掺Pd改性纳米晶Mg2Ni吸放氢氘特性研究

采用机械合金化法制备了Mg2Ni-1．0％Pd（质量分数，下同）合金粉末，用XRD及AFM等分析表征了球磨20h后粉末的相结构和微观形貌，测定了Mg2Ni-1．0％Pd合金吸放氢氘的P-C-T曲线和动力学曲线。结果表明，机械合金化制备的Mg2Ni-1．0％Pd合金粉末粒度在10nm～50nm之间；同熔炼法制备的Mg2Ni合金相比，纳米Mg2Ni-1．0%Pd合金吸氢时的焓变值减小，放氢时焓变值增大，可逆贮氢容量为1．06（H／M,原子比，下同）；与吸放氢相比，在相同温度下合金吸放氘的坪台压升高，焓变值减小，具有显著的同位素效应。纳米Mg2Ni-1．0％Pd合金的吸氢速率和吸氘速率与温度的关系在573K附近发生变化。     

PdY8．5Ru0．19合金吸放氢氘特性

在25℃～100℃的温度范围内,测定了PdY8.5Ru0.19合金吸放氢、氘的P-C-T曲线.与纯钯相比,合金的P-C-T曲线坪区变窄,坪压降低,有显著的同位素效应,但迟滞效应较小.合金吸放氢氘的P-C-T曲线可拟合成p=A(er/B-1)形式.吸氘热焓为-13.9 kJ/mol·D2,熵变为-9.4 J/mol K·D2.进行了25℃下合金吸氢、氘速率的测量,合金吸氢、氘速率常数分别为KH=2.39×10-4 mol·s-1,KD=1.16×10-4 mol·s-1.而且合金的氢化过程用渐进转化模型描述.     

Pd包覆TiZrNiCo的抗毒化及动力学性能

采用化学镀方法在TiZrNiCo合金颗粒表面包覆上0.4~2μm厚的Pd膜,并测得不同膜厚的Pd/TiZrNiCo试样在混合气体中的吸氢动力学。结果表明:Pd膜越薄,Pd/TiZrNiCo抗毒化性能及吸氢动力学性能越好,0.4μm厚Pd膜试样的吸氢量为2μm厚Pd膜试样的1.6倍。Pd/TiZrNiCo试样吸放氢后粉化,引发Pd膜破裂导致吸氢速率减缓与基体粉化引发吸氢速率加快的两种效果,吸氢量随吸放氢次数的增加而出现波动性的上升回落。根据吸氢机理及毒化机理,提出并采用相应的动力学模型,并对TiZrNiCo吸纯氢及Pd/TiZrNiCo吸氢动力学曲线进行了拟合。     

ZK60-Pd合金的高周吸放氢循环性能

对ZK60贮氢合金球磨时添加C和Pd元素,进行了500次吸放氢循环性能试验。结果表明,随循环次数的增加,合金吸放氢量降低,前50次明显,第50次时降为第1次的83.9%,后续高周循环吸放氢量基本相同,吸放氢速率变化不明显。高周吸氢动力学性能较好,表面没有阻碍吸氢的化合物生成,高周循环后合金颗粒发生明显粉化。     

纳米晶镁粉的吸放氢动力学模型分析

利用一种新模型分析了纳米晶镁粉的吸放氢动力学，量化了球磨和添加剂Pd对镁粉吸放氢动力学性能的改善效果。结果表明，球磨能大幅度降低氢化反应活化能，提高镁粉的氢化速率30倍。添加1％（质量分数）Pd的纳米镁粉（30nm）的吸放氢速率比未添加Pd的纳米镁粉（30nm）的吸氢速率提高6．6倍。模型计算出30nmMg-1％Pd（质量分数）合金的吸氢活化能为38．74kJ／molH2。     

镁基储氢材料颗粒尺寸对吸放氢动力学性能的影响

通过吸放氧动力学方程，计算了颗粒大小对镁-镍-氧化物储氢材料吸放氢动力学过程的影响。计算结果表明：不同颗粒直径的镁-镍-氧化物储氢材料的吸放氢反应速度差别较大；颗粒越小，其吸放氢动力学性能越优异。     

