HAc-KOH-KClO3抛光液中铜的钝化与磨损研究

用电化学测试技术研究了铜在Hac-KOH-KClO3化学机械抛光液中的腐蚀与钝化,分析了钝化膜的成分,研究了成膜的伏安曲线特征,考察了化学机械抛光过程中铜腐蚀电位随时间变化的轨迹、钝化膜的磨损与再钝化以及铜的极化曲线.结果表明,铜在Hac-KOH-KClO3化学机械抛光液中钝化膜主要由Cu2O和CuCl组成,CuCl的存在改善了铜的抛光特性.钝化膜的成膜过程符合Müller钝化成膜模型.氯酸钾的存在不仅加快了化学机械抛光过程中的钝化成膜速率和磨损除膜速率,而且降低了抛光磨损的压力和转速,大幅提高了抛光中的腐蚀电流密度,加快了铜的腐蚀.     

甲胺-铁氰化钾抛光液中铜钝化成膜的机理研究

用电化学循环伏安测试技术研究了铜在甲胺铁氰化钾抛光液中钝化成膜的机理。通过大幅度改变电位扫描速率,分析了氧化峰电流(IApa)、氧化峰电位(EApa)及阳阴峰电流的比值(IApa/IApc)与相应电位扫描速率的关系。结果表明,氧化峰电流和氧化峰电位均与电位扫描速率的平方根成线性关系,说明成膜复盖度θ与电位扫描速率无关,成膜过程符合M櫣ller模型。成膜过程中,电极反应存在后置化学转化,铜在去极化剂作用下发生失去一个电子的阳极溶解反应,然后再进行化学转化反应生成Cu4[Fe(CN)6]钝化膜。在CMP过程中,具有这种钝化膜的铜的腐蚀电流密度及抛光速率随抛光转速的增加而增大。     

新型奥氏体耐热钢钝化膜的XPS谱研究

为了比较新型耐热钢CHDG-A钝化处理前后的耐腐蚀性能,以及研究钝化膜的组成,采用6％FeCl3溶液浸泡法研究了3种不同表面粗糙度的CHDG-A合金试样的抗点蚀能力,并用X射线光电子能谱(XPS)研究了经硝酸钝化后合金表面钝化膜的主要成分.结果表明:表面粗糙度越大,合金的抗点蚀性能越差,而经过硝酸钝化后耐蚀性能大幅提高;钝化膜表面的主要成分是CrO3、Cr2O3、Fe2O3等氧化物,钝化膜内部主要为Cr2O3 Fe3O4、Cr单质、Fe单质、Ni单质等,Cr、Ni单质的存在有利于提高钝化膜的稳定性.     

激光合成Ni_3Al金属间化合物的腐蚀行为

通过激光技术合成单Ni3Al相金属间化合物,利用电化学方法及盐雾试验研究了Ni3Al金属间化合物在Na Cl溶液中的腐蚀行为特征、耐腐蚀性能及腐蚀机理。结果表明:激光合成Ni3Al金属间化合物在不同浓度的Na Cl腐蚀介质中均能形成保护性钝化膜,当Na Cl溶液浓度低于2%时,钝化膜具有良好的稳定性和耐腐蚀性能。当Na Cl溶液浓度高于3.5%时,钝化膜产生活化溶解,稳定性下降,Ni3Al金属间化合物表面形成点蚀坑,并且随腐蚀介质浓度增大,腐蚀加剧。Ni3Al金属间化合物表面点蚀坑边缘规整、腐蚀界限清晰,腐蚀机制为典型的晶内腐蚀,腐蚀过程中未形成应力腐蚀微裂纹等破坏性缺陷,具备在沿海湿热盐雾环境下使用的潜在价值。     

氨基磺酸中肉桂醛缩甲胺席夫碱对Q235钢的缓蚀吸附行为

为进一步研究肉桂醛缩甲胺席夫碱在氨基磺酸介质中对碳钢的腐蚀机理,利用极化曲线、原子力显微镜、X射线光电子能谱仪和量子化学计算,研究了5%氨基磺酸介质中肉桂醛缩甲胺席夫碱在Q235钢表面的缓蚀吸附行为。结果表明:在70℃、5%氨基磺酸介质中,肉桂醛缩甲胺在Q235钢表面的吸附行为符合Langmuir吸附等温式,是一种混合型缓蚀剂,且该缓蚀剂在Q235钢表面的吸附存在不均匀性;Q235钢在氨基磺酸溶液中的腐蚀产物主要为Fe SO4、Fe S,缓蚀剂的吸附抑制了Fe S的生成。     

