 h has the smallest crystallite size and the highest amount of lattice strain among the as-received and ball-milled Al_(2)O_(3) owing to its optimal nanocrystalline structure.In the case of developing MCrAlY/nano-Al_(2)O_(3) nanocompos-ite powder,the particle size of the nanocomposite powders decreased with increasing mechanical-milling duration of the powder mixture.

Structural characterization of AA 2024-MoSi_2 nanocomposite powders produced by mechanical milling

Nano-sized MoSi2 powder was produced successfully from commercially available MoSi2 by a mechanical milling process carried out for 100 h, and mechanical alloying was employed to synthesize AA 2024-MoSi2 nanocomposites, The effects of MoSi2 reinforcement and mechanical milling on the structure, morphology, and iron contamination of the produced materials were investigated using X-ray diffraction, scanning electron microscopy, and atomic absorption spectrometry. It is revealed that the morphology of the aluminum alloy changes continuously during milling from spherical to plate-like, irregular, and finally equiaxed. The presence of MoSi2 reinforcement accelerates the milling process and results in a smaller average particle size. The Williamson-Hall method determined that the crystallite size of the aluminum alloy in the composite powder is smaller than that of the unreinforced alloy at the same milling time and this size reaches 45 nm after 16 h milling time. The Fe contamination content is higher for the nanocomposite in comparison with the unreinforced alloy because of the wearing role of MoSi2 hard particles.

Gaseous hydrogen storage thermodynamics and kinetics of RE-Mg-Ni-based alloys prepared by mechanical milling

Nanocrystalline/amorphous La Mg11Ni+x Ni(x=100%, 200%, mass fraction) composite hydrogen storage alloys were synthesized by ball milling technology. The effects of Ni content and milling time on the gaseous hydrogen storage thermodynamics and dynamics of the alloys were systematically investigated. The hydrogen desorption properties were studied by Sievert's apparatus and a differential scanning calorimeter(DSC) connected with a H2 detector. The thermodynamic parameters(ΔH and ΔS) for the hydrogen absorption and desorption of the alloys were calculated by Van't Hoff equation. The hydrogen desorption activation energy of the alloy hydride was estimated using Arrhenius and Kissinger methods. The results indicate that a variation in the Ni content has a slight effect on the thermodynamic properties of the alloys, but it significantly improves their absorption and desorption kinetics performances. Furthermore, varying milling time clearly affects the hydrogen storage properties of the alloys. All the as-milled alloys show so fast hydrogen absorption rate that the absorbed amount in 10 min reaches to at least more than 95% of the saturated hydrogen absorption capacity. Moreover, the improvement of the gaseous hydrogen storage kinetics of the alloys is found to be ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and prolong milling time.

Influence of Mechanical Milling on Photocatalytic Activity of g-C_3N_4 Prepared by Heating Melamine

Using X-ray diffraction,transmission electron microscopy,Brunauer-Emmett-Teller surface area measurement,ultraviolet-visible diffuse reflection spectra,and photoluminescence spectroscopy,the effect of mechanical milling on the photocatalytic activity of g-C3N4 photocatalyst was investigated.The rhodamine B,as a photodegrading goal,was used to evaluate the photocatalytic activity of g-C3N4.The experimental results indicate that the milling treatment is an effective method to improve the photocatalytic activity of g-C3N4.The enhanced photocatalytic activity was attributed to the improvement in catalyst＇s surface area and dye adsorption on catalyst surface.Moreover,checking the luminescence properties of g-C3N4,it is found that the photocatalytic active sites on g-C3N4 are likely the same as luminescence sites.

Effects of the deep rolling process on the surface roughness and properties of an Al-3vol%SiC nanoparticle nanocomposite fabricated by mechanical milling and hot extrusion

Deep rolling is one of the most widely used surface mechanical treatments among several methods used to generate compressive residual stress. This process is usually used for axisymmetric components and can lead to improvements of the surface quality, dimensional accuracy, and mechanical properties. In this study, we deduced the appropriate deep rolling parameters for Al-3vol%Si C nanocomposite samples using roughness and microhardness measurements. The nanocomposite samples were fabricated using a combination of mechanical milling, cold pressing, and hot extrusion techniques. Density measurements indicated acceptable densification of the samples, with no porosity. The results of tensile tests showed that the samples are sufficiently strong for the deep rolling process and also indicated near 50% improvement of tensile strength after incorporating Si C nanoparticle reinforcements. The effects of some important rolling parameters, including the penetration depth, rotation speed, feed rate, and the number of passes, on the surface quality and microhardness were also investigated. The results demonstrated that decreasing the feed rate and increasing the number of passes can lead to greater surface hardness and lower surface roughness.