V55Ti20.5Cr18.1Fe6.4合金的吸放氢循环性能研究

对V55Ti20.5Cr18.1Fe6.4（原子分数，下同）贮氢合金进行了155次吸放氢循环性能实验研究。结果表明：随循环次数的增加，合金吸放氢量减小，放氢量的衰减呈减缓趋势，放氢平台区缩短，平台压力增大，合金表面有影响吸放氢性能的化合物生成，合金结构呈bcc与fcc的双相结构，合金颗粒由于微裂纹的不断累积而逐渐粉化。     

Pd/Y薄膜在气态吸放氢过程中的表面形貌和可转换光学特性

利用直流磁控溅射法制备了Pd／Y稀土薄膜，研究了薄膜在气态吸放氢过程中表面形貌及光学特性变化。研究表明，采用磁控溅射法制备的薄膜具有柱状晶结构，最外层的Pd层为纳米级的孤岛状颗粒结构，室温气态充氢过程中，在Pd颗粒催化作用下，Y可形成氢化物YH3和YH2，形成氢化物的局部区域发生膨胀开裂，在气态充氢过程中，薄膜的透光率随充氢时间和入射光波长的增加而增加，由于YH3自身禁带宽度的原因，在λλ=400nm处存在吸收限，放氢过程中，YH3分解为YH2，薄膜在λ=689nm处透光率最大。     

成份调整对V-Ti-Cr-Fe合金吸放氢性能的影响

分别调整Ti／Cr比及V含量，对V-Ti-Cr-Fe系四元合金的室温吸放氢性能进行了研究。结果表明：随V30Ti31＋xCr29-xFe10合金中Ti／Cr增大，合金吸氢量增大，放氢平台压降低，Ti／Cr〉1．2时放氢量减小，298K最大吸氢量3．66％（质量），最大放氢量2．0％（质量）；随Vx（TiCrFe）100-x（Ti-Cr-Fe=7：5：2）中V含量增大，合金吸氢量增大，放氢量增大，放氢平台压降低，V含量20％（原子）的合金中出现Laves相，298K最大吸氢量3．73％（质量），最大放氢量2．08％（质量）。     

NdFeB母合金吸氢和脱氢过程的研究

研究了吸氢过程中氢压和合金成分的变化对饱和吸氢量及活化时间的影响，脱氢过程中温度对脱氢量的影响以及歧化反应发生的温度条件。调节吸氢过程中的氢压分别为0．1MPa、0．6MPa，结果发现，随氢压的提高饱和吸氢量增大，活化时间减少。制备(Nd0．935Dy0.065)xFe79．7B6.1(x＝13，13.5，14，14．5，15，15．5)的鳞片，保持氢压不变，发现随稀土含量的提高，也具有上述规律。通过差热分析方法测量脱氢过程中几种反应发生的温度条件，在设定的温度下脱氢，并测量脱氢量。结果发现在恒压条件下，600℃下脱氢量为53％，700℃下脱氢，合金已发生歧化反应。     

氚老化对海绵钯吸、放氕氘热力学性质的影响

钯是氚处理工艺中的关键功能材料,氚衰变及其产生的氦会引起钯的贮氢性能下降。对室温下贮氚老化1.6年的海绵钯进行了预处理,采用变温法获得了老化钯吸、放氕和氘的PCT曲线,作为对比,同时给出了新鲜钯的实验结果。在此基础上,进行了氚老化钯吸、放氕和氘热力学性质分析。结果显示,氚老化会导致钯氢体系的α相右移、坪台压降低、坪台区变窄,且老化效应对钯氢体系的滞后效应、焓变及熵变产生影响。     

Thermodynamic Characteristic and Phase Evolution in Immiscible Cr–Mo Binary Alloys

