铜钴镍离子对镁合金微弧氧化膜的影响

目的提高镁合金微弧氧化膜的耐蚀性。方法在Na_2SiO_3-NaOH-Na_2B_4O_7组成的电解液体系中,分别加入铜离子、钴离子和镍离子对AZ91D镁合金进行微弧氧化,研究离子种类和组成对膜层性能的影响。采用点滴实验测试膜层的耐蚀性,采用电化学工作站测试膜层的电化学性能,采用扫描电子显微镜(SEM)和能谱分析(EDS)对微弧氧化膜层的表面形貌和元素组成进行分析。结果电解溶液中加入钴离子、铜离子、镍离子后,镁合金微弧氧化膜的耐腐蚀性能均有提高。其中铜离子的影响最大,加入1.5 g/L的铜离子后,镁合金微弧氧化膜的点滴时间提高了77.3 s,膜层耐腐蚀性能显著提高。电化学测试结果得出,不加金属离子的氧化膜的腐蚀电流密度为1.092×10~(-5) A/cm~2,腐蚀电位为-1.487 V;加入钴、铜、镍离子浓度分别为2、1.5、3 mol/L时,腐蚀电流密度分别为3.912×10~(-6)、6.027×10~(-6)、2.167×10~(-6) A/cm~2,腐蚀电位分别为-1.412、-0.832、-1.047 V;加入金属离子制得的微弧氧化膜的腐蚀电流密度均降低了1个数量级,腐蚀电位不同程度地正移,其中加入铜离子后腐蚀电位提高了0.655 V。加入金属离子后,陶瓷膜表面空隙和孔洞数量不同程度地变浅和减少,增加了膜层的致密性和均匀性。结论电解液中添加一定量的铜、钴、镍离子均能够提高AZ91D镁合金微弧氧化膜层的耐蚀性,其中铜离子的效果最明显。     

镁合金浸锌前处理对化学镀镍层的影响

目的优化出镁合金浸锌前处理的处理液络合剂及工艺条件。方法研究镁合金浸锌前处理处理液的络合剂,确定出适用的络合剂,并在最佳络合剂的条件下,研究前处理液pH值和温度的变化对化学镀镍层的影响。采用电化学测试、扫描电子显微镜(SEM)和X射线衍射(XRD)对化学镀镍层进行耐蚀性评价,并对其微观形貌进行表征,确定出最佳络合剂和工艺条件。结果通过对镀镍层厚度的测量及SEM微观形貌观测,确定最优的前处理液络合剂为苹果酸。在该条件下确定最佳的工艺条件为:pH=10,温度80℃。所制得的化学镀镍层的自腐蚀电位为-0.6 V,与镁合金基体的腐蚀电位-1.47 V相比,提高了0.87 V,腐蚀电流密度由镁合金基体的1.26×10~(-4) A/cm~2下降到1.26×10~(-6) A/cm~2,自腐蚀电流密度降低了2个数量级。镀层的钝化区间在-0.6~0.2 V,且结合力好,外形美观。结论镁合金浸锌前处理处理液的最佳络合剂为苹果酸,最佳工艺条件为pH=10、温度80℃。     

ABS塑料化学镀镍激光无钯活化工艺

化学镀是ABS塑料表面金属化最常用的方法之一,但在施镀前需要使用钯等贵金属对基体进行活化,使其具有催化活性。以NiSO_4与NaH_2PO_2混合配制活化液,涂覆于塑料基体表面,常温放置8~10min后,基体表面形成一层活化层;用激光均匀扫描基体表面,活化层在激光作用下反应生成活性Ni微粒使基体活化,再进行化学镀镍。采用正交试验优化激光活化各参数,通过扫描电镜对各阶段基体表面形貌进行表征,利用能谱和X衍射对活化及施镀后的基体表面成分进行分析,采用高低温冲击法检测镀层结合性。结果表明,当NiSO_4与NaH_2PO_2浓度分别为10g/L和40 g/L,光斑直径为1mm,扫描速率为5 mm/s,涂覆次数为2次时,镀覆效果最好;基体活化后,表面附着一层均匀的平均直径为30nm的活性Ni微粒催化核心;施镀后,镀层均匀致密,结合性较好。     

