Hydrogen storage properties of (Ti0.85Zr0.15)1.05Mn1.2Cr0.6V0.1M0.1 (M=Ni, Fe, Cu) alloys easily activated at room temperature

The(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)M_(0.1)(M=Ni, Fe, Cu) alloys with a single C14-type Laves phase have been fabricated by arc melting. They are able to be easily activated by one hydrogen absorption and desorption cycle under 4 MPa hydrogen pressure and vacuum at room temperature. Partial substitution of M for Mn results in the increase of hydrogenation and dehydrogenation capacities in an order of Ni Fe Cu. M elements increase the absorption and desorption plateau pressure in an order of(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Fe_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Ni_(0.1). The(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1) alloy has reversible hydrogen capacities of 1.81 wt% at 273 K and 1.58 wt% at 318 K with formation enthalpy(ΔH_(ab)) of-20.66 kJ mol~(-1) and decomposition enthalpy(ΔH_(de)) of 27.37 kJ mol~(-1). The differences in the hydrogen storage properties can be attributed to the increase of the interstitial size for hydrogen accommodation caused by the increase of unit cell volumes in the order of(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Ni_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Fe_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1).     

Hydrogen absorption-desorption characteristic of (Ti0.85Zr0.15)1.1Cr1-xMoxMn based alloys with C14 Laves phase

The microstructure and hydrogen absorption-desorption characteristic of (Ti_0.85Zr_0.15)_1.1Cr_1-xMo_xMn (x ?= ?0.05, 0.1, 0.15, 0.2 ?at.%) alloys were investigated. The results showed that the corresponding alloys were determined as a single phase of C14-type Laves structure. With the increase of Mo content, the maximum and reversible hydrogen absorption capacity decreased, the slope factor H_f increased. Among the studied alloys, (Ti_0.85Zr_0.15)_1.1Cr_0.95Mo_0.05Mn had the best overall properties for practical application of hydrogen storage materials. The maximum and reversible hydrogen storage capacity were 1.76 ?wt% and 1.09 ?wt%, the slope factor H_f was 0.51, and its dissociation enthalpy (ΔH_d) and entropy change (ΔS_d) were 23.1 ?kJ ?mol^?1H₂, 93.8J ?K^?1mol^?1H₂ at 303K, respectively. By studying the dissociation pressures of the synthesized metal hydrides, it was found that Mo had a special effect on the dissociation pressure of Ti–Zr–Cr–Mo–Mn alloys. Among the four alloys, (Ti_0.85Zr_0.15)_1.1Cr_0.95Mo_0.05Mn alloy had the largest hydrogen absorption capacity and the fastest hydrogen desorption rate, which can meet the commercialization demand of hydrogen fuel cell hydrogen supply system.     

Reversible hydrogenation of AB2-type Zr–Mg–Ni–V based hydrogen storage alloys

The development of hydrogen energy is hindered by the lack of high-efficiency hydrogen storage materials. To explore new high-capacity hydrogen storage alloys, reversible hydrogen storage in AB₂-type alloy is realized by using A or B-side elemental substitution. The substitution of small atomic-radius element Zr and Mg on A-side of YNi₂ and partial substitution of large atomic-radius element V on B-side of YNi₂ alloy was investigated in this study. The obtained ZrMgNi₄, ZrMgNi₃V, and ZrMgNi₂V₂ alloys remained single Laves phase structure at as-annealed, hydrogenated and dehydrogenated states, indicating that the hydrogen-induced amorphization and disproportionation was eliminated. From ZrMgNi₄ to ZrMgNi₂V₂ with the increase of the degree of vanadium substitution, the reversible hydrogen storage capacity increased from 0.6 ?wt% (0.35H/M) to 1.8 ?wt% (1.0H/M), meanwhile the lattice stability gradually increased. The ZrMgNi₂V₂ alloy could absorb 1.8 ?wt% hydrogen in about 2 ?h ?at 300 ?K under 4 ?MPa H₂ pressure and reversibly desorb the absorbed hydrogen in approximately 30 ?min ?at 473 ?K without complicated activation process. The prominent properties of ZrMgNi₂V₂ elucidate its high potential for hydrogen storage application.     

