纤维状超细银粉前驱体制备热力学分析

根据同时平衡原理和质量平衡原理,从理论上推导出了Ag(Ⅰ)-C2O42--NH3-NH4+-H2体系中金属银离子和草酸盐在水溶液中热力学平衡的数学模型,计算并绘制出该体系的lg[Ag]T-pH图。在此基础上,分析液相沉淀过程中溶液的lg[Ag]T与pH之间的关系并推断出制备纤维状银粉前驱体粉末的理想pH值为5.0~6.0之间,为液相沉淀过程的实验操作提供了理论依据。最后通过验证实验证明了热力学计算结果的准确性。     

形貌控制法合成一种新型的纤维状镍钴合金粉末前驱体(英文)

通过选择性控制合成条件,制备一种新型的纤维状镍钴合金粉末前驱体。该前驱体中镍、钴摩尔配比精确。采用X-射线衍射仪(XRD)、扫描电镜(SEM)、红外光谱(FT-IR)和能谱(EDS)研究前驱体粉末的成分与形貌;考察溶液pH值、反应温度、金属离子浓度和表面活性剂对前驱体粉末的形貌和分散性的影响。结果表明:前驱体的形貌取决于前驱体中氨的含量,这种纤维状前驱体为一种复杂的含氨草酸镍钴复盐。形貌控制合成纤维状镍钴合金粉末前驱体的最佳条件为:氨作为配位剂和pH值调节剂,草酸为沉淀剂,反应温度为50～65°C,镍、钴离子总浓度为0.5～0.8mol/L,PVP为分散剂,溶液pH值控制在8.0～8.4.     

高硬度纳米镍钴合金镀层的制备与表征

采用植酸与有机胺盐复合添加剂制备了纳米镍钴合金镀层.试验表明,在较低的溶液pH值和电流密度(2.4～3.2A/dm2)时,镍钻合金镀层晶粒度为20～50nm.采用扫描电镜(SEM)、X射线分析仪(XRD)和透射电镜(TEM)等技术对镀层进行了表征,当纳米镍钴镀层中钻含量达到20%时,镀层硬度为577.2HV.     

煅烧方式对草酸盐前驱体制备氧化锆性能的影响

采用非线性加热法煅烧锆、钇的草酸盐前驱体, 制备了8%Y2O3(摩尔分数)稳定ZrO2(8YSZ)超细粉末. 研究了金属离子与草酸的摩尔比及热处理方法对8YSZ的晶体结构、晶粒大小、形貌、比表面积、粒子团聚的影响. 通过改变不同温度范围的加热速度来优化草酸盐前驱体热分解工艺. 采用优化前驱体热分解工艺即非线性加热法, 于600～700.℃煅烧得到的粉末为等轴晶形, 粒子大小在90～100.nm之间, 粒子间仅有较弱的软团聚. 煅烧过程晶粒生长动力学的研究表明: 当煅烧温度高于700.℃时, 晶粒生长的质量传输受晶粒扩散过程控制; 低于700.℃时, 晶粒生长的质量传输由表面扩散过程控制.     

钴含量对电铸镍钴合金模芯微纳结构复制质量的影响

为探明电铸液中钴含量对仿荷叶表面镍钴合金模芯微纳结构复制质量的影响,采用阴极竖直旋转的微电铸技术,制备不同钴含量的仿荷叶表面镍钴合金模芯,采用扫描电子显微镜（SEM）、能谱仪（EDS）分析仿荷叶表面镍钴合金模芯表面的复制质量及成分。结果表明：由于铸层表面内应力的影响,在常规镍电铸中添加钴以后,仿荷叶镍钴合金模芯表面出现了波纹型的褶皱;观测模芯微观形貌发现其表面微米级的孔洞沿特定方向出现不同程度的拉伸,随着电铸液中钴含量（体积分数）的增加,拉伸程度先增加后降低（拉伸程度：钴含量0 g/L<钴含量40 g/L<钴含量10~30 g/L）;铸层中添加元素钴有利于晶粒细化,随电铸液中钴含量的增加,模芯表面微纳结构越细小,复制质量越高。     