纯镁材微弧氧化膜在硫酸铜溶液中的电化学腐蚀行为

研究镁材微弧氧化膜在含Cu2+介质中的腐蚀行为对扩大其使用范围具有十分重要的意义。采用微弧氧化技术对纯镁材进行表面硅酸盐氧化处理,制备了陶瓷膜。采用扫描电镜、X射线衍射、交流阻抗谱等方法分析了微弧氧化膜在0.1 mol/L Cu SO4溶液中的腐蚀形貌、腐蚀产物组成及腐蚀行为;采用极化曲线分析了Cu2+对Cl-腐蚀的影响。结果表明:因为微弧氧化膜中的Mg O与溶液中的H+发生反应,促进了溶液中Cu2+的水解,生成更多Cu(OH)2,并吸附于膜层表面,从而阻止了腐蚀介质向膜基面的进一步扩渗,减弱了腐蚀介质对膜层的腐蚀作用;腐蚀介质Na Cl溶液中加入Cu SO4后,未加剧微弧氧化膜的破坏,反而产生了缓蚀效果。     

双稀土处理液对H62黄铜成膜耐蚀性能的影响

为了提高H62黄铜合金的表面性能,通过正交试验获得了最佳锅、钵双稀土处理液配方。利用硝酸点滴、中性盐雾试验评价了H62黄铜合金钝化膜的耐蚀性能,通过电子探针(EPMA)观测了其表面形态结构及元素分布,利用电化学方法表征了 H62黄铜表面钝化膜在3.5%NaCl溶液中的缓蚀行为,采用XRD对H62黄铜表面钝化膜的成分进行了检测。结果表明:H62黄铜合金由镉、钵双稀土处理液钝化成膜的主要成分为Cu2O,CeO2,La(OH)3,Ce(OH)4;致密的钝化膜耐硝酸点滴时间达到21.98s,在3.5%NaCl溶液自腐蚀电位增加,腐蚀电流降低,腐蚀速度明显降低,耐蚀性能增加,耐中性盐雾性能明显优于鋪单一稀土处理液。     

Cu的加入对Fe3Si材料在NaCl溶液中的腐蚀行为的影响

以原子比为3：1的Fe粉和Si粉球磨20h后，将球磨得到的Fe（si）粉末和混合了质量分数为5％Cu的Fe（Si）-Cu粉末，在1O00±30℃，20MPa的压力下通过热压烧结的方法制备了Fe3Si和Fe3Si--Cu复合材料。文章通过浸泡腐蚀和电化学腐蚀两种方法讨论了Fe3Si和Fe3Si--5％Cu复合材料在NaCl溶液中的腐蚀行为。实验表明，两种材料在NaCl溶液中的腐蚀过程都是活化过程，Fe3Si在不同摩尔浓度的NaCl溶液中的腐蚀性能要比Fe3Si-5％Cu要好，浸泡腐蚀速率要小，自腐蚀电流也小。     

铜镍合金在NaCl溶液中点蚀行为的研究

对铜镍合金BFe30-1-1在NaCl溶液中出现的点腐蚀行为进行了研究.首先测试其在不同pH值的0.5 mol/L Nacl溶液中的阳极极化曲线以确定点蚀电位,并在点蚀电位之上进行恒电位腐蚀.通过原子吸收光谱测定腐蚀后溶液中的Cu2 和Ni2 含量,采用扫描电镜进行形貌观察以及分析试样断面的微区成分,并对点蚀坑内的腐蚀产物进行X射线衍射分析,以了解不同条件下铜镍合金的点腐蚀行为.结果表明,BFe30-1-1合金在酸性和弱碱性的0.5 mol/L NaCl溶液中的腐蚀规律基本相似;在强碱性溶液中的低电位下,合金表面可以形成较稳定的钝化膜,因而耐腐蚀性能较好;铜镍合金BFe30-1-1的点蚀坑内发生了脱镍腐蚀.     

H13钢在不同环境介质中的磨损性能

金属材料在不同介质中的腐蚀磨损特性不同,以往对H13钢在不同介质中的腐蚀行为研究较少.采用销盘式磨损试验机,对H13钢在空气、蒸馏水、3.5％NaCl溶液、5.0％ NaOH溶液中及不同载荷下进行滑动摩擦磨损试验,考察其磨损特性.结果表明:H13钢在空气中的磨损率最大,3.5％NaCl溶液中的磨损率最小;H13钢在空气中摩擦过程中具有较大的剪切力并产生较大的热量,使其磨损率较大,其主要磨损机制为黏着磨损,并伴有少量氧化物产生;在3种湿环境下,由于介质具有良好的润滑和冷却作用,且表面含有少量氧化物,呈现轻微磨损;蒸馏水中磨损机制为典型的疲劳磨损,3.5 ％NaCl溶液、5.0％ NaOH溶液中呈现腐蚀疲劳磨损.     

