一步电沉积法制备Ni-Mo-Nd/NF复合电极及其析氢性能研究

目的 采用一步恒电流沉积法在泡沫镍基底上制备出镍-钼-钕三元析氢电极,提高碱性条件下的析氢性能。方法 使用电化学工作站研究工艺参数对Ni-Mo-Nd/NF析氢电极性能的影响,同时制备Ni-Mo/NF析氢电极,使用扫描电镜(SEM)、X射线衍射分析仪(XRD)、能谱仪(EDS)和X射线光电子能谱(XPS)对合金镀层表面形貌、相结构、元素含量及成键状态进行表征。通过线性扫描伏安法(LSV)、循环伏安法(CV)及电化学阻抗技术(EIS)测试电极析氢性能。结果 最佳工艺参数为:pH=4.5,电流密度30 mA/cm²,沉积时间60 min,温度30 ℃。在1.0 mol/L KOH溶液中,Ni-Mo-Nd/NF电极在10 mA/cm²下的析氢过电位仅为73 mV,Tafel斜率为147 mV/dec,表明析氢反应机理遵循典型的Volmer-Heyrovsky步骤。此外,Ni-Mo-Nd/NF电极在长时电解24 h时电流密度保持稳定,2 000次循环伏安测试后,催化剂的活性衰减微小。结论 稀土元素Nd的掺杂,能够细化电极表面的球形颗粒并提高电极表面粗糙度,从而提升电极的比表面积,为析氢反应提供更多的活性位点,利于析氢反应效率的提高。由于三元合金的协同作用,与二元合金Ni-Mo/NF相比,Ni-Mo-Nd/NF三元合金电极显示出更优异的HER催化性能。     

电沉积工艺参数对镍-钼-锌三元合金电极析氢催化性能的影响

目的采用直流电沉积法在铜基底上制备镍-钼-锌三元合金电极,提高电解水析氢过程中阴极电极的效率。方法使用电化学工作站研究不同电沉积工艺参数对镍-钼-锌三元合金镀层析氢性能的影响,使用扫描电镜(SEM)、X射线衍射分析仪(XRD)、能谱仪(EDS)对合金镀层表面形貌、相结构及元素含量进行表征。通过线性扫描伏安法(LSV)对析氢过电位进行测量,采用塔菲尔极化获得塔菲尔斜率,采用电化学阻抗法(EIS)表征合金镀层的析氢催化性能。结果最佳工艺参数为:温度45℃,p H=10.5,电流密度100 mA/cm~2。该合金在10 mA/cm~2下相对氢标电位仅为139 mV,塔菲尔斜率为103 mV/dec,活化电极电阻(Rct)随着电压的升高而降低。合金中Ni、Mo和Zn的原子比分别为68.23%、10.09%和21.68%。合金镀层为非晶结构,表面是纳米级颗粒堆叠而成的粗糙形貌。结论不同的工艺参数对Ni-Mo-Zn电极析氢性能有着重大影响,其析氢性能随着p H值的升高而上升,随着电流密度的升高而先增后减,随着电沉积温度的升高而上升。Ni-Mo-Zn高的析氢性能源于其元素协同作用、非晶结构和粗糙表面。     

电沉积Ni-Fe-P非晶合金析氢阴极材料及其去合金化处理

目的 提高Fe电极的催化析氢性能。方法 较低温度条件下,在Fe基体表面电沉积一层非晶态Ni-Fe-P镀层,探究沉积电流密度、去合金时间等参数对Ni-Fe-P/Fe电极在碱性电解质中的电催化析氢反应的影响。通过扫描电镜、能谱、X射线衍射对镀层的形貌、元素分布、物相进行分析。在碱性溶液中,利用电化学工作站对电极进行一系列性能测试。结果 在沉积温度为10 ℃的条件下,于Fe电极表面成功制备出了致密且元素分布均匀的Ni-Fe-P非晶合金镀层。获得的Ni-Fe-P/Fe电极电催化性能均优于Fe电极,其中电流密度30 mA/cm2条件下制备的Ni-Fe-P/Fe电极在析氢电流密度为10 mA/cm2时的过电位为174.2 mV,比Fe电极低约466.2 mV。在相同条件下制备的Ni-Fe-P/Fe电极,经240 s去合金化处理,电极过电位仅为121.6 mV,比Fe电极低约518.8 mV。结论 电沉积的Ni-Fe-P非晶合金镀层可以显著提高Fe电极的析氢性能。随着沉积电流密度的增加,Ni-Fe-P/Fe电极的析氢过电位减小,双电层电容和电化学工作表面积增大。对镀层进行适当的去合金化处理,形成的三维多孔结构可以减小电极的电荷转移电阻,有效降低电极的析氢过电位。     