This paper systematically reports the thermodynamic characteristic and phase evolution of immiscible Cr–Mo binary alloy during mechanical alloying(MA) process. The Cr–35Mo(in at%) powder mixture was milled at 243 and258 K, respectively, for different time. For comparative study, Cr–15Mo and Cr–62Mo powder mixtures were milled at 243 K for 18 h. Solid solution Cr(Mo) with body-centered cubic(bcc) crystal structure and amorphous Cr(Mo) alloy was obtained during MA process caused by high-energy ball milling. Based on the Miedema's model, the free-energy change for forming either a solid solution or an amorphous in Cr–Mo alloy system is positive but small at a temperature range between 200 and 300 K. The thermodynamical barrier for forming alloy in Cr–Mo system can be overcome when MA occurs at 243 K, and the supersaturated solid solution crystal nuclei with bcc structure form continually, and three supersaturated solid solutions of Cr–62Mo, Cr–35Mo and Cr–15Mo formed. Milling the Cr–35Mo powder mixture at 258 K, the solid solution Cr(Mo) forms firstly, and then the solid solution Cr(Mo) transforms into the amorphous Cr(Mo)alloy with a few of nanocrystallines when milling is prolonged. At higher milling temperature, it is favorable for the formation of the amorphous phase, as indicated by the thermodynamical calculation for immiscible Cr–Mo alloy system.     

Intrinsic diffusion and Kirkendall effect in Ni–Pd and Fe–Pd solid solutions

Intrinsic diffusion and the Kirkendall effect in the Ni–Pd (at 900–1200°C) and Fe–Pd (at 1100°C) solid solution systems were investigated. The diffusion couple technique including incremental and “multi-foil” couples was employed. A theoretical analysis of the Kirkendall effect, which manifests itself by migration of inert markers inside the interdiffusion zone, was performed for a binary solid solution system. It was demonstrated that depending upon the relative mobilities of the components in different parts of the interaction zone of such binary diffusion couples, the appearance of two or more “Kirkendall” planes as marked by inert particles can be expected. This phenomenon, which indeed was predicted and found in the multiphase Ni/Ti diffusion couple, was not observed in the experiments on the single-phase Ni–Pd and Fe–Pd systems. The diffusion process in these binary systems exhibiting a minimum in the liquidus curve was found to show special features with respect to the concentration dependence of the diffusion coefficients.     

Temperature effects for crystal growth: a distribution kinetics approach

The effect of temperature on the growth and dissolution dynamics of nonequilibrium crystal size distributions can be determined by solving the governing population balance equations. The model includes the effect of temperature through the diffusion-influenced growth coefficient, the phase transition energy, and the Gibbs–Thomson effect of particle curvature and interfacial energy. The time evolution of the average size of two polymorphs evolving from a single solute is also modeled. We show that the average sizes of the two polymorphs diverge, one continuing to increase, the other decreasing with time, indicating dynamic ripening. Strategies that allow temperature programming suggest how competing crystal or grain growth processes can be controlled.     

Vaporization behaviour and some thermodynamic properties of the Pd-In,Pd-Pb,Pd-Sn systems

In this study, the vaporization behaviour of solid Pd-rich phases in the Pd–Pb, Pd–In and Pd–Sn systems was investigated by Knudsen-effusion-cell coupled with mass-spectrometry. The Pb, Pd, In vapor pressures [no Sn(g) has been detected in the vapor of Pd-Sn system] were evaluated in the temperatures range 1190–1563 K from the ion intensities measured over two-phases regions. Thermodynamic quantities were derived from vapor pressure data. In particular, for the Pd–Sn binary, the intermediate phase Pd₇Sn₂, the existence of which has been recently proposed, has been studied here for the first time. Furthermore, preliminary thermochemical data are presented for the diatomic intermetallic molecules PdSn and PdPb, which have been for the first time identified in the vapors in equilibrium over liquid solutions of appropriate composition at higher temperatures (1935–2025 K).     

Hydrogenation properties of shape memory Ti(Ni,Pd) compounds

The effect of Pd substitution on the crystal structure and hydrogenation properties of TiNi compound has been investigated. Ti(Ni,Pd) are pseudo-binary compounds. The unit-cell volumes of B2 (Austenite) and B19 (Martensite) structures linearly increase with Pd substitution in Ti_1.04Ni_0.96?xPd_x samples. The hydrogenation properties of Pd-substituting Ti(Ni,Pd) compounds are not affected by the crystal structure of the parent compounds. For all samples, hydrogen absorption occurs without showing any clear plateau pressure in Pressure-Composition-Isotherm (PCI) curves. All hydrided samples crystallise in the tetragonal I 4/mmm space group. At 6 MPa of hydrogen pressure and T = 423 K, the hydrogenation capacity of Ti(Ni,Pd) compounds reaches 1.52 hydrogen atoms per formula unit (H/f.u.) for x = 0.1 and then gradually decreases with Pd content down to 0.93 H/f.u. for x = 0.5. Ti_1.04Ni_0.86Pd_0.10 sample yields a discharge capacity of 148 mAh/g at C/5 regime when used as negative electrode in Ni-MH battery. The hydrogenation properties of Pd-substituting Ti(Ni,Pd) compounds are discussed in detail by comparison with previous studies on Zr substituting, (Ti,Zr)Ni compounds.     