Atmospheric Corrosion of Copper Exposed in a Simulated Coastal-Industrial Atmosphere

The corrosion behavior of copper exposed in a simulated coastal-industrial atmosphere has been investigated using weight loss measurement, scanning electron microscopy, X-ray diffraction, potentiodynamic polarization and in-situ electrochemical impedance spectroscopy(EIS) with micro-distance electrodes.The results show that corrosion kinetics follows the empirical equation D = Atn. The main corrosion products are composed of Cu_2O, Cu_2Cl(OH)_3 and Cu_4Cl_2(OH)_6. A two-layer structure comprising a loose outer layer and a compact inner layer forms the corrosion products during corrosion process. SO_2 has been found to promote the formation of Cu_4Cl_2(OH)_6.     

Chemical etching of lead chalcogenides

Thermodynamic analysis of the Pb-S-H₂O, Pb-Se-H₂O, and Pb-Te-H₂O systems was carried out, and the φ-pH diagrams were constructed. An aqueous solution of KOH and K₃[Fe(CN)₆] was suggested for the chemical etching of lead chalcogenide crystals and films, and the etching rates of PbS and PbSe in this solution were measured. The etch composition was optimized for the stationary and dynamic chemical polishing of PbS and PbSe.     

Role of late transition metals on pitting resistance of Zr-Ti-(Cu,Ni,Co)-Al bulk metallic glasses in 0.6 M NaCl aqueous solution

Four quanternary Zr-based bulk metallic glasses(BMGs)were selected,including the Zr_(46)Ti_2Cu_(45)Al_7,Zr_(61)Ti_2Cu_(25)Al_(12),Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15),due to their robust glass-forming ability and containing a single species of late transition metal(LTM)in compositions.Their pitting resistances in 0.6 M Na Cl aqueous solution were investigated to examine the role of LTM elements in the alloys,with electrochemical measurements,surface morphology observation and x-ray photoelectron spectrometry analysis.It is shown that in comparision with two Cu-bearing BMGs,Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15)BMGs exhibited significantly superior resistance to pitting.Zr_(61)Ti_2Cu_(25)Al_(12),Zr_(55)Ti_4Ni_(22)Al_(19)and Zr_(55)Ti_2Co_(28)Al_(15)BMGs manifested distinct passivation behaviour,because of the formation of surface passive film mainly comprising of Zr O_2,Ti O_2and Al_2O_3.However,no significant differences in the electrochemical resistive properties and thicknesses of passive films were found between Zr_(61)Ti_2Cu_(25)Al_(12)and Zr_(55)Ti_4Ni_(22)Al_(19)BMGs.Nevertheless,at the passive film/metal interface,copper enrichment took place in Zr_(61)Ti_2Cu_(25)Al_(12),whereas the nickel was slightly deficient at the interface in Zr_(55)Ti_4Ni_(22)Al_(19).During pitting propagation,selective dissolution of the zirconium,titanium and aluminum over the copper took place in Zr_(61)Ti_2Cu_(25)Al_(12),but it was not the case in Zr_(55)Ti_4Ni_(22)Al_(19).For the two Cu-bearing BMGs,reduction of passive base metal elements in composition resulted in local selective dissolution,even absence of the passivation.     

The Nature of Mechanically Polished Surfaces of Copper

Surfaces of copper polished with diamond abrasives were examined by transmission electron microscopy; surfaces abraded on silicon carbide papes were also studied for comparison. There was no evidence of an amorphous layer, known as the Beilby layer, on any of the polished surfaces; the surface layers were crystalline and all showed evidence of plastic deformation. Slab-shaped cells were present at the surfaces that appear to correspond to the microbands or shear bands that have been observed in heavily cold-rolled copper. Some recrystallization occurred in the surfaces polished with 6-μm diamond abrasive, indicating some relaxation and modification of the microband-shear band structure; small subgrains were also observed, and it is concluded that they were also recrystallized grains. The degree of deformation at the surface decreased with increasing fineness of polish (i.e., from 6-μm diamond abrasive to 1 μm). The abraded surfaces consisted almost entirely of small subgrains, indicating that the shear band structure at these surfaces had nearly all recrystallized. It was concluded, however, that the highest surface temperature was attained when polishing with 6-μm diamond abrasive and then was only 100-150°C.     