电沉积非晶/纳米晶Ni-Mo-La合金电极的析氢性能

在非晶/纳米晶Ni-Mo合金镀液中添加适量的LaCl3溶液,获得了非晶/纳米晶混合结构的Ni-Mo-La合金电极。结果表明:稀土La元素的加入,有利于镀层Mo含量的提高,形成非晶态Ni-Mo合金,细化镀层晶粒,减小镀层微应变,并使镀层表面积增加。在25℃、7 mol/L的NaOH溶液中的电化学实验表明:Ni-Mo-La合金电极比Ni-Mo合金电极具有更高的析氢催化活性,在电流密度为150 mA/cm2条件下,Ni-Mo-La合金电极的析氢过电位比Ni-Mo合金电极的降低了约80 mV。Ni-Mo-La合金具有储氢材料的特性,其析氢过程含有吸氢—储氢—脱附的过程。     

多级结构FeS@Ni3S2/NF催化电极的一步水热法制备及析氧行为

通过简单一步水热法在泡沫镍表面原位生长多孔纳米片自组装成纳米花结构的FeS@Ni₃S₂/NF催化电极。借助X射线衍射仪(XRD)、X射线光电子能谱(XPS)、透射电镜(TEM)等进行物相及结构表征,并测试催化电极在1 mol/L KOH溶液中的电催化析氧(OER)性能。电化学测试结果表明：FeS@Ni₃S₂/NF-1.2电极在100 mA·cm-2电流密度下仅需278 mV的过电位,且具有较低的Tafel斜率(22.71 mV/dec),与纯NF(493 mV,214.65 mV/dec)、纯Ni₃S₂(327 mV,91.87 mV/dec)以及IrO2/NF(385 mV,172.93 mV/dec)相比,其优势明显。证明具有独特多孔结构的FeS@Ni₃S₂/NF纳米片自组装成的纳米花可以作为一种贵金属基电催化剂的理想替代品。     

不同搅拌方式对Ni-Fe-Co镀层组织结构和电催化析氢性能的影响

目的得到具有更高电催化析氢活性的Ni-Fe-Co镀层电极。方法采用不同的搅拌方式电沉积制备了Ni-Fe-Co镀层,通过SEM、EDS和XRD等分析手段研究了其微观形貌、成分及物相组成,并利用电化学测试分析技术探究了不同搅拌方式对其电催化析氢活性的影响。结果三种镀层电极均为简单固溶体BCC结构,其中磁力搅拌条件下制得的镀层电极的表面组织更致密均匀,具有更大的真实表面积,分别为不搅拌和超声搅拌下的6倍和2倍。在电位为-1.6 V时,磁力搅拌条件下制得的镀层电极析氢电流密度达到173m A/cm~2,明显高于另外两种镀层电极,其交流电流密度为45.9μA/cm~2,分别是不搅拌和超声搅拌条件下的2倍和3倍。结论磁力搅拌有效地增大了镀层的比表面积,进而提高了镀层的电催化析氢活性。     

添加剂Pr2O3和Er2O3对电沉积Ni-S合金电极性能的影响

以氧化镨、氧化铒为添加剂,在泡沫镍基体上电沉积制备Ni-S镀层电极。对镀层的表面形貌、镀层结构、电沉积行为及镀层的电化学性能进行研究。结果表明：电镀液中添加稀土氧化物后电沉积过程的阴极极化增强,沉积层晶粒细化,比表面积增大,因而电极的析氢过电位降低;其中,添加Pr203的Ni-S镀层在250mA／cm2下碱性水电解时过电位降低达37mV,且该镀层电极在碱性介质下具有较高的析氢活性和耐腐蚀性能,在100h水电解实验中表现出较强的稳定性。     

镀液pH值对Ni-Mo-C合金镀层析氢性能的影响

通过电沉积法在纯铜表面制备Ni-Mo-C合金镀层,采用能谱仪(EDS)、扫描电镜(SEM)、线性伏安扫描法(LSV)和电化学阻抗谱(EIS)等方法研究了镀液pH值对Ni-Mo-C合金镀层元素组成、沉积速率、表面形貌及析氢性能的影响。结果表明:随着镀液pH值的增大,镀层中Ni、C的含量先减小后增大,Mo的含量先增大后减小;当镀液pH=4.5时,电沉积速率最大;能量因素和几何因素的优化均可增强合金镀层的析氢性能,能量因素对析氢性能的促进作用大于几何因素;当镀液pH=4.5时,镀层中Mo含量最大,吸附氢的脱吸附能力最强,析氢性能最好。     

