Effect of heat treatment on hydrogen storage properties and thermal stability of V68Ti20Cr12 alloy

Effect of heat treatment on the crystal structure, microstructure, hydrogen storage properties and thermal stability of V68Ti20Cr12 alloy prepared by arc-melting was studied in this work. It was found that both the as-cast and annealed (973 K/72 h) V68Ti20Cr12 alloys consisted of a single body-centered cubic (bcc) phase. After heat treatment, the hydrogen absorption/desorption kinetic characteristics of the as-cast alloy was improved greatly due to the homogeneous composition and perfect structure. The mechanism of hydrogen absorption/desorption process in the as-cast and annealed alloys was further investigated according to the Johnson-Mehl-Avrami (JMA) equation. The hydrogen absorption process of the as-cast and annealed alloys would be controlled by the one-dimensional diffusion process, while the hydrogen desorption process in the as-cast and annealed alloys was dominated by the geometrical contraction model. The pressure-composition-temperature (PCT) measurements show that the plateau pressure of the annealed alloy becomes comparatively flat. Furthermore, the activation energies of the dehydrogenation in the as-cast and annealed alloys were calculated using the Kissinger method, indicating that heat treatment is a very beneficial way to improve hydrogen absorption/desorption kinetics of the alloy.     

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.     

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

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.     

Microstructural characterization and hydrogenation performance of Zr_xV_5Fe(x=3-9) alloys

Zr_xV_5 Fe(x=3,5,7,8,9) alloys were designed to investigate the influence of Zr addition on hydrogenation performance.The alloys were prepared by arc melting and then annealed at 1273 K for 168 h.The results showed that the alloys were composed of α-Zr and C15-ZrV2 phases.The cell volume of C15-ZrV_2 phase firstly increased and then decreased as the content of Zr increased,while the reversed trend was found for the cell volume of α-Zr phase,which was related to the stoichiometric ratio of elements.α-Zr phase distributed in C15-ZrV2 phase matrix in Zr_xV_5 Fe(x=5,7,8,9) alloys,among which Zr7 V5 Fe alloy showed the best distribution.The PCT curves of the alloys under 623 K,673 K and 723 K showed that the hydrogen absorption plateau pressure of the phases in different alloys decreased gradually with the increasing content of Zr.However C15-ZrV2 phase in Zr7 V5 Fe alloy had the lowest hydrogen absorption plateau pressure at room temperature,which was consistent with the change tendency of the corresponding cell volume.Moreover,the kinetic curves of hydrogen absorption at 623 K revealed that Zr7 V5 Fe alloy with the smallest average particle size and the largest phase boundary area showed the fastest hydrogen absorption kinetics.Compared with other four alloys(including St707 alloy),Zr_7 V_5 Fe alloy is more suitable for the use of getter.     

快淬Mg2Ni型合金的结构及贮氢动力学

用快淬技术制备Mg2-xLaxNi(x=0,0.2,0.4,0.6)贮氢合金,用XRD,SEM和HRTEM分析合金的微观组织结构;测试合金的气态及电化学贮氢动力学。结果表明:快淬二元Mg2Ni合金具有典型的纳米晶结构,而快淬La替代合金明显地具有非晶结构,La替代Mg提高Mg2Ni型合金的非晶形成能力。La替代Mg明显地改变Mg2Ni型合金的相组成,当x=0.4时,合金的主相改变为(La,Mg)Ni3+LaMg3。快淬及La替代明显影响合金的气态及电化学贮氢动力学,La替代使合金的吸氢动力学先降低后增加,但使合金的气态脱氢及电化学贮氢动力学先增加后降低。快淬对合金气态及电化学贮氢动力学的影响与合金的成分相关,对于La0.4合金,合金的气态吸氢动力学随淬速的增加先增加后减小,其放氢动力学随淬速的增加而增加。     

Phase evolution process and hydrogen storage performances of V72Ti18Cr10 alloy prepared by Co-precipitation-reduction method