Ti – Cu– Zr–Fe– Nb ultrafine structur e-dendrite composites with good mechanical properties and biocompat ibility

Ti-Cu-Zr-Fe-Nb ultrafine structure-dendrite composites were designed by inducing Nb and more Ti to a Ti-Cu-Zr-Fe glass-forming alloy composition and prepared by copper mold casting.The composite alloys consist of β-Ti dendrites and ultrafine-structured CuTi₂ and CuTi phases as well as a trace amount of glassy phase.The volume fraction of β-Ti dendrites increases with the increase in content of Nb which acted as the β-Ti phase stabilizer in the alloys.The composites exhibit high compressive yield strength exceeding1200 MPa,maximum strength around 1800 MPa and low Young’s modulus around 48 GPa.The plasticity of the alloys is strongly influenced by the volume fraction and morphology of the dendritic β-Ti phase,and the compressive plastic strain was enlarged from 5.9%for the 4 at%Nb alloy to 9.2%for the 8 at%Nb alloy.The preliminary cell culture experiment indicated good biocompatibility of the composite alloys free from highly toxic elements Ni and Be.These Ti-based composite alloys are promising to have potential structural and biomedical applications due to the combination of good mechanical properties and biocompatibility.     

Improvement on hydrogen generation properties of Zr(BH_4)_4·8NH_3

Hydrolysis of Zr(BH_4)_4·8NH_3 in deionized water can generate high purity hydrogen at room temperature.However, the sluggish hydrolysis kinetics of Zr(BH_4)_4·8NH_3 hinders its practical use. To improve its hydrogen generation properties, the effects of magnetic stirring, changing hydrolysis solution and tuning the ammonia coordination number on the hydrolysis properties of Zr(BH_4)_4·8NH_3 were investigated. Results show that both changing hydrolysis solution and tuning the ammonia coordination number can enhance the hydrolysis kinetics.The hydrolysis kinetics properties of Zr(BH_4)_4·8NH_3 were significantly improved in MgCl_2 and CoCl_2 solutions.The Zr(BH_4)_4·8NH_3(x ≤ 8) samples were synthesized by a ball-milling method with different ammonization time(10, 60 and 180 min). Both the hydrolysis kinetics and hydrogen yield of Zr(BH_4)_4·8NH_3(x ≤ 8) were enhanced as the ammonia coordination number(x) decreased. Thus, tuning ammonia coordination number is an effective way to control the hydrolysis properties of Zr(BH_4)_4·8NH_3(x ≤ 8).     

Minor-alloyed Cu-Ni-Si alloys with high hardness and electric conductivity designed by a cluster formula approach

Cu-Ni-Si alloys are widely used due to their good electrical conductivities in combination with high strength and hardness. In the present work, minor-alloying with M =(Cr, Fe, Mo, Zr) was conducted for the objective of further improving their hardness while maintaining their conductivity level. A cluster-plus-glue-atom model was introduced to design the compositions of M-alloyed Cu-Ni-Si alloys, in which an ideal composition formula[(Ni,Si,M)-Cu_(12)]Cu_3(molar proportion) was proposed. To guarantee the complete precipitation of solute elements in fine δ-Ni_2 Si precipitates, the atomic ratio of(Ni,M)/Si was set as 2/1. Thus the designed alloy series of Cu_(93.75)(Ni/Zr)_(3.75)Si_(2.08)(Cr/Fe/Mo)_(0.42)(at%) were arc-melted into ingots under argon atmosphere, and solidsolutioned at 950 ℃ for 1 h plus water quenching and then aged at 450 ℃ for different hours. The experimental results showed that these designed alloys exhibit high hardness(HV 1.7 GPa) and good electrical conductivities(≥ 35% IACS). Specifically, the quinary Cu_(93.75)Ni_(3.54)Si_(2.08)(Cr/Fe)_(0.42)Zr_(0.21) alloys(Cu-3.32 Ni-0.93 Si-0.37(Cr/Fe)-0.30 Zr wt%) possess both a high hardness with HV = 2.5-2.7 GPa, comparable to the highstrength KLFA85 alloy(Cu-3.2 Ni-0.7 Si-1.1 Zn wt%,HV= 2.548 GPa),and a good electrical conductivity(35-36% IACS).     