柠檬酸钠对Ni-Sn-Mo合金电沉积机理及析氢行为的影响

目的 在酸性柠檬酸钠体系中,研究了柠檬酸钠对Ni-Sn-Mo合金电沉积机理的影响,明确最大电极反应速率和析氢性能最好的合金镀层对应的柠檬酸钠浓度。方法 采用循环伏安法、电化学阻抗谱、计时电流法和阴极极化曲线,对不同柠檬酸钠浓度下Ni-Sn-Mo合金电沉积行为及析氢性能进行研究,采用扫描电镜对Ni-Sn-Mo合金的表面形貌进行表征,并用能谱仪检测合金的成分。结果 由循环伏安曲线得出Ni-Sn-Mo合金的电沉积是一个不可逆过程,当柠檬酸钠浓度为0.2 mol/L时,合金共沉积还原峰的电位最正（-0.96 V(vs. Ag/Ag+)）。由电化学阻抗谱可知,当柠檬酸钠浓度为0.1 mol/L时,在低频端出现扩散特征;当柠檬酸钠浓度为0.2~0.4 mol/L时,反应不受扩散影响;当柠檬酸钠浓度为0.2 mol/L时,极化电阻（Rp）达到最小值（11 718.1 Ω?cm2）,电极反应最容易发生。由计时电流曲线可知,随着柠檬酸钠浓度的增大,Ni-Sn-Mo合金晶核形成始终遵循连续成核规律。由SEM和EDS分析表明,随着柠檬酸钠浓度增大,Ni-Sn-Mo合金的晶粒尺寸先减小后增大;随着合金中Sn含量增加,合金的晶粒由胞状转变为不规则形状。由阴极极化曲线和电化学阻抗谱可知,当柠檬酸钠浓度为0.1 mol/L时,析氢电位（-1.05 V）最正,电荷转移电阻（4.906 Ω?cm2）最小,析氢性能最好,从能量因素和几何因素上都改善了合金的析氢性能。结论 当柠檬酸钠浓度为0.2 mol/L时,还原峰电位最正,电极反应最容易发生。在Ni-Mo合金镀层中添加Sn,增加了镀层的比表面积,并且提高了电子传输速率,有利于析氢性能的提高。     

泡沫基材-Ni-石墨烯复合镀层制备及电催化析氢性能研究

目的 采用电沉积技术在泡沫基材上沉积制备Ni-石墨烯复合镀层,期望借助泡沫基材的三维多孔结构和石墨烯的超高比表面积来改变复合材料的表面状态,进而获得高镀层的电催化析氢性能。方法 采用电沉积技术将石墨烯作为第二相粒子沉积,制备了泡沫基材-Ni-石墨烯复合电极,通过SEM和EDS研究了其微观形貌及成分,并利用电化学工作站完成了镀层电极的极化曲线、交流阻抗和电解水稳定性测试,使用控制变量法探究了镀层厚度、镀液石墨烯浓度和基材形貌对镀层电催化析氢活性的影响。结果 SEM和EDS表征发现,镀层表面形貌受镀液中石墨烯浓度影响较大,石墨烯作为第二相嵌入镀层后,明显改变了复合镀层的表面形貌,其存在形态为颗粒状,在150 mg·L^–1时颗粒堆积最多。进一步利用电化学分析技术探究了镀层厚度、镀液石墨烯浓度和基材形貌对电极电催化析氢性能的影响,发现在一定范围内,不同厚度镀层的电催化析氢活性基本相同;石墨烯质量浓度为150mg·L^–1时制得的电极的电催化析氢性能最优,析氢过电位为211.2m V(vs.RHE),且电解水稳定性良好;泡沫基材镀层的电催化析氢活性明显优...     

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.     

Growth Kinetics of Single Inclusion Particle in Molten Melts

On the basis of the single-particle framework, a new theory on inclusion growth in metallurgical melts is developed to study the kinetics of inclusion growth on account of reaction and collision. The studies show that the early growth of inclusion depends on reaction growth and Brawnian motion collision, and where the former is decisive, the late growth depends on turbulence collision and Stokes＇ collision, and where the former is dominant; collision growth is very quick during the smelting process, lessened in the refining process, but nearly negligible in the continuous casting process.     

Theoretical Analysis for the Motion and Temperature of Melt Droplets in Spray Degassing Process

The motion of melt droplets in spray degassing process was analyzed theoretically. The height of the treatment tank in spray degassing process could be determined by the results of theoretical calculation of motion of melt droplets. To know whether the melt droplets would solidify during spraying process, the balance temperature of melt droplets was also theoretically analyzed. Then proof experiments for theoretical results about temperature of melt droplets were carried. In comparison, the experimental results were nearly similar to the calculation results.     

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.