The V₇₂Ti₁₈Cr₁₀ alloy was prepared by a co-precipitation-reduction method in order to consume less energy during whole-life alloy manufacturing, and the phase evolution process in hydrogenation/dehydrogenation process was investigated. The structure refinement analysis of the alloy contented with 1 ?wt% hydrogen after hydrogenation shows that BCC phase, BCC-hydride phase and FCC phase coexisted, but little BCT phase was found. It indicates that the phase evolution process during hydrogenation was BCC→ BCC-hydride→ FCC, nevertheless the formation of BCT phase was restrained. The limited particle sizes of the alloy in the range of 0.1–5 ?μm and fewer defects than the normal alloy ingot contributed to the suppression of BCT formation. The annealed alloy, which had similar particle sizes with the unannealed alloy, has less unevenness of the compositions than the unannealed alloy, and the annealed alloy showed flatter plateau in the hydrogenation PCT (pressure-composition-temperature) curves. However, the BCT phase in the annealed alloy appeared in its dehydrogenation process owing to the produced defects during the following dehydrogenation and the hydrogenation process. The alloy with the limited particle sizes even in the range from 0.1 ?μm to 5 ?μm could not prevent the generation of BCT phase in the dehydrogenation process.     

TiFe基储氢合金的BaZrO3坩埚熔炼制备及其储氢性能

利用自制25 kg 级BaZrO3坩埚,通过ZG-0．05型真空感应熔炼制备 TiFe 基储氢合金。熔炼条件为：0．6 MPa氩气保护气氛,精炼时间5～10 min,精炼温度1450℃左右。采用ICP原子发射光谱分析仪分析所熔合金的化学成分,利用金相显微镜、扫描电子显微镜、XRD 衍射仪研究了合金的金相组织、表面形貌、微区元素分布、物相结构,用气体反应控制器测定了合金的PCT曲线。研究表明：由BaZrO3坩埚熔炼的TiFe基储氢合金氧质量分数与石墨坩埚熔炼的合金氧质量分数均小于0．1％,而石墨坩埚熔炼的合金碳质量分数为0．417％。BaZrO3坩埚熔炼后的合金完全由等轴晶构成,而石墨坩埚熔炼后的合金则由等轴晶组织和在晶粒内或沿晶界分布的球形TiC颗粒组成。BaZrO3坩埚所熔炼的合金不仅最大吸氢量比石墨坩埚熔炼的合金的最大吸氢量大,而且吸放氢平台压力也低。     

添加硼对La-Mg-Ni系(PuNi3-型)贮氢合金微观结构及电化学性能的影响

为了提出La-Mg-Ni(PuNi3型)系贮氢合金的电化学循环稳定性,在La2Mg(Ni0.85Co0.15)9合金中添加微量的B,用铸造及快淬工艺制备La2Mg(Ni0.85Co0.15)9Bx(x=0,0.05,0.10,0.15,0.20)贮氢合金,分析测试铸态及快淬态合金的微观结构与电化学性能,研究硼对合金微观结构及电化学性能的影响。结果表明:铸态合金具有多相结构,包括主相(La,Mg)Ni3相(PuNi3型)和LaNi5相,一定量的LaNi2相和微量的Ni2B相经快淬处理后,Ni2B相消失,且其他相的相对量随淬速的变化而变化。硼的加入提高了铸态及快淬态合金的循环稳定性,但使铸态合金的容量下降;铸态合金的电化学容量随B含量的增加单调下降,而快淬态合金的容量随B含量的增加有一极大值,B对铸态及快淬态合金电化学性能的影响机理是完全不同的。     

LaNi4.25Al0.75储氢合金的改性

为了提高LaNi4．25Al0．75合金的储氢性能,采用退火、表面镀铜和表面包覆SiO2对合金进行改性,并对处理前、后合金的微观结构和吸放氢性能的变化进行研究。研究结果表明,退火消除了LaNi4．25Al0．75合金中的偏析,减少了内应力,使合金具有平坦的吸氢平台;表面镀铜处理加快了合金的吸、放氢速度,但吸氢含量略有降低,另外,镀铜合金抗粉化性能加强,经10次吸、放氢循环后没有出现粉化现象;表面包覆SiO2前、后,合金的吸氢量变化不大,抗粉化性能加强,经10次吸、放氢循环后没有出现粉化现象。     

Improvement in hydrogen storage performance of Mg by mechanical grinding with molten salt etching Ti3C2Clx