Formation and properties of high Fe-content Fe-(B-Si)-Zr bulk amorphous alloys

The present work is devoted to the development of Fe-(B-Si)-Zr amorphous alloys with high glass-forming ability and good magnetic properties. Using the cluster-plus-glue-atom model proposed for ideal amorphous structures, [FeFe₁₁B₃Si](Fe_1?xZr_x) was determined as the cluster formula of Fe-(B-Si)-Zr alloys. The glass formation and thermal stability of the serial alloys, namely, [FeFe₁₁B₃Si](Fe_1?xZr_x) (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.75, and 1.0), were studied by the combination of copper mold casting, X-ray diffraction, and differential thermal analysis techniques. The maxima of glass-forming ability and thermal stability were found to occur at the compositions of [FeFe₁₁B₃Si](Fe_0.6Zr_0.4) and [FeFe₁₁B₃Si](Fe_0.5Zr_0.5). The alloys can be cast into amorphous rods with 1.5 mm diameter, and upon reheating, the amorphous alloys exhibit a large undercooled liquid span of 37 K. The saturation magnetization of the [FeFe₁₁B₃Si](Fe_0.5Zr_0.5) amorphous alloy was measured to be 1.4 T.     

Hydrogen storage performance of LaNi3.95Al0.75Co0.3 alloy with different preparation methods

Rare-earth AB₅-type La–Ni–Al hydrogen storage alloys are widely studied due to their extensive application potentials in hydrogen isotope storage, hydrogen isotope isolation and hydrogen compressors, etc. Good hydriding/dehydriding kinetics, easily activation, high reversibility are important factors for their practical application. However, their overall hydrogen storage performance, especially plateau pressure and hydrogen absorption/desorption durability need to be further optimized. In this study, the microstructures and the hydrogen storage properties of as-cast, annealed, and melt-spun LaNi_3.95Al_0.75Co_0.3 alloys were investigated. The experimental results of XRD and SEM showed that all alloys contained a pure CaCu₅ type hexagonal structure LaNi₄Al phase. The cell volume increased in an order of annealed ?> ?melt-spun ?> ?as-cast, resulting in a lower hydrogen absorption/desorption plateau pressure and a more stable hydride phase. The hydrogen storage capacity of three alloys was almost the same. The slope factor of the annealed and melt-spun alloys is smaller than the as-cast alloy, indicating that heat-treatment process can make the alloys more uniform. For the cycle stability of the alloys, the hydrogen absorption rate of the annealed alloy and melt-spun alloy was much faster than that of the as-cast alloy after 500 cycles. The melt-spun alloy showed high pulverization resistance during hydrogen absorption/desorption, and exhibited an excellent cycling retention of 99% after 500 cycles, suggesting that melt-spinning process can enhance the cycle stability and improve the cycle life of the alloy.     

Eutectic reaction and cored dendritic morphology in yttrium doped Zr-based amorphous alloys

The microalloying effect of yttrium on the crystallization behaviors of (Zr_0.525Al_0.10Ti_0.05Cu_0.179Ni_0.146)_100-x Y_x, and (Zr_0.55Al_0.15-Ni_0.10Cu_0.20)_100-x Y_x (x=0, 0.4, and 1, thus the two alloy systems were denoted as Zr52.5, Zr52.5Y0.4, Zr52.5Y1, and Zr55, Zr55Y0.4, Zr55Y1, respectively) was studied. Transmission electron microscopy (TEM) results suggested that the crystalline phases were different in the two Zr-based alloys and with different yttrium contents. ZrNi-phase and Al₃Zr₅ phase precipitations can be well explained by the mechanisms of nucleation and growth. Al₃Zr₅ phase is mainly formed by a peritectic-like reaction, while ZrNi-phase by a eutectic reaction. The contents of elements Y, Al, and Ti may dominate the reaction types. The orientation relationship between Y₂O₃ particles and Al₃Zr₅ phase is also discussed.     

