柠檬酸盐水溶液中二价钴的电化学还原过程（英文）

采用循环伏安法(CV)和电化学交流阻抗法(EIS),研究不同柠檬酸盐浓度和pH下钴的电化学还原过程。结果表明:在组成为0.05 mol/L CoSO4·5H2O、0.20 mol/L Na2SO4和0~0.40 mol/L C6H5O7Na3·2H2O,pH为3~9的溶液中,二价钴以游离Co2+离子和[Co(C6H5O7)]配合物两种形态存在,并在电极表面被还原。溶液的pH对钴的电化学还原过程有显著的影响。当柠檬酸盐溶液的pH为3时,钴主要以游离Co2+离子的形态被还原;当溶液为弱酸性(pH=4~6)时,钴主要以[Co(C6H5O7)]-的形态被还原为Co0,还原过程分两步进行,中间产物在电极表面发生吸附;当柠檬酸盐水溶液的pH大于7时,形成的柠檬酸钴配合物主要是[Co(C6H5O7)]-和[Co(C6H4O7)]2-,这两种配合物非常稳定,其还原电位负于溶液的析氢电位,因此难以从该溶液中还原得到Co0。     

油酸钠作用下金红石的浮选行为及作用机理

通过纯矿物试验,研究金红石在油酸钠为捕收剂体系中的浮选行为。当油酸钠用量为20 mg/L、pH值为6~8时,金红石浮选回收率均在80%以上;当pH=7.5时,金红石浮选回收率最高,为85.27%。Zeta电位及红外光谱测试结果表明,油酸钠在金红石表面主要发生了化学吸附,同时也可能存在物理吸附。根据油酸钠溶液化学计算,当pH值为6~8时,油酸钠溶液的优势组分为C17H33COO-和(C17H33COO)22-;而金红石表面Ti4+的羟基化合物主要以[Ti(OH)2]2+和[Ti(OH)3]+形式存在。结合金红石在油酸钠捕收剂体系中的浮选行为,油酸钠在金红石表面的相互作用原理是,金红石表面解离的Ti4+在水溶液中形成羟基化合物[Ti(OH)2]2+和[Ti(OH)3]+络合在金红石表面成为浮选的活性质点,再与C17H33COO-和(C17 H33COO)22-作用形成Ti(C17H33COO)4,从而使金红石疏水上浮;油酸(C17H33COOH(aq))分子和离子-分子缔合物(C17H33COOH·C17H33COO-)的物理吸附也可能存在。     

HNO_3-Al(NO_3)_3络合浸出包头稀土精矿中的氟元素及其络合机理

根据Al3+与F-能形成稳定的络合离子[Al F6]3-,采用HNO3-Al(NO3)3溶液络合浸出包头稀土精矿中的氟元素。讨论HNO3浓度、Al(NO3)3浓度、液固比、搅拌速度、温度和搅拌时间等工艺条件对氟浸出的影响。结果表明:在HNO3浓度为3 mol/L、Al(NO3)3浓度为1.5 mol/L、液固比(mL/g)为30:1、搅拌速度为300 r/min、温度为100℃、搅拌时间为90 min的条件下,稀土精矿中氟浸出率达到97.59%,从而使氟碳铈矿进入溶液中,达到与独居石分离的目的。F-与Al3+的络合机理研究表明:F-与Al3+能形成配位数是1~6的复杂稳定配合物,并随着氟铝比的增大,氯铝配合物向高配位方向移动。     

正丁基苯并噻唑亚砜从硫脲介质中萃取金的机理研究

研究了正丁基苯并噻唑亚砜 (ASO)萃取酸性硫脲介质中金的机理。考察了[H+]和萃取剂浓度对分配比的影响 ,通过红外光谱法确定了其萃取过程为酸性离子缔合机理 ,萃取反应为 :ASO +H++Au(Tu) +2 +SO2 -4 [Au(Tu) 2 HSO4·ASO]采用斜率法确定萃合物的组成为Au[SC(NH2 ) 2 ]2 HSO4·ASO。并通过电导法判断在萃合物中Au(Tu) +2 与SO2 -4 以离子对形式存在。     

Fe2+-Ni2+-NH3-NH4+-C2O42-H2O体系的沉淀配合平衡热力学

针对草酸盐配位共沉淀热分解还原法制备超细铁镍合金粉过程中Fe2+-Ni2+-NH3-NH4+-C2O42--H2O体系的溶液平衡建立热力学分析模型,并根据模型进行相关计算,揭示反应体系中各物质随pH值、氨及草酸浓度的变化关系。结果表明:溶液中的Fe主要以[Fe(C2O4)n]2 2n络合物形式存在,而铁氨络合物含量很低。当氨含量较低时,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在;氨含量较高时,在酸性条件下,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在,在碱性条件下,则主要以[Ni(NH3)n]2+存在。低pH值下,Ni的沉淀率较Fe的高,而高pH值下,Ni的沉淀率则较Fe的低。     