Mg-based materials are currently a hot research topic as hydrogen storage materials due to their considerable theoretical hydrogen storage capacity. However, the kinetic performance of hydrogen absorption and desorption of Mg is too slow and requires high temperature, which seriously hinders the application of this material. MXene is a new type of two-dimensional material with significant role in improving thermodynamics and kinetics. In this experiment, a two-dimensional layered MXene containing Cl functional group was prepared by molten salt etching using the Ti-containing MAX phase as the raw material. Then different ratios of Ti₃C₂Cl_x were uniformly dispersed onto the surface of Mg by high energy ball milling. The samples were characterized by hydrogen absorption and desorption kinetics, SEM, XRD, XPS, and DSC to investigate the effect of Ti₃C₂Cl_x on the hydrogen absorption and desorption performance of Mg. The onset hydrogen absorption temperature can be reduced to room temperature and the hydrogen release temperature is reduced by 200 ​°C by doping Ti₃C₂Cl_x. And there is also 5.4 ​wt% hydrogen storage in the isothermal hydrogen absorption test at 400 ​°C. The results of DSC demonstrate that the E_a of Mg+15 ​wt% Ti₃C₂Cl_x was reduced by 12.6% compared to pristine Mg. The ΔH is almost invariable. The results of XPS show that the presence of multivalent Ti promotes electron transfer and thus improves the conversion between Mg²⁺/Mg and H⁻/H. This study provides a guideline for further improving the hydrogen absorption and desorption performance of Mg-based hydrogen storage materials.     

Effect of Ce addition on hot corrosion behaviours of a cast γ′-strengthened Co–Al–W–Mo–Ta–B alloy at 800 ​°C

Hot corrosion behaviours of a novel Co–9Al-4.5W-4.5Mo–2Ta-0.02B alloy doped with 0.01, 0.05, 0.1 and 0.2 ?at% Ce exposed at 800 ?°C in a solution of 75%Na₂SO₄/25%NaCl were investigated. The alloys comprised a coherent γ-Co_SS/γ′-Co₃(Al, W) microstructure (0.01Ce and 0.05Ce alloys) and κ-Co₃(W, Mo) precipitates (0.1Ce and 0.2Ce alloys) at grain boundaries. Hot corrosion kinetics curves demonstrated the parabolic time dependency profile with two stages: the first parabolic stage is within the beginning ～50 ?h corrosion and follows by the second parabolic stage. With an increasing nominal Ce content the weight gain of the alloy significantly decreased from approximately 70.1 ?mg ?cm^?2 (0.01Ce) to 40.8 ?mg ?cm^?2 (0.2Ce) when exposed for 100 ?h. A two-layer corrosion scale formed, and the scale was composed of an outer layer of Co₃O₄ oxide with spinel compounds of CoAl₂O₄, CoWO₄and CoSO₄, and an inner γ/needle-like Co₃W/sulphide layer adhered to the substrate. Heavy spallation of the corrosion scale occurred in the 0.01Ce～0.1Ce alloys, however, spallation was slight in the 0.2Ce alloy. The excellent corrosion resistance of the 0.2Ce alloy could be attributed mainly to the formation of continuous Al₂O₃ lines in the corrosion scale, as well as the prolongation of the incubation period of the corrosion product spallation.     

Hydrogen storage and low-temperature electrochemical performances of A2B7 type La-Mg-Ni-Co-Al-Mo alloys

The effect of Mo-addition on hydrogen storage and low-temperature electrochemical performances of La-Mg-Ni-Co-Al alloys is investigated. The alloys were synthetized via vacuum induction melting followed by annealing treatment at 1123 K for 8 h. The major phases in the annealed alloys are consisted of (La, Mg)2Ni7, (La, Mg)5Ni19 and LaNi5 phases. Mo-addition facilitates phase transformation of LaNi5 into (La, Mg)2Ni7 and (La, Mg)5Ni19 phases. Hydrogen absorption/desorption PCI curves indicates that the hydrogen storage capacity of the alloy increases remarkably with the addition of Mo. Furthermore, the La0.75Mg0.25Ni3.05Co0.2Al0.05Mo0.2 alloy shows excellent hydriding/dehydriding kinetics with a higher capacity, requiring only 100 s to reach its saturated hydrogen capacity of 1.58 wt% at low temperature of 303 K, and releasing 1.57 wt% hydrogen within 400 s at 338 K. Electrochemical experiments manifest that the Mo-added alloy electrode has perfect activation properties and the maximum discharge capacity. The low-temperature dischargeability shows that the La0.75Mg0.25Ni3.05Co0.2Al0.05Mo0.2 alloy exhibits the excellent low-temperature discharge performance, and the maximum discharge capacity is improved from 231.0 to 334.6 mAh/g at 253 K. The HRD property of the alloy electrode is enhanced, suggesting that Mo enhances the kinetic ability at low-temperature.     