超细球形铜粉的制备工艺研究

以水合肼为还原剂,采用液相化学法对超细铜粉的制备工艺进行了研究。结果表明,直接还原Cu2O获得的铜粉粒度分布很不均匀,抗氧化性能差。在添加微量亚铁氰化钾和2,2’-联吡啶后,铜粉的形貌、粒度分布以及抗氧化性能得到很大改善。经两步还原硫酸铜可制备平均粒度0.5μm以下且分布范围窄的近球形铜粉,热分析表明,该粉末在空气中120℃以下无氧化。     

Settlement and growth of copper-tolerantEctocarpus siliculosus (Dillw.) Lyngbye on different copper-based antifouling surfaces under laboratory conditions

The first paper of this series reports the development of an algal culture system suitable for monitoring marine antifouling characteristics of copper-based alloy materials under standardized laboratory conditions, using the marine-fouling algaEctocarpus siliculosus. The physical and chemical conditions necessary for both the formation of corrosion films typical of those formed at sea and vigorous growth of the alga in the incubating medium were investigated using copper-nickel 90/10 as a test material. Preincubation of sample plates in seawater for up to 140 days proved necessary in order to generate passive corrosion films which continued to release copper at sufficiently low rates to permit algal growth, spore production and settlement. Seawater sterilization and addition of supplementary algal nutrients did not significantly affect the equilibrium rates of copper loss or the composition of the corrosion films. Aeration of the medium accelerated the attainment of this equilibrium but the addition of Fe²⁺ ions had no effect. Surface preparation and orientation of sample plates had little effect on rates of copper loss. Corrosion rates recorded in these trials compare favourably with those reported for similar materials exposed at sea.     

常温磷化过程中的开路电位-时间曲线以及成膜规律

目前,对常温磷化成膜机理及规律的认识十分有限,进而影响了常温磷化膜的开发和应用.通过测量常温磷化过程中磷化液的开路电位-时间曲线分析了成膜规律,采用扫描电镜(SEM)考察了成膜过程中磷化膜的形貌变化,测定了膜层的耐蚀性、孔隙率随成膜时间的变化,通过X射线衍射(XRD)分析了磷化膜的相结构.结果表明:常温磷化成膜过程主要...     

A simple chemical method for deposition of electrochromic Prussian blue thin films

This paper is about a recently developed new chemical method for deposition of Prussian blue thin films. The films are easily prepared by successive immersion of the substrates into an acidic aqueous solution of Fe₂(SO₄)₃ and K₄[Fe(CN)₆]. It is calculated of the results from AFM analysis that the growth in the film thickness by one immersion cycle corresponds to an average increase of 6 nm. The characterization of the films with X-ray diffraction, SEM-EDS analysis and FTIR spectroscopy shows that the deposited material is amorphous hydrated Fe₄[Fe(CN)₆]₃. The electrochromic properties are characterized by cyclic voltammetry and VIS spectrophotometry. The PB thin films exhibit stability and excellent reversibility, which make these films favorable for electrochromic devices.     

钒基普鲁士蓝类似物VHCF用于水系铜电池正极

针对开发高性能水系铜电池电极材料的迫切需求,通过简易的共沉淀法制备钒基普鲁士蓝类似物铁氰化钒(VHCF)用作水系铜电池正极,考察反应温度及转速对VHCF样品表面形貌及微观结构的影响,探究不同VHCF样品在电化学性能上的差异,并分析VHCF样品的铜离子储存机理。研究结果表明：通过适当提升反应温度及搅拌器的转速,可以制备出[Fe(CN)₆]^4-含量多,粒径小且结构稳定的立方相VHCF;丰富的[Fe(CN)₆]^4-可以为Cu²⁺离子提供更多的化学活位点,较小的粒径有利于提高Cu²⁺离子的扩散速率,与普鲁士蓝骨架结合更稳定的结晶水则能改善电池循环稳定性;电化学反应过程中,Cu²⁺离子会取代VHCF骨架中的V⁵⁺离子形成不可逆新相。VHCF正极在0.1 A/g电流密度下的首次放电比容量高达146.5 m A·h/g,循环500次后,保留了56.1 m A·h/g的可逆容量;在1.0 A/g的大电流密度下的放电比容量仍有60...     

乳酸体系抛光液中锇的化学机械抛光

本文研究了乳酸(HL)体系抛光液中金属锇的化学机械抛光(CMP)行为,采用电化学分析方法和X射线光电子能谱仪(XPS)分析氧化剂和腐蚀抑制剂的作用机理,利用原子力显微镜(AFM)观察抛光前后锇的表面形貌.结果表明,当抛光液仅含有H2O2时,金属锇表面腐蚀不明显;在一定浓度范围内H2O2浓度的增加可以提高金属锇表面的腐蚀速度,但是不利于金属锇表面钝化膜的形成.当抛光条件为:压力为6.895 kPa,转速为50 r/min,抛光液流量为50 mL/min,pH值为5.0;抛光液组成为:SiO2质量分数为1%,HL质量分数为1%,H2O2质量分数为3%时,得到最大去除速率为23.34 nm/min,表面粗糙度Ra为6.3 nm,而将缓蚀剂BTA加入到抛光液后,在同样的抛光条件下得到的锇表面粗糙度更低,表面粗糙度Ra达到2.1 nm.