合金熔体遗传现象的热力学分析

】从热力学角度阐述了在液态无限互溶的合金熔体中微观不均匀结构形成的可能性。当不均匀体尺寸在1 ～10nm 时,在合金熔体中形成相对稳定的原子团簇,可以把它视为传递结构信息的遗传因子,并讨论了从基料到熔体,再从熔体到铸锭遗传规律的形成实质,为分析合金熔体遗传现象产生的原因提供了依据。     

真空碳热还原制备Mg-Li合金热力学分析

提出了真空碳热还原制备Mg-Li合金的新思路,并对还原反应进行了热力学分析,研究了还原反应的反应式、吉布斯自由能及临界还原温度。结果表明:真空碳热还原制备Mg-Li合金具备热力学可行性,且其吉布斯自由能随真空度和反应温度的升高而降低;相同真空度下,该反应的临界反应温度低于真空碳热还原制备金属Mg、金属Li的临界温度,反应更容易进行;当真空度为10 Pa,Li_2O的相对比例为0.1时,真空碳热还原制备Mg-Li合金的临界反应温度为1345 K;在常规皮江法(真空硅热还原法)制镁的反应条件下,不论反应物料中Mg O、Li_2O相对比例为多少,真空碳热还原制备Mg-Li合金均具有热力学可行性。     

电镀 Cu-W-Ni 合金的热力学分析

借助25℃下的Cu-H2O,Ni-H2O和W-H2O的E-pH图,说明了电镀Cu,W,Ni的可能性及范围,并重点分析了电镀Cu-W-Ni合金的可能性。Cu-Ni能在Cu-H2O与Ni-H2O系E-pH图叠合形成的共沉积区里析出。因Cu-H2O与W-H2O系的E-pH图叠合时无法形成Cu-W的共沉积区,Cu-W不能在其对应离子的水溶液中析出,但Ni-W能在Ni2+,WO42-水溶液里诱导共沉积。理论和实验证明,在含Cu2+,Ni2+,WO42-的水溶液中能电镀制备Cu-W-Ni合金。     

Fe3Al合金的流动性及热力学分析

Fe3Al合金是优秀的耐热工程材料,在测定合金流动性工艺参数的基础上,用热力学观点分析了主要添加元素Al对合金流动性的影响规律。根据合金凝固动态曲线的测定结果,Al含量的增加,使凝固区域增宽,由于发达的枝晶阻碍了合金的流动,使流动性下降。合金的液相线温度随Al量的增加而降低,Al含量从24%增至35%时,其过热度约增加1倍。过热度的提高,将有利于合金的流动性提高。研究认为:Al对合金过热带来的有利作用远不及合金结晶温度范围增宽以及高熔点Al2O3数量增多而造成的不利影响。因此,Al含量的增加将导致合金的流动性降低。测试结果表明:Cr元素由于提高合金的液相线温度,使合金的流动性下降。Mo和Zr元素有利于合金流动性的提高。     

热力学分析合金元素对7055合金的影响

采用CALPHAD技术及热力学计算软件模拟7055合金的凝固路径、TTT曲线,以及η(MgZn_2)相和S(CuMgAl_2)相生成温度和生成数量随Zn、Mg、Cu含量变化的关系曲线,并进行DTA曲线测试,测试结果与热力学结果相一致。热力学计算结果表明,随Zn、Mg、Cu元素含量增加,液相线温度降低,低熔点共晶相析出温度升高;凝固组织中η相(MgZn_2)的生成温度在408～448℃范围内,生成量为5.7%～6.9%;S相(CuMgAl_2)的生成温度在436～469℃之间,生成量为0.5%～1.9%;随着Mg含量增加,合金的淬火敏感性提高,Zn、Cu元素含量的变化对合金的淬火敏感性影响不大。     