La-Mg-Ni系储氢合金的容量衰减与其组织结构

为了研究AB2型La-Mg-Ni系储氢合金的容量衰减以及循环前后合金的组织结构,采用Sieverts法测试了LaSmMgNi4.1快淬态合金的吸放氢量,用X射线衍射分析（XRD）、扫描电子显微镜（SEM）和高分辨透射电子显微镜（HRTEM）分别测试和观察了循环前后合金的相结构、颗粒形貌以及原子排列。结果表明,合金的吸放氢量随着循环次数增加发生衰减,合金的吸放氢衰减速率与循环阶段有关。合金由不同生长方向、不同尺寸的柱状晶组成,成分基本均匀,主要由(LaSm)MgNi4主相和LaNi5相组成,相组成的组织为晶态。经过吸放氢循环后,合金由大量非晶和少量晶态组成。随着循环次数增加,合金颗粒粉化与蓬松严重。     

Creep behavior and effect factors of a TiAl–Nb alloy at high temperature

The effect of solution treatment on the microstructure and creep properties of forged TiAl–Nb alloys was investigated. The results showed that the microstructure of forged alloy mainly consisted of γ/α₂ lamellar colonies and fine equiaxed recrystallized γ/α₂ grains. During the solution treatment the microstructure of the alloy transformed into a fully lamellar structure due to the lamellar colonies growth by consuming equiaxed grains. Compared with the forged alloy the creep life of the solution treated alloy at 800 ?°C/220 ?MPa increased from 116 ?h to 339 ?h. The better creep resistance may be attributed to the transform of fine equiaxed γ/α₂ grain to the lamellar colonies with serrated grain boundaries due to the solution treatment. The deformation mechanism of the solution treated alloy during creep is considered to be dislocation slipping within the lamellar γ/α₂ phases, and the dislocation movement may be hindered by the γ/α₂ interface and the formation of dislocation tangles. The interaction of the dislocations with the tangles may increase the resistance of the dislocation motion and hence improve the creep resistance of the alloy. It was found that during the creep of the forged alloys the cracks mainly initiated at the equiaxed grain, and in the solution treated alloy the cracks initiated at the grain boundaries. As creep continued the cracks propagated and connected to each other, leading to the damage and rupture of the forged and solution treated alloys.     

添加Ti0.9Zr0.1Mn1.5复合球磨对Ti9.6V86.4Fe4 合金储氢性能的影响

系统研究了Ti9.6V86.4Fe4储氢合金中掺入10%（质量分数）的Ti0.9Zr0.1Mn1.5进行复合球磨对其相结构及储氢性能的影响.X射线衍射分析表明,Ti9.6V86.4Fe4铸态合金具有单一的体心立方（BCC）结构固溶体相,当添加10%的Ti0.9Zr0.1Mn1.5复合球磨后,复合物由BCC主相和C14型Laves第2相组成.扫描电子显微镜及X射线能量色散谱仪分析表明,Ti9.6V86.4Fe4合金粉颗粒表面包覆了一层Ti0.9Zr0.1Mn1.5微粒.储氢性能测试表明,Ti9.6V86.4Fe4中掺入10%的Ti0.9Zr0.1Mn1.5复合球磨后,虽然室温最大吸氢量（质量分数）从3.86%略微降低至3.61%,但其有效储氢量（质量分数）由2.01%提高到2.11%,活化性能和P-C-T曲线平台特性都得到了明显改善.     

Effect of minor Sc on the microstructure and mechanical properties of AZ91 Magnesium Alloy

The as-cast and heat-treated microstructures and mechanical properties of the AZ91 magnesium alloys with and without minor Sc addition were investigated and compared in this paper. The results indicated that adding0.15–0.45 wt% Sc to the as-cast AZ91 alloy not only could modify and refine the Mg_(17)Al_(12) phase but also suppress the formation of the Mg_(17)Al_(12) phase. At the same time, the grains of the Sc-containing as-cast AZ91 alloys were also effectively refined. As a result, the mechanical properties at room temperature(RT) for the Sccontaining as-cast AZ91 alloys were effectively improved. In addition, adding 0.15–0.45 wt%Sc to the AZ91 alloy promoted the formation of the continuous precipitates(CP) during the aging treatment in spite of that the formation of the discontinuous precipitates(DP) was simultaneously suppressed. Accordingly, the Sc-containing as-aged AZ91 alloys obtained the relatively higher mechanical properties at RT than the as-aged AZ91 alloy.     

