新型贮氢材料的开发

铝系贮氢材料与锂系贮氢材料的研制铝氢酸盐(Alanate)即含四氢铝酸离子([AlH4]^-)的盐的总称,LiAlH4含氢量为10．6％(质量),NaAlH4含氢量为7．5％(质量),但是这些氢化物并不能进行氢化反应,所以不适合作贮氢材料。近年来发现在乙醚中掺入NaAlH4和TiCl3之后则发生两阶段的     

Ti掺杂对NaAlH4储氢性能的影响

采用基于密度泛函理论(DFT)的平面波赝势(PW-PP)方法,分别计算纯净以及掺杂Ti的NaAlH4和Na3AlH6的晶格结构参数、能量变化和电子态密度(DOS),分析比较Ti掺杂对NaAlH4和Na3AlH6储氢性能的影响。结果表明:Ti掺杂后的晶格结构比原纯净的NaAlH4和Na3AlH6稳定,且脱氢所需能量减少。Ti替代Na后,Ti吸引周围的H原子,使Al-H键变弱;Ti替代Al,Ti-H键比原Al-H键明显减弱,使掺杂后脱氢所需能量降低。通过对比分析Ti掺杂对NaAlH4和Na3AlH6结构和态密度的影响,得出Ti的催化作用主要发生在脱氢反应的第一步。     

LiBH4/Li3AlH6复合物的放氢性能与机理

采用机械球磨法制备LiBH4/Li3AlH6复合体系,通过TG/DSC/MS、XRD等方法对其储氢性能及机理进行研究,并对其放氢反应激活能进行计算。结果表明,LiBH4-Li3AlH6复合体系从室温加热到500℃条件下发生3步放氢反应:首先,Li3AlH6分解生成Al并放出氢;然后部分生成的Al与LiBH4发生反应放出氢气;最后,剩余的Al与LiH反应放出氢气。复合体系总的放氢量达到8.5%(质量分数,下同),完全放氢后的复合物在8MPa和400℃条件下最大吸氢量达到4.9%。并对LiBH4-Li3AlH6复合体系放氢过程机理进行了分析。     

掺杂稀土类催化剂对LiAlH4放氢性能和相结构的影响

采用球磨的方式在LiAlH4中分别掺入3种稀土催化剂LaCl3、CeCl3和Ce(SO4)2,研究了稀土催化剂对LiAlH4的相结构和放氢性能的影响。结果表明,在球磨过程中,掺杂Ce(SO4)2对LiAlH4的分解基本没有影响,而掺杂LaCl3和CeCl3则造成LiAlH4部分分解,产生了LiCl和Al3RE（RE=La,Ce）相。在LiAlH4放氢反应中,稀土催化剂的加入均使LiAlH4初始放氢温度降低,特别是Ce(SO4)2使第1步的放氢温度降低了约25 ℃。稀土催化剂有助于加快LiAlH4分解反应速率,提高LiAlH4的放氢性能。     

过渡金属氧化物掺杂NaAlH4放氢性能

采用PCT (Pressure-Content-Temperature)、XRD、SEM等测试方法对掺杂不同过渡金属氧化物(TiO2,ZrO2,Cr2O3,ZnO)的NaAlH4试样的放氢性能进行研究.结果表明,掺杂TiO2和ZrO2的NaAlH14试样的放氢性能较好.此外,所研究球磨工艺明显改善了NaAlH4的放氢性能.SEM结果发现,球磨3h的Zr-NaAlH4试样效果最佳,此时粉体吸附在较大颗粒四周,随球磨时间的延长,NaAlH4粉体颗粒发生团聚.XRD结果表明,NaAlH4球磨后的结构并未发生明显变化,这说明NaAlH4具有良好的稳定性.     