An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg12-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg_（12）-type LaMg_（11）Ni ＋ x wt% Ni（x = 100, 200） alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter（DSC） connected with a H_2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability（HRD） and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.

Sintering kinetics of Ni_2FeSb powder alloys produced by mechanical milling

A ternary Ni2FeSb shape memory alloy was fabricated by powder metallurgy route. Sintering kinetics was estimated from dilatometry tests; whereas the microstructure and morphology of the powder and consolidated bulk samples were evaluated by XRD and SEM, respectively. Microhardness tests were performed on the surface of sintered samples. The results indicated that milling time has an effect on the shape and particle size as well as the homogeneity of the crystalline structures of the powders. Samples with longer milling time presented higher relative densities, better distribution of the elements on the alloy as well as the L21 and martensite phases, which will give the shape memory effect. The estimated activation energy values ranged from 109 to 282 kJ/mol at temperatures between 750 and 1273 K, indicating that sintering is controlled mainly by volume diffusion. Microhardness was improved by increasing the milling time and the heating rate.

Preparation of Ce(SO_4)_2-doped Phosphosilicate Gels by Mechanical Milling

Ce（SO4） 2-doped phosphosilicate gel was prepared by mechanical milling.Complex impedance analysis proved that the 15 h-ball-milled sample showed a maximum conductivity of 2.97 S/m at 130 °C,which is about 40% higher than that of the sol-gel-prepared sample with the same compositions.NMR results proved that the ball-milled samples contained more Q1 structural units helpful to an increase in both proton conduction and chemical durability.

Study of Reactions Induced by Mechanical Milling in ZnO-α-Fe_2O_3 System

Spinel ferrite ZnFe 2O 4 powders were synthesized directly from ZnO and α Fe 2O 3 mixtures by high energy mechanical milling. X ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM) were used to investigate the chemical reaction processing at different milling time. It has been found that the solid reactions between metal oxides are characterized by stages. Once the solid chemical synthesized reaction is initialized, it proceeds quickly and can be completed in very short time. Grain sizes of ZnFe 2O 4 are less than 10 nm.

Structural Evolution of Fullerene during Mechanical Milling

Mechanical milling of fullerene (C60(C70)) was investigated to understand the structural evolu-tion. Mechanical milling could not destroy the molecular structure of C60(C70), while the longrange periodicity of the fCc crystalline structure was easiIy damaged. Longer miIIing time couldresult in the formation of C60(C70) polymer, including C60 dimer.

Synthesis of Tantalum Hydride Using Mechanical Milling and Its Characterization by XRD,SEM,and TGA

In this paper, we report the results obtained from different phases of metal hydrides. The synthesis and characterization of tantalum hydrides were obtained “in situ” during mechanical milling. Elemental Ta with purity of 99.8% was used in this investigation to obtain the hydrides. A highenergy ball milling technique was utilized to prepare hydrogenated phases. Ta hydrides and oxides were formed as function of milling process time. Milling times of 5, 10 and 20 hours were programmed, and the ball-to-powder weight ratio was 10:1. The material was first characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Before and after hydrogenation process the material was also analyzed by TGA. X-ray diffraction analysis demonstrated that only tantalum hydrides (Ta2H and TaH0.5) were obtained after 20 h of milling. We will discuss the effect of the ball-milling process about formation “in situ” of nanometric tantalum hydrides with methanol as a hydrogen source.

Effect of process parameter on the flowability of nanocrystalline CoNiCrAlY powder synthesized by mechanical milling

The present study concerns understanding the effect of process parameters on the characteristics and flowability of nanocrystalline CoNiCrAlY powder synthesized by mechanical milling.Mechanical milling has been conducted in a planetary ball mill with tungsten carbide(WC)ball,with ball to powder ratio of 10:1 at 300 rpm speed,using 1%stearic acid and toluene as process control agent(PCA)with time varying from 10 h to 36 h.The synthesized nanocrystalline powder were characterized by Scanning Electron Microscopy,X-ray Diffraction technique,X-ray Photoelectron Spectroscopy,and Differential Scanning Calorimetry.Subsequently,flowability in terms of Hausner ratio was assessed by Tap Density Tester.Average particle size of the powder was found to decrease from 33μm to 22μm after 10 h of milling and further increases to 43μm and 38μm after 25 and 36 h of milling,respectively,in stearic acid medium.However,in toluene medium particle size continuously decreases from 33μm to 9.7μm with increasing milling time.The particle morphology changes from spherical to platelet shape at low milling hours in both of the media.After 25 h of milling,the shape of the particles is nearly spherical for stearic acid and irregular for toluene used as a PCA.Crystallize size was found to decrease with increasing milling time from 147 nm to 7.7 nm and to 6.4 nm in stearic acid and toluene media,respectively.There was presence ofγ,γʹ,β,hcp-Co,Al_(2)O_(3)and AlOOH phases on the powder particles milled in both the medium.The measured Hausner ratio of the powders was found to vary from 1.18 to 1.32 in stearic acid medium,and was found to increase with increasing milling time.On the other hand,in toluene media flowability decreases(Hausner ratio increases from 1.33 to 1.44)with increasing milling time.