Catalytic effect of a novel MgC_(0.5)Co_3 compound on the dehydrogenation of MgH_2

The application of magnesium hydride(MgH_2) is limited due to the high reaction temperature and slow kinetics during dehydrogenation. In order to ameliorate the dehydrogenation property of MgH_2, MgC_(0.5)Co_3 compound with induction and catalytic effects was introduced into the Mg/MgH_2 system via ball-milling and hydriding combustion methods in present study. Compared to the pure MgH_2,the initial hydrogen desorption temperature of MgH_2–MgC_(0.5)Co_3 composite lowered to 237°C, decreasing by 141°C. At 325°C the MgH_2–MgC_(0.5)Co_3 composite could release 4.38 wt% H_2 within 60 min, which is 4.5 times the capacity of hydrogen released by as milled-MgH_2. Besides, the hydrogen desorption activation energy of the MgH_2–MgC_(0.5)Co_3 composite was dramatically reduced to 126.7 ± 1.4 k J/mol. It was observed that MgC_(0.5)Co_3 was chemically stable and no chemical transformation occurred after cycling, which not only inhibited the nucleation and growth of composite particles, but also had a positive effect on the hydrogen desorption reaction of MgH_2 due to its catalytic effect.This study may provide references for designing and synthesizing Mg–C–Co alloy compound for the Mg-based hydrogen storage area.     

Optimization of mechanical properties of Sn-3.8Ag-0.7Cu alloys by the additions of Bi,In and Ti

Bi, In and Ti were added to Sn-3.8Ag-0.7Cu (SAC387) solder alloy to optimize the mechanical performance. The alloying effects of Bi, In and Ti on the microstructure, thermal and mechanical properties of SAC387 based solder alloys were investigated. The results demonstrate that adding 3.5 ?wt % of Bi could refine the microstructure, optimize the thermal properties, and improve the tensile strength. Meanwhile, the ductility of the solder alloys reduced evidently. Adding 2.8 ?wt % of In into SAC387–3.5 ?wt %Bi alloy could increase both the strength and ductility, which is attributed to the beneficial effect of In addition, as adding In could improve the solubility of Bi in the β-Sn matrix. Meanwhile, the melting point was reduced, and the wettability improved with the addition of In. Introducing amounts of Ti into SAC387–3.5 ?wt % Bi-2.8 ?wt % In alloy could further increase the strength. However, the ductility was significantly reduced when 0.8 ?wt % of Ti was added due to the formation of the coarse Ti₂Sn₃ phase. The undercooling was remarkably reduced with the addition of Ti. The nanoindentation tests demonstrate that the hardness increased mainly due to the hardening effect of the Bi addition. Among all the samples prepared, alloy SAC387–3.5 ?wt % Bi exhibited the highest creep resistance at the ambient temperature. Further adding In and Ti into SAC387–3.5 ?wt % Bi alloys reduced the creep resistance of the solder alloys. The mechanism associated with the different mechanical responses is also discussed in this study.     

球磨改性处理对Ti9.6Cr11V75.4Fe4合金储氢性能的影响

系统研究了机械球磨改性处理时间(t=0,1,2,4,8 h)对Ti9.6Cr11V75.4Fe4合金相结构和储氢性能的影响.XRD及扫描电镜分析表明,Ti9.6Cr11V75.4Fe4合金在球磨前后均为体心立方结构的固溶体单相,随着球磨时间的增加,合金的晶胞体积略微减小,合金颗粒逐渐细化并发生团聚.储氢性能测试表明,球磨改性处理能有效地改善合金的活化性能,随着球磨时间的增加,合金的室温可逆有效储氢量先增加后降低.其中,当球磨时间为2 h时,合金具有最佳的综合储氢性能,其室温最大吸氢量(质量分数)为3.7%,可逆有效储氢量(质量分数)为2.23%.