TiC催化剂对铝氢化钠吸放氢行为和微观结构的影响

采用氢化NaH/Al＋xTiC（x=0,5%,8%,10%,摩尔分数）混合物的方法制备TiC掺NaAlH4配位氢化物,系统研究TiC催化剂含量对样品吸放氢行为的影响。结果表明：TiC能有效改善铝氢化钠的吸放氢动力学性能,样品的加氢速率随着TiC含量的增加而提高;TiC掺NaAlH4复合物具有良好的吸放氢循环稳定性,掺杂10%TiC（摩尔分数）的NaAlH4复合物经过8次吸放氢循环后,其吸、放氢容量仍可稳定保持为4.5%和3.8%（质量分数）;TiC掺NaAlH4复合物的颗粒尺寸可降低到50-100nm,这对改善体系吸放氢反应动力学起到主要作用。     

Study on Influence of Processes on the Dehydrogenation Performance of NaAlH4

分析了制备工艺过程、球磨设备、试样放置时间以及球磨时间对NaAlH4放氢性能的影响。其中除了试样3是采用高能球磨机外,其它所有试样均采用行星式球磨机。结果表明,这些因素对NaAlH4放氢性能的影响非常明显。试样在球磨过程中经过上下翻转后,其放氢量明显比不翻转高出了50%(质量分数)。不同球磨设备研究结果显示,试样3经过高能振动球磨机球磨后,其放氢量比行星式球磨机制备的试样的放氢量明显提高了。试样放置时间与试样球磨时间的研究结果显示,制备好的球磨试样经过24 h放置后,其放氢量明显提高。此外,试样经过不同时间球磨后,其放氢量也有明显的不同。经研究发现,球磨80 min试样的放氢量比球磨100 min和球磨40和60 min试样的放氢量要高,但和其它的影响因素相比,球磨时间对NaAlH4放氢性能的影响相对较小     

掺杂NaAlH4放氢性能的研究

采用PCT(pressure-conten-temperature)、XRD等测试方法对掺杂Ag2SO4、SrCO3、TiO2和ZnO的NaAlH4放氢性能进行研究。结果显示,掺杂TiO2的NaAlH4试样具有最大的放氢量,而掺杂SrCO3的试样放氢量最小,并且对比所有掺杂试样在第1阶段的放氢速率发现,掺杂TiO2的NaAlH4试样具有最大的放氢速率,在整个放氢性能的测试过程中,试样表现出了明显的2个分解阶段,并且在第1阶段的分解速率明显大于第2阶段。此外,掺杂TiO2和ZnO试样的XRD结果表明,掺杂试样经过30min的球磨之后,试样的晶体结构没有发生明显变化,并且没有新的物相生成,这说明NaAlH4具有很好的稳定性。     

Al添加对LiBH4可逆吸放氢性能影响的研究

研究了Al对LiBH4吸放氢性能的影响.结果表明,Al的添加可使LiBH4起始放氢温度降低至300 ℃左右,且主要放氢过程的温度范围随着Al含量的增加而逐渐降低;可逆性研究表明,放氢后的LiBH4/Al混合体系在600 ℃、10 MPa条件下实现可逆吸氢,这明显低于单一LiBH4的可逆吸氢条件.LiBH4/Al吸放氢性能改善的原因是由于化合物LiAl和AlB2的生成.     

Ti6Al4V合金吸氢行为研究

研究了Ti6Al4V合金在不同置氢温度、保温时间和氢压下的吸氢行为,利用光学显微镜研究了氢在钛合金中的分布规律。研究结果表明,Ti6Al4V合金的氢含量是由置氢温度、保温时间和氢压来控制的。随着置氢温度的升高,氢含量先增加后降低。随着氢压的增加,氢含量直线增加。钛合金的吸氢过程实质上是氢的扩散过程,随着保温时间的增加,合金中的氢分布逐渐趋于一致。     

Effects of Post-weld Heat Treatment on Microstructure,Mechanical Properties and the Role of Weld Reinforcement in 2219 Aluminum Alloy TIG-Welded Joints

In as-welded state, each region of 2219 aluminum alloy TIG-welded joint shows diff erent microstructure and microhardness due to the diff erent welding heat cycles and the resulting evolution of second phases. After the post-weld heat treatment, both the amount and the size of the eutectic structure or θ phases decreased. Correspondingly, both the Cu content in α-Al matrix and the microhardness increased to a similar level in each region of the joint, and the tensile strength of the entire joint was greatly improved. Post-weld heat treatment played the role of solid solution strengthening and aging strengthening. After the post-weld heat treatment, the weld performance became similar to other regions, but weld reinforcements lost their reinforcing eff ect on the weld and their existence was more of an adverse eff ect. The joint without weld reinforcements after the post-weld heat treatment had the optimal tensile properties, and the specimens randomly crack in the weld zone.     