Ni^2＋-C2H8N2-2-24CO-H2O体系的热力学分析及Ni微米纤维的制备

根据同时平衡和质量平衡原理,建立了Ni2＋-C2H8N2-2-24C O -H2O体系的沉淀-配合平衡热力学模型,并对该模型进行计算来揭示该体系中各物种浓度随pH值、草酸及乙二胺浓度的变化规律。结果表明,当pH〈1和pH=1-6时,溶液中的Ni分别主要以游离Ni2＋及[Ni（C2O4）n]2-2n形式存在。当pH〉6时,Ni2＋与乙二胺的配合作用占优势。当用乙二胺作配位剂,采用草酸盐沉淀法制备了 Ni 微米纤维前驱体,并讨论了乙二胺在前驱体生长机制中的作用。将前驱体在N2和H2混合气氛中热分解还原,可得到直径0.2-1μm、长径比20-30的Ni微米纤维。     

溶液配位化学研究:IX.Pt(Ⅱ)-Phen-PCA体系

用pH电位滴定法测定了含 1 ,1 0 -邻菲咯啉 (Phen )和羧酸 (CA )配体的三元混配配合物Pt(Phen) (CA ) +体系的稳定常数 ,比较和讨论了各种三元混配配合物之间的稳定性差异。实验结果表明 :在三元混配配合物Pt(Phen) (PCA) +中 (PCA为苯基羧酸 )存在分子内芳环堆积作用 ,堆积程度依赖于苯基和配位的羧酸根之间的亚甲基数目 ,其中以 2 -苯乙酸和 3-苯丙酸与邻菲咯啉为最佳堆积。     

铑(Ⅲ)氯水配合物的制备及紫外可见光谱的研究

采用封管氯化的方法[1 ] ,制得铑的标准溶液。在一定条件下处理H3[RhCl6]溶液 ,获得K2 [Rh(H2 O)Cl5]、K3[RhCl6]和 [Rh(H2 O) 6]·(ClO4) 3种态。以K2 [Rh(H2 O)Cl5]和K3[RhCl6]为起始物 ,利用国产 71 7阴离子树脂 ,分别得到trans - [Rh(H2 O) 4 Cl2 ]+、cis- [Rh(H2 O) 4 Cl2 ]+、mer- [Rh(H2 O) 3Cl3]、fac- [Rh(H2 O) 3Cl3]和cis- [Rh(H2 O) 4 Cl4]- 种态。研究它们的紫外 -可见吸收光谱发现 ,随着配位内界水分子数的增加 ,其特征吸收峰表现为紫移。通过分析和研究它们的极性及特性吸收峰 ,提出了铑 (Ⅲ )氯水配合物新的鉴别方法。     

一种新的铽发光配合物的合成、晶体结构及表征

在水热合成条件下合成一个新的吡啶-3,5-二羧酸的稀土铽配合物[Tb2(pydc-3,5)3(H2O)9]n3nH2O,通过X射线单晶衍射、元素分析和红外等手段的表征确定该化合物的组成和晶体结构。结果表明,吡啶-3,5-二羧酸(pydc-3,5)配体与稀土金属Tb形成了一维链状配位聚合物,中心稀土金属有两种配位形式,每个金属均与氧原子形成九配位的结构。配体中的羧酸根采用两种配位方式,即单齿配位和双齿配位。同时配合物能发出三价铽离子的特征绿色荧光,荧光光谱的研究表明,配合物表现出很好的荧光性能。     

2,2,2-胺三乙酰-苯胺及其稀土配合物的合成、表征与荧光性质

为了研究三脚架型配体稀土配合物的组成、可能的配位状态及荧光性质,合成了三脚架型配体——2,2,2-胺三乙酰苯胺（L）及其6个稀土配合物。用红外光谱,核磁共振波谱,元素分析,差热-热重,摩尔电导等方法表征了配体及其配合物的组成、配位形式及荧光性质。结果表明,L的化学式为C24H24N4O3,与稀土硝酸盐配位,且n（L）∶n（Re）=1∶1,在DMF中为2∶1型电解质,其中,2个NO3-均与金属离子以单齿形式配位;荧光分析表明Tb（Ⅲ）配合物的荧光强度与溶液的pH值有关,并且在中性溶液中荧光强度最大;在分子偶极矩较大的溶剂中,荧光强度最强。说明该配体是较好的稀土荧光敏化剂。     

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).     

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.