La、Ba的添加对Pd/Y2O3-ZrO2催化氧化CH4性能的影响

以浸渍法制备了1.0%Pd/Y2O3-ZrO2催化剂,考察了Pd负载过程中La和Ba的添加对Pd/Y-ZrO2催化氧化CH4性能的影响,用BET、XRD、CO脉冲、TEM和H2-TPR等方法对所制备的催化剂进行表征。结果表明,La和Ba的添加降低了Pd/Y2O3-ZrO2催化剂氧化CH4的活性。催化剂中活性金属的分散度及体相PdO的还原性影响催化剂对CH4的氧化活性,La、Ba的添加降低了Pd/Y2O3-ZrO2催化剂中活性金属Pd的分散性,使Pd在高温老化后更容易团聚,同时增强了PdO与载体的相互作用,使PdO不容易被还原。     

La助剂对Pd-AL2O3催化C3H8氧化性能的研究

采用不同稀土La前驱体浸渍掺杂改性Pd/γ-Al2O3催化剂,利用多功能催化性能评价装置测试不同催化剂的C3H8催化氧化性能,并通过H2-TPR、XRD、XPS等手段对催化材料进行结构表征,结果表明：La能促进贵金属钯分散,增强钯与载体相互作用,稳定高活性Pd2+物种,从而提高了催化剂的C3H8催化氧化性能。在选用不同La前驱体改性的Pd/γ-Al2O3催化剂中,硝酸镧改性效果最佳,能更好地促进活性金属钯的分散和Pd2+高活性物种的稳定。相比Pd/γ-Al2O3,La改性催化剂均降低了C3H8和NO的反应转化温度。选用不同La前驱体对催化活性影响存在差异的主要原因是La前驱体添加而引起的金属-载体相互作用和活性贵金属钯的分散状态变化。     

金属蜂窝负载Pd催化甲烷部分氧化制合成气

采用浸渍法制备负载金属Pd(其中金属Pd含量0.6g/L)活性组分的金属蜂窝载体催化剂,应用于甲烷部分氧化制合成气。实验表明,焙烧温度为950℃的催化剂较600℃的催化剂甲烷转化率、CO和H2的选择性更高,焙烧温度为950℃的催化剂在反应温度800℃,GHSV=1×105ml/g·h条件下,甲烷转化率为91%,CO和H2的选择性分别达到90%和89%。用SEM与XPS对催化剂进行表征,结果表明,950℃焙烧催化剂并没有出现明显的烧结现象,且可能由于更多零价Pd的出现,使得该催化剂的性能更好。由于金属蜂窝载体优良的导热性,对950℃焙烧温度制备的金属蜂窝催化剂,催化剂床层的飞温点温度小于880℃,可以解决其它类型催化剂在甲烷部分氧化反应中出现的飞温问题,具有一定的工业化意义。     

Pd基催化剂的性能对比

在催化剂中添加镧可抑制活性位的长大和PdO颗粒的分解,增强催化剂的催化活性和热稳定性。研究了老化前和老化后的Pd／CZ／La—Al2O3系列、Pd／La—Al2O3、Pd／CZ催化剂,Pd／CZ／La—Al2O3系列中Pd、CZ（Ce1-xZrxO2）、La—Al2O3材料添加顺序不同对催化剂涂层性能的影响。对于老化前和老化后的催化剂,Pd、CZ、La—Al2O3材料添加顺序对催化活性影响较小,Pd／W有利于CO转化,Pd／CZ有利于HC、NOx转化。通过XRD、XPS、化学吸附仪、BET表征证明了老化过程中发生了催化失活。     

不同载体负载的Pd催化剂上CO氧化性能比较

采用沉淀-沉积法制备了一系列不同载体负载的纳米Pd催化剂.以CO氧化为模型反应,考察了载体差异对催化剂CO催化氧化性能的影响.结果发现,载体对Pd催化剂的CO催化氧化性能影响较大,以分子筛为载体的Pd催化剂的活性明显优于金属氧化物担载的催化剂.同时,考察了反应温度、时间、空速及加湿条件等对催化剂CO氧化活性的影响,并利用XRD和XPS等测试手段对催化剂体相结构和表面状态进行了表征.结果表明:催化剂的活性随着反应温度的升高而增加,随着空速的增加而降低.XRD和XPS结果证实不同载体负载的催化剂其表面活性Pd物种的状态有较大差异,分子筛载体利于活性Pd物种向催化剂表面迁移,这种作用以及Pd物种的高分散与催化剂的活性直接相关.     