The First Phase of the SRIF Industrialized Base in ＂West Area＂ Has Been Put into Operation

After nearly two years＇ tense construction, the first phase of industrialized base of Shenyang Research Institute of Foundry （SRIF）, located at the Tiexi Casting and Forging Industrial Park in the west of Tiexi District, has now been completed and formally put into operation.     

Thermodynamics Study on the Decomposition of Chromite with KOH

Institute of Process Engineering, Chinese Academy of Sciences, China, has proposed a method for oxidative leaching of chromite with potassium hydroxide. Understanding the mechanism of chromite decomposition, especially in the potassium hydroxide fusion, is important for the optimization of the operating parameters of the oxidative leaching process. A traditional thermodynamic method is proposed and the thermal decomposition and the reaction decomposition during the oxidative leaching of chromite with KOH and oxygen is discussed, which suggests that chromite is mainly destroyed by reactions with KOH and oxygen. Meanwhile, equilibrium of the main reactions of the above process was calculated at different temperatures and oxygen partial pressures. The stable zones of productions, namely, K2CrO4 and Fe2O3, increase with the decrease of temperature, which indicates that higher temperature is not beneficial to thermodynamic reactions. In addition, a comparison of the general alkali methods is carried out, and it is concluded that the KOH leaching process is thermodynamically superior to the conventional chromate production process.     

Influence of Heat Treatment on Damping Behaviour of the Magnesium Wrought Alloy AZ61

The effect of isochronal heat treatments for 1h on variation of damping, hardness and microstructural change of the magnesium wrought alloy AZ61 was investigated. Damping and hardness behaviour could be attributed to the evolution of precipitation process. The influence of precipitation on damping behaviour was explained in the framework of the dislocation string model of Granato and Lücke.     

Effect of Rare Earth Doping on Impedance,Modulus and Conductivity Properties of Multiferroic Composites:0.5(BiLa_xFe_(1-x)O_3)–0.5(PbTiO_3)

The Lanthanum-doped bismuth ferrite–lead titanate compositions of 0.5(Bi LaxFe1-xO3)–0.5(Pb Ti O3)(x = 0.05,0.10,0.15,0.20)(BLxF1-x-PT) were prepared by mixed oxide method.Structural characterization was performed by X-ray diffraction and shows a tetragonal structure at room temperature.The lattice parameter c/a ratio decreases with increasing of La(x = 0.05–0.20) concentration of the composites.The effect of charge carrier/ion hopping mechanism,conductivity,relaxation process and impedance parameters was studied using an impedance analyzer in a wide frequency range(102–106Hz) at different temperatures.The nature of Nyquist plot confirms the presence of bulk effects only,and non-Debye type of relaxation processes occurs in the composites.The electrical modulus exhibits an important role of the hopping mechanism in the electrical transport process of the materials.The ac conductivity and dc conductivity of the materials were studied,and the activation energy found to be 0.81,0.77,0.76 and 0.74 e V for all compositions of x = 0.05–0.20 at different temperatures(200–300 °C).     

Quantitative Analysis of the Crystallographic Orientation Relationship Between the Martensite and Austenite in Quenching–Partitioning–Tempering Steels

The orientation relationships(ORs)between the martensite and the retained austenite in low-and medium-carbon steels after quenching–partitioning–tempering process were studied in this work.The ORs in the studied steels are identified by selected-area electron diffraction(SAED)as either K–S or N–W ORs.Meanwhile,the ORs were also studied based on numerical fitting of electron backscatter diffraction data method suggested by Miyamoto.The simulated K–S and N–W ORs in the low-index directions generally do not well coincide with the experimental pole figure,which may be attributed to both the orientation spread from the ideal variant orientations and high symmetry of the low-index directions.However,the simulated results coincide well with experimental pole figures in the high-index directions{123}_(bcc).A modified method with simplicity based on Miyamoto’s work was proposed.The results indicate that the ORs determined by modified method are similar to those determined by Miyamoto’method,that is,the OR is near K–S OR for the low-carbon Q–P–T steel,and with the increase of carbon content,the OR is closer to N–W OR in medium-carbon Q–P–T steel.     