Effect of Zr addition on the stability of precipitated Laves phase and mechanical properties of Fe–Cr–Al-based alloys at high temperatures

The effect of a small amount of Zr addition on the temperature-dependent stability of Laves phase particles and mechanical properties of Fe-13.5Cr-4.73Al-2.07Mo-(0.34–0.5)Nb-(0.65–0.98)Ta-(0–0.33)Zr (wt. %) ferritic alloys was investigated in the present study. The designed alloy ingots were hot-rolled, aged at 1073 ?K for 24 ?h, and then re-treated at 1273 ?K, 1323 ?K, 1373 ?K, and 1473 ?K for 1 ?h, respectively. It was found that the Zr addition could not only stabilize the Fe₂M Laves phase (M ?= ?Mo,Nb,Ta,Zr) to a much higher temperature, but also induce the formation of stable Fe₂₃Zr₆ phase. The high-temperature (HT) microstructural stability of the alloys significantly was improved, as evidenced by the fact that a certain amount (0.66–1.19%) of precipitates (Fe₂M, Fe₂₃Zr₆, and core(Fe₂₃Zr₆)-shell(Fe₂M)-structured particles) with an appropriate size (～1.0 ?μm) uniformly distributed in the ferritic matrix even after being re-treated at 1473 ?K. Particularly, the formation of core-shell-structured particles at HTs was studied from the viewpoint of both solid solubility and diffusion coefficient of M in the matrix. All these aged alloys exhibited prominent mechanical properties at both room and elevated temperatures, showing high yield strength with σ_YS ?= ?490–560 ?MPa at room-temperature and σ_YS ?= ?80–85 ?MPa at 1073 ?K. The strengthening effect was further discussed in light of various strengthening mechanisms, and the calculated strength are in good agreement with the experimental results.     

Centimeter-sized Ti-based bulk metallic glass with high specific strength

Based on the quaternary Ti₄₁Zr₂₅Be₂₉Al₅ glassy alloy with a critical diameter of 7 mm reported not long ago, an obvious enhancement of glass-forming ability (GFA) has been realized in this alloy by the addition of Cu element. A series of (Ti₄₁Zr₂₅Be₂₉Al₅)_100?xCu_x (x=0, 2, 5, 7, 9, 11 at%) glassy alloys have been developed and some of them can be cast into one-centimeter diameter fully glassy rods by copper mold suction casting. It has been found that Cu addition could stabilize the liquid phase and suppress the crystallization, resulting in improvement of the GFA of the alloy. The addition of Cu also increases the compressive strength of the alloy and the (Ti₄₁Zr₂₅Be₂₉Al₅)₉₁Cu₉ glassy alloy possesses a specific strength (defined as yield strength/density) of 4.13×10⁵ Nm/kg, which is much higher than most other reported centimeter-sized bulk metallic glasses. The present result suggests that the newly developed (Ti₄₁Zr₂₅Be₂₉Al₅)₉₁Cu₉ glassy alloy is a good candidate for structural applications because of its good glass-forming ability and mechanical properties.     

Hydrogen absorption properties of amorphous (Ni0.6Nb0.4−yTay)100−xZrx membranes

Ni based amorphous materials have great potential as hydrogen purification membranes. In the present work the melt spun(Ni_(0.6)Nb_(0.4-y)Ta_y)_(100-x)Zr_x with y=0, 0.1 and x=20, 30 was studied. The result of X-ray diffraction spectra of the ribbons showed an amorphous nature of the alloys. Heating these ribbons below T 400 °C, even in a hydrogen atmosphere(1-10 bar), the amorphous structure was retained. The crystallization process was characterized by differential thermal analysis and the activation energy of such process was obtained. The hydrogen absorption properties of the samples in their amorphous state were studied by the volumetric method,and the results showed that the addition of Ta did not significantly influence the absorption properties, a clear change of the hydrogen solubility was observed with the variation of the Zr content. The values of the hydrogenation enthalpy changed from ~37 k J/mol for x=30 to ~9 k J/mol for x=20. The analysis of the volumetric data provides the indications about the hydrogen occupation sites during hydrogenation, suggesting that at the beginning of the absorption process the deepest energy levels are occupied, while only shallower energy levels are available at higher hydrogen content, with the available interstitial sites forming a continuum of energy levels.     