贵金属和载体对催化剂催化脱氧裂化性能的影响

采用浸渍法制备了一系列分别负载活性组分Pt,Pd,Ru的γ-Al2O3载体催化剂和分别以固体酸γ-Al2O3,Si O2-Al2O3,USY-Al2O3为载体的Pd催化剂。通过XRD、HRTEM、H2-TPR、NH3-TPD、BET等分析表征技术和以油酸甲酯为模型化合物的反应体系,考察了贵金属及载体性质对催化剂催化加氢脱氧性能和催化裂化性能的影响。结果表明:贵金属及其粒子大小是影响催化剂催化加氢脱氧活性的主要因素;载体的酸强度、酸量是影响催化剂催化裂化性能的主要因素。同时,该性能也受比表面积和孔结构特征的影响;Pd/USY-Al2O3在系列催化剂中表现出了良好的催化加氢脱氧活性和最佳的催化裂化活性。     

Pd/ZrO2-Al2O3催化剂中载体制备对CH4转化活性的影响

为推动ZrO2-Al2O3在天然气汽车尾气净化催化剂中的实际应用,并阐明其制备条件对负载催化剂转化活性的影响机制,文章以ZrO2-Al2O3复合氧化物为载体,采用等体积浸渍法制备了Pd/ZrO2-Al2O3催化剂,并在连续流动固定床反应器上研究了ZrO2-Al2O3复合氧化物的制备对催化剂低温CH4氧化活性的影响。结果表明：制备方法中,相比于浸渍法和胶溶法,沉淀法更能提高催化剂活性;锆源、铝源优选中,以Zr(NO3)4为锆源、拟薄水铝石为铝源时能获得较高的催化活性;组分配比中,以w (ZrO2): w (Al2O3)=10:90的催化活性最高。XRD、低温N2吸附、CO脉冲吸附的结构表征表明,ZrO2-Al2O3复合氧化物的大的比表面积、孔容、孔径是促进贵金属Pd分散,提升催化剂低温CH4转化活性的关键因素。     

Ce改性ZSM-5分子筛载Pd催化剂的CeO2-Pd协同作用研究

采用XRF、XRD、SEM和CH4-TPR表征手段,研究了Ce改性ZSM-5分子筛载Pd催化剂在CO、CH4氧化过程中的CeO2-Pd协同作用。结果表明,经Ce改性后ZSM-5分子筛的载Pd量提高;Pd/Ce-ZSM-5催化剂对 CH4的起始吸附温度降低;Pd/Ce-ZSM-5催化剂中 Ce 主要以 CeO2形态存在。Pd是CO的催化氧化活性物种,CeO2-Pd协同作用可促进CO的氧化。Pd和PdO均是CH4的催化氧化活性物种,CeO2的供氧-储氧特性有助于Pd→PdO的转化,CeO2与Pd的相互作用使Pd/Ce-ZSM-5催化剂具有高的CO和CH4催化氧化活性。     

储氧量及空燃比对钯催化剂选择氧化CH_4和CO的影响

制备了Pd/AlLaZrTiO_x(Pd/A),Pd/AlCeZrLaO_x(Pd/CZ)和Pd/(AlLaZrTiO_x+AlCeZrLaO_x)(Pd/CZA)3种催化剂,用热分析仪测试其储氧值(OSC),用红外光谱仪测试在过量空气系数(α)分别为0.8、1.0和1.4时3种催化剂对CH_4和CO的选择氧化性能。结果表明,催化剂的储氧性能和空燃比氛围均对CH4和CO的选择氧化性能有较大影响。储氧能力较差的Pd/A和Pd/CZA催化剂在α=1(理论空燃比)时有利于CH_4的催化燃烧,在α=1.4(富氧条件)时对CO的完全氧化有利;储氧能力较好的Pd/CZ催化剂对CH_4的催化燃烧和CO的完全氧化均在α=1左右时比较有利。贫氧条件下,Pd/CZ催化剂有利于CH_4的催化燃烧和CO的完全氧化;富氧条件下,Pd/CZA催化剂有利于CH_4的催化燃烧和CO的完全氧化;在理论空燃比附近,Pd/A催化剂对CH_4的催化燃烧较好,Pd/CZ催化剂对CO的完全氧化较好。     

SnO_2纳米棒负载Pd-Sb催化甲酸电氧化

采用溶剂热法制备了SnO_2纳米棒载体,用溶剂热还原法制备了Pd/SnO_2催化剂和不同Pd/Sb原子数比的系列PdSb/SnO_2复合催化剂。用XRD、SEM、TEM、EDS等手段对样品进行分析表征,并以循环伏安法对比评价催化剂对甲酸的电催化氧化性能。表征结果表明,制备所得SnO_2纳米棒载体为针状,大小均匀,平均直径为100 nm;负载所得催化剂中活性粒子大小约为13.5 nm,掺杂Sb后,粒径约为9.5 nm。电催化氧化性能对比结果表明,Pd/Sb原子数比为4:1的Pd_4Sb/SnO_2复合催化剂对甲酸的氧化具有较好的催化能力,当E=0.25 V(vs SCE)时,Pd_4Sb/SnO_2上甲酸氧化的峰电流密度达到25 mA/cm~2,远远高于Pd/SnO_2催化剂。     

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).     

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.     

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.     

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。