Using Finite Element and Contour Method to Evaluate Residual Stress in Thick Ti-6Al-4V Alloy Welded by Electron Beam Welding

This work was to reveal the residual stress profile in electron beam welded Ti-6Al-4V alloy plates(50 mm thick) by using finite element and contour measurement methods.A three-dimensional finite element model of 50-mmthick titanium component was proposed,in which a column–cone combined heat source model was used to simulate the temperature field and a thermo-elastic–plastic model to analyze residual stress in a weld joint based on ABAQUS software.Considering the uncertainty of welding simulation,the computation was calibrated by experimental data of contour measurement method.Both test and simulated results show that residual stresses on the surface and inside the weld zone are significantly different and present a narrow and large gradient feature in the weld joint.The peak tensile stress exceeds the yield strength of base materials inside weld,which are distinctly different from residual stress of the thin Ti-6Al-4V alloy plates presented in references before.     

Microstructures and Tensile Properties of Ultrafine-Grained Ni–(1–3.5) wt% SiC_(NP) Composites Prepared by a Powder Metallurgy Route

Silicon carbide nanoparticle-reinforced nickel-based composites(Ni–Si CNP),with a Si CNPcontent ranged from1 to 3.5 wt%,were prepared using mechanical alloying and spark plasma sintering.In addition,unreinforced pure nickel samples were also prepared for comparative purposes.To characterize the microstructural properties of both the unreinforced pure nickel and the Ni–Si CNPcomposites transmission electron microscopy(TEM) was used,while their mechanical behavior was investigated using the Vickers pyramid method for hardness measurements and a universal tensile testing machine for tensile tests.TEM results showed an array of dislocation lines decorated in the sintered pure nickel sample,whereas,for the Ni–Si CNPcomposites,the presence of nano-dispersed Si CNPand twinning crystals was observed.These homogeneously distributed Si CNPwere found located either within the matrix,between twins or on grain boundaries.For the Ni–Si CNPcomposites,coerced coarsening of the Si CNPassembly occurred with increasing Si CNPcontent.Furthermore,the grain sizes of the Ni–Si CNPcomposites were much finer than that of the unreinforced pure nickel,which was considered to be due to the composite ball milling process.In all cases,the Ni–Si CNPcomposites showed higher strengths and hardness values than the unreinforced pure nickel,likely due to a combination of dispersion strengthening(Orowan effects) and particle strengthening(Hall–Petch effects).For the Ni–Si CNPcomposites,the strength increased initially and then decreased as a function of Si CNPcontent,whereas their elongation percentages decreased linearly.Compared to all materials tested,the Ni–Si CNPcomposite containing 1.5% Si C was found more superior considering both their strength and plastic properties.     

Directional Growth of Tin Crystals Controlled by Combined Solute Concentration Gradient Field and Static Magnetic Field

A new method was introduced to achieve directional growth of Sn crystals. Microstructures in liquid(Pb)/liquid(Sn) diffusion couples were investigated under various static magnetic fields. Results show that the β-Sn crystals mainly reveal an irregular dendritic morphology without or with a relatively low static magnetic field(B0.3 T). When the magnetic field is increased to 0.5 T, the β-Sn dendrites close to the final stage of growth begin to show some directional character. With a further increase in the magnetic field to a higher level(0.8–5 T), the β-Sn dendrites have an enhanced directional growth character, but the dendrites show a certain deflection. As the magnetic field is increased to 12 T, the directional growth of the β-Sn dendrites in the center of the couple is severely destroyed. The mechanism of the directional growth of the β-Sn crystals and the deflection of the β-Sn crystals with the application of static magnetic field was tentatively discussed.     

电化学噪声数据处理方法概述

综述了常见的电化学噪声数据处理方法,介绍了直流趋势剔除、统计分析、快速傅立叶变换(FFT)法计算功率谱密度(PSD)以及小波变换处理电化学噪声信号的基本过程,并阐释了各种数学处理及所得参数的物理意义。