The interaction of dissolved H with internally oxidized Pd–Rh alloys

Homogeneous fcc Pd–Rh alloys have been internally oxidized in the atmosphere at several temperatures from 1023 to 1123 K forming oxide precipitates within a Pd matrix. As shown from electron diffraction patterns of the internally oxidized Pd_0.97Rh_0.03 alloy, the oxide that forms is a mixed oxide, PdRhO₂. Internally oxidized Pd–Rh alloys can be reduced with H₂ (573–623 K) forming PdRh precipitates within the Pd matrix. This is a technique for segregating components of a substitutional solid solution binary alloy. The segregated alloy can be returned to the homogeneous Pd–Rh alloy by annealing at an elevated temperature and thus, in contrast to the internal oxidation of, e.g., Pd–Al alloys, the process can be readily reversed. The oxidation and (reduction+H₂O loss) were monitored from weight changes.After internal oxidation/reduction “diagnostic” hydrogen isotherms (323 K) were measured to follow the extent of oxidation and to determine the extent of H trapped at the internal interfaces from the positive intercepts along the H/Pd axis in the dilute phase. The H capacities in the steeply rising hydride region of the H₂ isotherms for the internally oxidized alloys are smaller than for Pd unless the Pd in the PdRh precipitates is considered to be inactive for H₂ absorption for the calculation of H/Pd values.In the two-phase region the absorption plateau pressures were significantly greater than for Pd–H, however, they were much closer to the Pd plateau p_H2 than to that of the unoxidized Pd–Rh alloys. The desorption plateaux were very close to those of Pd–H for X_Rh=0.01 to 0.05 alloys and therefore it can be concluded that the matrix is pure Pd whose absorption plateaux are affected by the presence of the precipitates.The techniques of TEM, SEM and SANS (small angle neutron scattering) were employed to examine the alloys after internal oxidation both before and after reduction. SANS confirmed directly that internal precipitates form from the internal oxidation and that they are rather large with an appreciable fraction having diameters greater than 100 nm.     

Effect of pressure on microstructures and mechanical properties of Al-Cu-based alloy prepared by squeeze casting

A new high-strength aluminum alloy with better fluidity than that of ZL205A was developed. The effect of applied pressure during squeeze casting on microstructures and properties of the alloy was studied. The results show that the fluidity of the alloy is 16% and 21% higher than that of ZL205A at the pouring temperature of 993 K and 1 013 K, respectively. Compared with permanent-mold casting, mechanical properties of the alloy prepared by squeeze casting are much higher. The tensile strength and elongation of the alloy are 520 MPa and 7.9% in squeeze casting under an applied pressure of 75 MPa, followed by solution treatment at 763 K for 1 h and at 773 K for 8 h, quenching in water at normal temperature and aging at 463 K for 5 h. The improvement of mechanical properties is attributed to the remarkable decreasing of the secondary dendrite arm spacing(SDAS) and eliminating of micro-porosity in the alloy caused by applied pressure.     

Change in form of palladium plate during one-sided saturation with hydrogen: I. Effect of rate of increase in gaseous-hydrogen pressure

The effect of the rate of gaseous-hydrogen pressure rise on changes in the form of a palladium plate has been studied during its one-sided saturation with hydrogen in the ?? region of the Pd-H system under isothermal conditions at temperatures of 170?C320°C. The dependences of the principal characteristics of hydrogen-induced changes in the form of a plate on the rate of gaseous hydrogen pressure rise were determined. The decrease in the rate of increase in hydrogen pressure was found to lead to a decrease in the maximum bend of the plate.     

Self-propagating high-temperature synthesis in Ti-W-C system

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