A Ti–Zr–Cu–Ni–Co–Fe–Al–Sn amorphous filler metal for improving the strength of Ti–6Al–4V alloy brazing joint

Ti_(50)Zr_(27)Cu_8Ni_4Co_3Fe_2Al_3Sn_3(at%) amorphous filler metal with low Cu and Ni contents in a melt-spun ribbon form was developed for improving mechanical properties of Ti–6Al–4V alloy brazing joint through decreasing brittle intermetallics in the braze zone. Investigation on the crystallization behavior of the multicomponent Ti–Zr–Cu–Ni–Co–Fe–Al–Sn amorphous alloy indicates the high stability of the supercooled liquid against crystallization that favors the formation of amorphous structure. The Ti–6Al–4V joint brazed with this Ti-based amorphous filler metal with low total content of Cu and Ni at 1203K for 900s mainly consists of α-Ti, β-Ti,minor Ti–Zr-rich phase and only a small amount of Ti_3Cu intermetallics, leading to the high shear strength of the joint of about 460 MPa. Multicomponent composition design of amorphous alloys is an effective way of tailoring filler metals for improving the joint strength.     

Co80+xZr20-x合金的永磁性能

利用X射线衍射和磁性测量研究Co_80+xZr_20-x（x=0,1,2,3,4）合金、 快淬薄带的结构与磁性. 结果表明, 所有样品的比饱和磁化强度均较大, 且在实验范围内随退火温度的升高而增加; 经750℃热处理2 h后, Co₈₁Zr₁₉样品的比饱和磁化强度达到最大值128 (A·m2)/kg; Co₈₂Zr₁₈快淬样品在25 m/s速率下的矫顽力最大, 为60 kA/m, 根据该样品中Co5Zr相的含量较大可知, Co₅Zr相为Co-Zr合金的硬磁相; 由初始磁化曲线可知, 所有样品的矫顽力机制为成核模型.      

Microstructure evolution and phase transformation of traditional cast and spray-formed hypereutectic aluminium-silicon alloys induced by heat treatment

Microstructural evolution and phase transformation induced by different heat treatments of the hypereutectic aluminium-silicon alloy, Al-25Si-5Fe-3Cu (wt%, signed as 3C), fabricated by traditional cast (TC) and spray forming (SF) processes, were investigated by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) combined with energy dispersive X-ray spectroscopy and X-ray diffraction techniques. The results show that Al₇Cu₂Fe phase can be formed and transformed in TC- and SF-3C alloys between 802–813 K and 800–815 K, respectively. The transformation from β-Al₅FeSi to δ-Al₄FeSi₂ phase via peritectic reaction can occur at around 858–870 K and 876–890 K in TC- and SF-3C alloys, respectively. The starting precipitation temperature of δ-Al₄FeSi₂ phase as the dominant Fe-bearing phase in the TC-3C alloy is 997 K and the exothermic peak about the peritectic transformation of δ-Al₄FeSi₂→β-Al₅FeSi is not detected in the present DSC experiments. Also, the mechanisms of the microstructural evolution and phase transformation are discussed.     