Thermodynamic analysis on preparation of fibrous NiO precursor powders with oxalate precipitation process

According to the principles of simultaneous equilibrium and mass balance, a series of thermodynamic equilibrium equations of Ni（ Ⅱ）-C2 O4^2--NH3-NH4^＋-H2O system at ambient temperature are deduced theoretically and the logarithm concentration versus pH value（lg[Ni^2＋ ]r-pH） diagrams at different solution compositions are drawn. The results show that when pH is above 8.0, nickel ions coordinate with ammonia, the precipitation proceeds slowly accompanying with the release of nickel ions from the multi-coordinated Ni（NH3）n^2＋ （n= 1, 2,…, 6） and the morphology of NiO powder precursor is fibrous; when pH is below 8.0, nickel ion directly reacts with C2O4^2- and the morphology of NiO powder precursor is of cubic-shape. Some experiments were made to confirm the relation between the total concentration of nickel ion and pH. It is shown that the thermodynamic mathematical model is correct and the calculated values are basically accurate.     

Influences of stoichiometric ratio B/A on structures and electrochemical behaviors of La0.75Mg0.25Ni3.5Mx (M=Ni, Co; x=0-0.6) hydrogen storage alloys

In order to investigate the influences of the stoichiometric ratio of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structures and electrochemical performances of the AB3.5-4.1-type electrode alloys, the La-Mg-Ni-Co system La0.75Mg0.25Ni3.5Mx (M=Ni, Co; x= 0, 0.2, 0.4, 0.6) alloys were prepared by induction melting in a helium atmosphere. The structures and electrochemical performances of the alloys were systemically measured. The results show that the structures and electrochemical performances of the alloys are closely relevant to the B/A ratio. All the alloys exhibit a multiphase structure, including two major phases, (La, Mg)2Ni7 and LaNi5, and a residual phase LaNi2, and with rising ratio B/A, the (La,Mg)2Ni7 phase decreases and the LaNi5 phase increases significantly. When ratio B/A=3.7, the alloys obtain the maximum discharge capacities. The high rate discharge(HRD) capability of the alloy (M=Ni) monotonously rises with growing B/A ratio, but that of the alloy (M=Co) first mounts up then declines. The cycle stability of the alloy (M=Co) monotonously increases with rising B/A ratio, but it first decreases slightly then increases for the alloy (M=Ni). The discharge potential of the alloy (M=Ni) declines with increasing B/A ratio (x＞0.2), but for the alloy (M=Co), the result is contrary. The substitution of Co for Ni significantly ameliorates the electrochemical performances. For a fixed ratio B/A=3.7, the Co substitution enhances the discharge capacity from 365.7 to 401.8 mA-h/g, the capacity retention ratio (S100) after 100 charging-discharging cycles from 50.32% to 53.26% and the HRD from 88.65% to 90.69%.     

Thermodynamic equilibrium calculation on preparation of copper oxalate precursor powder

According to the principles of simultaneous equilibrium and mass balance, a series of thermodynamic equilibrium equations of Cu^2＋-C2O4^2--NH3-NH4^＋＋-H2O system at ambient temperature were deduced theoretically and the logarithm concentration versus pH value （lg[Cu^2＋]T--pH） diagrams at different solution compositions were drawn. The results show that when pH is below 5.0, copper ion reacts with C2O4^2- directly and the morphology of copper precursor powder is of pie-shape, when pH is above 5.0, copper ion coordinates with ammonia, and the precipitation proceeds slowly accompanying with the release of copper ions fi＇om the multi-coordinated Cu（NH3）n^2＋（n =1, 2,…, 5） and the morphologies of copper precursor powder are respectively of rod aggregation shape （when 5.0〈pH〈8.0） and of rod-shape （when pH〉8.0）. Some experiments were performed to confirm the relation between the total concentration of copper ion and pH value. It is shown that the thermodynamic mathematical model is correct and the calculated values are basically accurate.     