Hydrogen storage thermodynamics and dynamics of La-Mg-Ni-based LaMg12-type alloys synthesized by mechanical milling

Nanocrystalline/amorphous LaMg(12)-type alloyNi composites with a nominal composition of LaMg(11)Ni+x wt% Ni(x=100,200) were synthesized by mechanical milling.Effects of Ni content and milling time on the gaseous hydrogen storage thermodynamics and dynamics of alloys were systematically investigated.The hydrogen desorption properties were studied by Sievert apparatus and a differential scanning calorimeter(DSC).Thermodynamic parameters(△H and ΔS) for the hydrogen absorption and desorption of alloys were calculated by Van't Hoff equation.Hydrogen desorption activation energy of alloy hydride was estimated by Arrhenius and Kissinger methods.The increase in Ni content has a slight effect on the thermodynamic properties of alloys,but it significantly enhances the hydrogen absorption and desorption kinetics performance of alloys.Moreover,variation of milling time clearly affects the hydrogen storage properties of alloys.Hydrogen absorption capacity(C(100)~a) and hydrogen absorption saturation ratio(R(10)~a)(a ratio of the hydrogen absorption capacity at 10 min to the saturated hydrogen absorption capacity) have maximum values with milling time varying.But hydrogen desorption ratio(R(20)~d)(a ratio of the hydrogen desorption capacity at 20 min to the saturated hydrogen absorption capacity) always increases with milling time prolonging.Particularly,prolonging milling time from 5 to 60 h makes R(20)~d increase from 10.89% to 16.36% for the x=100 alloy and from 13.93% to 21.68% for the x=200 alloy,respectively.

Structure and electrochemical hydrogen storage characteristics of Ce-Mg-Ni-based alloys synthesized by mechanical milling

The substituting Mg with Ni and milling as-cast alloy with Ni were adopted to obtain nanocrystalline/amorphous CeMgnNi＋x wt.%Ni（x=100,200） alloys and promote the electrochemical hydrogen storage performances of CeMg_（12）-type alloys.Analyzing the structural features of the alloys provided a mechanism for ameliorating the electrochemical hydrogen storage properties.The electrochemical tests demonstrated that all the alloys just needed one cycle to be activated.Rising Ni proportion had an obvious role on charge-discharge reaction.The discharge capacities of the as-milled（60 h） alloys increased sharply from 182.0 mAh/gfor x=100 alloy to 1010.2 mAh/gfor x=200 alloy at current density of 60 mAh/g.Furthermore,milling time largely determined the performances of electrochemical reaction.The discharge capacity continued to grow along with prolonging milling time,while the cycle stability obviously decreased for x=100 alloy,and first declined and then augmented for the x=200 alloy with milling time extending.In addition,there was an optimal value with milling time varying for the high rate discharge abilities（HRD）,which was 80.3%for x=100 alloys and 86.73%for x=200,respectively.

Hydriding/dehydriding behaviors of La_2Mg_(17)-10 wt.%Ni composite prepared by mechanical milling

The structure and hydriding/dehydriding behaviors ofLa2Mgl7-10 wt.%Ni composite prepared by mechanical milling were investigated. Compared with the tin-milled sample, the as-milled alloys were ready to be activated and the kinetics of hydrogen ab- sorption was relatively fast even at environmental temperature. The composite milled for 10 h absorbed 3.16 wt.% hydrogen within 100 s at 290 K. The kinetic mechanisms ofhydriding/dehydriding reactions were analyzed by using a new model. The results showed that hydrogenation processes for all composites were controlled by hydrogen diffusion and the minimum activation energy was 15.3 kJ/mol H2 for the composite milled for 10 h. Mechanical milling changed the dehydriding reaction rate-controlling step from surface penetration to diffusion and reduced the activation energy from 204.6 to 87.4 kJ/mol H2. The optimum milled duration was 5 h for desorption in our trials.