Study on the hydrogen storage property of (TiZr0.1)xCr1.7-yFeyMn0.3 (1.05

Jigang Li  Li Xu  Xiaojing Jiang  Xingguo Li 《自然科学进展(英文版)》2018,28(4):470-477

Composition design of superhigh strength maraging stainless steels using a cluster model

The composition characteristics of maraging stainless steels were studied in the present work investigation using a cluster-plus-glue-atom model. The least solubility limit of high-temperature austenite to form martensite in basic Fe–Ni–Cr corresponds to the cluster formula [NiFe12]Cr3,where NiFe12is a cuboctahedron centered by Ni and surrounded by 12 Fe atoms in FCC structure and Cr serves as glue atoms. A cluster formula [NiFe12](Cr2Ni) with surplus Ni was then determined to ensure the second phase(Ni3M) precipitation,based on which new multicomponent alloys [(Ni,Cu)16Fe192](Cr32(Ni,Mo,Ti,Nb,Al,V)16) were designed. These alloys were prepared by copper mould suction casting method,then solid-solution treated at 1273 K for 1 h followed by water-quenching,and finally aged at 783 K for 3 h. The experimental results showed that the multi-element alloying results in Ni3M precipitation on the martensite,which enhances the strengths of alloys sharply after ageing treatment. Among them,the aged [(Cu4Ni12)Fe192](Cr32(Ni8.5Mo2Ti2Nb0.5Al1V1)) alloy(Fe74.91Ni8.82Cr11.62Mo1.34Ti0.67Nb0.32Al0.19V0.36Cu1.78wt%) has higher tensile strengths with YS?1456 MPa and UTS?1494 MPa. It also exhibits good corrosion-resistance in 3.5 wt% NaCl solution.     

α′ Type Ti– Nb– Zr alloys with ultra-low Young's modulus and high strength

a’ phase based Ti-Nb-Zr alloys with low Young’s modulus and high strength were prepared,and their microstructure and mechanical properties were characterized.It was revealed that the lattice expansion by Nb and Zr addition as well as the presence of a few of a" martensite might be responsible for the low modulus achieved.Ti-15Nb-9Zr alloy,with ultralow modulus of 39 GPa and high strength of850 MPa,could be a potential candidate for biomedical applications.     

热处理对Fe_(40)Co_(40)Zr_7V_2B_9Ta_2合金微观结构及磁性能的影响

采用单辊快淬法制备Fe40Co40Zr7V2B9Ta2非晶合金薄带,并对该合金在不同温度下进行热处理.利用差热分析(DTA)、X射线衍射(XRD)、扫描电镜(SEM)和振动样品磁强计(VSM)测量合金的热性能、微观结构及磁性能.结果表明:Fe40Co40Zr7V2B9Ta2合金的初始晶化产物为α-FeCo相,高温时析出ZrCo3B2,Co23Zr6和ZrB2相;薄带横断面的形貌在快淬态和300℃退火后,合金的自由面呈网状结构,贴辊面呈枝状结构;高于550℃退火,横断面呈颗粒状;550℃退火后合金的矫顽力(Hc)最小,高于550℃退火,Hc随退火温度的升高而增大.     

Microstructure evolution and mechanical properties of Ti_2AlNb/TiAl brazed joint using newly-developed Ti–Ni–Nb–Zr filler alloy

Joining of Ti_2AlNb alloy to TiAl intermetallics was conducted by the newly-developed Ti–Ni–Nb–Zr brazing filler alloy.The microstructure evolution of the joints was investigated by scanning electron microscope (SEM),energy dispersive spectrometer (EDS) and electron backscatter diffraction (EBSD).The macro-micro mechanical properties were studied by shear test and nano-indentation test.Typical interfacial microstructures across the brazing seam were Ti_2AlNb substrate,α_2-Ti_3Al+β-Ti,γ-TiAl+Ti_2Ni+TiNi+α_2-Ti_3Al,α_2-Ti_3Al+β-Ti,TiAl substrate.The Ti_2Ni phase were firstly dissolved in the joints brazed at 1000°C for 10 min and then precipitated after a prolonged holding time of 15 min.The nano-indentation test revealed that Ti_2Ni phase exhibited the highest hardness of 12.60 GPa.The joints brazed at 1000°C/15 min presented the maximum shear strength of271 MPa.The dissolution and precipitation behavior of Ti_2Ni phase was also discussed.