Effect of Hf/Ni ratio on microstructure and hydrogen permeation of Nb-Hf-Ni ternary alloys

The effect of the Hf/Ni ratio on the microstructures and hydrogen permeabilities of the Nb-Hf-Ni ternary alloys is studied in particular. The results demonstrate that with the increase in the Hf/Ni ratio, (i) the quantity of the primary (Nb, Hf) phase increases; (ii) a new HfNi phase with more Hf content appears; (iii) the Φ value decreases except that of the alloys with the same Hf and Ni contents.     

Co替代Ni对快淬Mg2Ni型合金结构及电化学贮氢性能的影响

为了改善Mg2Ni型贮氢合金的电化学贮氢性能,以Co部分替代合金中的Ni,用快淬工艺制备Mg2Ni型Mg2Ni1-xCox(x=0,0.1,0.2,0.3,0.4)合金,获得长度连续、厚度约为30μm、宽度约为25 mm的快淬合金薄带。并用XRD、SEM、HRTEM分析快淬态合金薄带的微观结构;用DSC研究快淬薄带的热稳定性;用程控电池测试仪测定合金薄带的电化学贮氢性能;探索Co替代Ni对快淬Mg2Ni型合金结构及电化学贮氢性能的影响。结果表明:在快淬无Co合金中没有发现非晶相,但快淬含Co合金中存在明显的非晶结构,证明Co替代Ni提高了Mg2Ni型合金的非晶形成能力。Co替代Ni使快淬态合金的热稳定性略有提高,显著地改善了合金的电化学贮氢性能,包括放电容量、电化学循环稳定性以及高倍率放电性能,这主要归因于Co替代Ni导致结构的变化以及非晶形成能力的提高。     

95W-5（Ni／Fe／Co）合金高温变形及影响因素

通过温度、应变速率对95W-5（Ni／Fe／Co）合金流变应力曲线的影响，分析了该合金的变形特点。结果表明：该合金在200℃～600℃温度范围内变形时，初始加工硬化十分显著。宏观上表现为合金的屈服强度较高。95W-5（Ni／Fe／Co）合金在700℃～1300℃的流变应力曲线有一明显的特点就是曲线的斜率变小，而且出现短暂稳定态的流动。这是由于粘结相发牛动态回复的结果。此外该合金的高温塑性亦随应变速率的增大而增加。扫描电镜分析结果从微观上验证了该合金高温塑性变化的原因。     

激光熔覆Ni60A+WC/12Co复合涂层的组织及性能

采用激光熔化同步输送Ni60A 30wt%WC/12Co复合粉末，在适度预热后的45钢表面激光熔覆获得了一定厚度的复合涂层。涂层中镶嵌着大量与基体合金结合良好的Co包WC颗粒。熔覆过程中Co包WC颗粒很少发生溶解。涂层与基板为冶金结合，对基板的适度预热避免了涂层的开裂。所得涂层具有很高硬度，涂层基体硬度为1030HV0.3，Co包WC颗粒硬度达2050HV0.3。     

Property of cobalt nickel silicide by thermal annealing of Co/Ni bilayer on a silicon substrate

15 nm-Co/15 nm-Ni/p−Si (100) was thermally annealed using rapid thermal annealing for 40 s at 700∼1100°C. The annealed bilayer structure developed into the composite CoNiSi_x and the resulting changes in sheet resistance, microstructure, and composition were investigated using a four-point probe, transmission electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy. The final thickness of the composite CoNiSi_x was approximately 100 nm and it maintained its sheet resistance below 5 Ω/sq after silicidation annealing at 1100°C. The proposed CoNiSi_x silicides may be superior to conventional single phased silicides due to their improved thermal stability and thickness adjustment.