He+离子辐照Inconel 718合金表面形貌改变及机理研究

研究了3种不同剂量He⁺离子辐照后Inconel 718合金的形貌变化规律及其形成机理。结果表明，He⁺离子辐照会在合金表面形成纳米多孔结构，其孔径会随辐照剂量的增加而增大。此外，He⁺离子辐照还会破坏合金表面δ相并导致碳化物的持续溅射损耗，且这一现象会随着辐照剂量的增加而愈发严重。由于辐照过程中氦泡间微观应力σ n作用会引起毗邻材料断裂及氦泡合并长大，且辐照溅射作用又会导致氦泡上层薄膜的损耗甚至破裂，因而这也是He⁺离子辐照Inconel 718合金表面纳米多孔结构的形成机制。     

‘Nickel Allergy’ arising from decorative nickel plated and alloyed articles: prevention at source

This work builds on papers published in Transactions during 2015 and 2018 reporting research into low-cost commercial methods for the prevention of nickel release from decorative nickel plated articles, rendering them suitable for placement on the European market in accordance with the requirements of REACH. ‘Nickel Allergy’ sometimes occurs when nickel-containing articles are in direct and prolonged contact with the skin, leading to corrosion of elemental nickel by sweat, liberating sufficient nickel ions to be absorbed through the skin and initiate an allergenic effect. The EU ‘Nickel Restrictions’ impose limits on the amount of nickel released from articles intended for use in this application, but permits a non-nickel surface coating that can ensure the rate of nickel release does not exceed 0.5?µg?cm^?2 week^?1 after 2 years of normal use. The official tests for coated items are simulated wear and corrosion under EN 12472 followed by determination of nickel release under EN 1811. Earlier work concluded that suitable barrier coatings over bright electrodeposited nickel are regular chromium deposited from a hexavalent electrolyte, microporous trivalent chromium from a chloride electrolyte and UV cured PU electrophoretic coatings. Further tests reported here focused on nickel release from examples of wearable articles such as costume jewellery and watch cases. A typical flash coating of gold over bright nickel is thin and porous and being more noble, causes the rate of nickel release to be accelerated; but this can be prevented by an intermediate barrier coating of electrodeposited palladium. To round out the relevance of this study on wearable articles, nickel release tests were also conducted on nickel-containing Grades 304 (UNS S30400) and 316 (UNS S31600) austenitic stainless steels, plus a typical gold alloy containing nickel. All passed the nickel release tests satisfactorily.     

单晶/多晶镍轴向拉伸力学性能的分子动力学模拟

为提高航空发动机推重比采用整体叶盘新技术却带来了盘叶连接区域高风险失效问题。本文采用分子动力学对连接区单晶/多晶镍(SPSNi)的力学性能进行模拟,首先通过对比了不同晶态镍拉伸原子图。发现,由于单晶/多晶界面的存在使得拉伸后界面处的非晶化程度加剧,易于孔洞萌生,加剧了SPSNi突然断裂的风险。最后重点研究了单晶/多晶镍的应变率效应与温度效应。当应变率大于1í10_⁸s_^-1小于2í10_¹⁰s_^-1时,SPSNi对加载应变率几乎不敏感,屈服强度小幅上升。超过2í10_¹⁰s_^-1之后,其屈服强度随着应变率的增加而迅速下降。这是因为在高应变率下,SPSNi的FCC原子大规模迅速转变为无序的非晶结构,导致了晶体镍承载能力迅速下降。可以将应变率2í10_¹⁰s_^-1作为SPSNi拉伸变形的阈值。不同温度下,SPSNi屈服强度随温度的增大而线性下降。这是由于在温度的影响下,位错网络的初始镶嵌结构逐渐变得不规则,初始失配应力随着温度的升高而下降。     

碱激发铜镍水淬冶炼渣制备充填胶凝材料研究

为研究某铜镍矿产出的铜镍水淬冶炼渣大宗量处置技术,基于铜镍水淬冶炼渣制备充填胶凝材料的可行性和技术工艺,本研究开展了冶炼渣粉磨试验和激光粒度分析、基于冶炼渣的碱激发胶凝材料配比正交试验、充填体试块单轴抗压强度试验、充填体试块及胶凝材料净浆试块SEM测试,结果表明:该铜镍矿冶炼厂产出的铜镍水淬冶炼渣有一定的火山灰活性,但其火山灰活性较低;实验室配制的碱激发剂对该铜镍水淬冶炼渣激发作用不明显;该冶炼渣的最佳粉磨时间为50min,D(0.5)为28μm。在普通硅酸盐水泥为主要胶凝材料的碱性充填料浆中,冶炼渣的掺入引起了钙矾石生成量的增加,随着粉磨冶炼渣粒径的减小,冶炼渣颗粒表面的溶蚀现象越来越明显。     

Optimization of biohydrogen production using acid pretreated corn stover hydrolysate followed by nickel nanoparticle addition

The dilute acid hydrolysis using corn stover (CS) to produce reducible sugars was optimized by the response surface methodology. The electron-equivalent balances of the main metabolites during the dark fermentation (DF) using acid hydrolysate were investigated to identify the evolutions of the electron sinks over the course of DF. The additions of nickel ion and Ni⁰ nanoparticles (NPs) were found to effectively enhance the hydrogen production at experimental conditions. The optimal condition (HCl 2.5 wt%, hydrolyzing duration 105 minutes, pH=5, S/B=3.5, Ni⁰ NPs=10 mg/L^-1) was achieved with Y_H2/S reaching 1.18 (mol.mol^-1-glucose). The Y_H2/S increased from 0.7 (mol.mol^-1-glucose) to 1.18 (mol.mol^-1-glucose) reaching 40% hydrogen yield increase when Ni⁰ NPs was added to the fermentation broth. Among the investigated significant soluble metabolites, the butyric acid was found to serve as the largest e-sink in the electron-equivalent balance. The additions of Ni⁰ NPs at low level (below 10 mg/L) were found to appreciably increase the hydrogen production. The increased pH and substrate to biomass ratio were found to skew the metabolic balance from hydrogen production to the biosynthesis (an increase of biomass). The proposed anaerobic digestion model with consideration of the inhibitory factors model presents a good agreement with the experimental data. The chemical addition such as nickel ions, Ni⁰ NPs was found to be a practical approach in enhancing biohydrogen production using CS acid hydrolysate as cultivation broth.     

Incorporation of pyridinic and graphitic N to Ni@CNTs: As a competent electrocatalyst for hydrogen evolution reaction

Cheap production of hydrogen (H₂) from eco-friendly routes is preeminent for solving future energy challenges. This study explores the hydrogen evolution reaction (HER) activity of nickel (Ni) nanoparticles and nitrogen doped carbon nanotubes (NiNCNTs), which are fabricated by a cheap and one-step pyrolysis method. The most active catalyst synthesized at 800°C exhibits an overpotential of 0.244 V to reach a current density of 10 mA cm⁻², Tafel slope of 93.3 mV dec⁻¹ and a satisfactory 10 hours stability. Low resistance and large ECSA value of the sample also favor the competent response for HER in alkaline media. The robust HER activity of the catalyst is as a result of the nickel nanoparticles which are the active spots of reaction; while the presence of well-developed nitrogen containing carbon nanotubes with large content of pyridinic and graphitic nitrogen may provide high-electron density and feasible routes for its transportation to deliver an outstanding HER performance.     

Electrochemical properties of free‐standing polypyrrole/graphene oxide/zinc oxide flexible supercapacitor

We report the preparation of a polypyrrole/graphene oxide/zinc oxide nanocomposite on a nickel foam using a simple and rapid single‐step electrochemical deposition process under ambient conditions. A free‐standing flexible supercapacitor was fabricated by sandwiching a polyvinyl alcohol hydrogel polymer electrolyte between two layers of the as‐prepared ternary nanocomposite electrodes. The electrochemical properties of the free‐standing supercapacitor were analyzed using a two‐electrode system. The supercapacitor achieved a specific capacitance of 123.8 F/g at 1 A/g, which was greater than its single (39.1 F/g) and binary (81.3 F/g) counterparts. This suggests that ZnO acts as a spacer and support that hinders the ternary structure from collapsing and subsequently enhances the diffusion of ions within the matrix. The flexible supercapacitor exhibited remarkable electrochemical stability when subjected to bending at various angles. The cycling stability of the ternary nanocomposite showed a favorable specific capacitance retention of more than 90% after 1000 cycles for mild alkaline electrolytes compared with strong alkali electrolytes. The presence of glycerin in the polymer electrolyte enabled the supercapacitor to perform better under the vigorous cycling condition. The potential of the as‐fabricated supercapacitor for real applications was manifested by its ability to light up a light‐emitting diode after being charged. Copyright © 2014 John Wiley & Sons, Ltd.