A novel process for copper protection in the simulated industrial cooling water based on click synthesis and self‐assembling method

The triazole inhibitor of 1‐(p‐tolylthio)‐1H‐1,2,3‐triazole‐4‐carboxylic acid (TTC) was synthesized via the Cu(I)‐catalyzed azide‐alkyne 1,3‐dipolar cycloaddition reaction. The self‐assembling method was performed to fabricate the self‐assembled film of TTC on the copper surface. The electrochemical measurement results indicate that the TTC film can efficiently protect the copper from corrosion in high concentrated industrial cooling water. The protection efficiency of TTC film for copper is 92.2%. Surface characterizations imply that the copper with TTC film after corrosion is covered with multiple protective layers. It probably contains Cu(I) and Cu(II) complexes mixed with nitrogenous compound, Cl^? and SO₄^2?. The result of quantum chemical calculation shows that the superior performance of TTC film is related to the adsorption of TTC molecules on copper surface horizontally. This kind of adsorption is mainly achieved via the adsorption centers of triazole ring and O atoms in TTC molecule.     

Relationship between structure and electrical resistivity in nano-structured copper-containing carbon films

The microstructure evolution of carbon/copper (C/Cu) films and its relation to the variation of film electrical resistivity has been studied. The films doped with copper in the range of 1.4-22.6 at.% Cu, were deposited by dc magnetron sputtering of composite graphite-copper target. The microstructure of films was studied by Raman spectroscopy and electron diffraction. The electrical resistivity was measured parallel and perpendicular to the substrate surface. The introducing of copper atoms into carbon matrix which consists of disordered graphite-like nano-clusters results in additional distortion of film microstructure at low copper content and some ordering of it at high copper content. At low copper concentrations the additional distortion of graphite-like clusters prevails over the input to electrical conductivity from copper atoms thus increasing the electrical resistivity of C/Cu films. At high copper concentrations the input to electrical conductivity is predominant and the film resistivity decreases.     

Fabrication of thin copper mesh for electromagnetic interference of display panel by pulse reverse current method and study on the microstructure by small angle neutron scattering

A copper sheet with mesh was mass-produced by continuously combining three techniques, electroforming with pulse-reverse current, transfer technique onto a transparent polyimide (PI) film and oxidation processes. Thiourea as an organic additive in a modified copper sulfate bath changes the reduction potentials of copper complexes, which results in effectively controlling the crystal orientation, surface roughness and microstructure of the copper layer. An electroformed copper layer without thiourea has a relatively rough surface with an average surface roughness of about 144.7 nm, whereas, the copper layers with thiourea have a smooth surface with an average surface roughness in the range of 6.3 to 12.1 nm. The copper layers with thiourea have a preferred orientation of crystal structure such that Cu (111) peak intensity increases, whereas, Cu(220) peak intensity decreases with thiourea addition. Electroforming with a rectangular pulse current density including etching at +640 mAcm^?2 for 1.8 msec and plating at ?160 mAcm^?2 for 4 msec in a modified copper sulfate bath with 200 ppm-thiourea at 25 °C is one of optimum conditions to massproduce a copper mesh sheet roll with 300 ??m pitch, 10 ??m mesh width and thickness, and 200 m long.     

Continuous Converting of Copper Matte to Blister Copper in a High-Intensity Molten-Layer Reactor

Continuous converting of copper matte or white metal into blister copper is carried out in a new, high-intensity falling film type of molten-layer reactor that operates with dry, high-grade matte or white metal ground to ?65 mesh and technical oxygen. The reactor operates at up to 1500°C to 1600°C producing a blister copper with 0.5–0.8% S, which can be refined in a conventional manner, and a slag containing less than 8% Cu. The reactor is designed to operate continuously producing an off-gas containing over 50% SO₂. The developed phenomenological model of the molten-layer reactor was found to predict with good agreement the results obtained in a one-tonne-per-day pilot reactor.     

Etude Electrochimique Du Comportement Du Cuivre En Solution Alcaline Et De L'action Inhibitrice De La Cyclohexylamine

The behaviour of copper in a basic solution (pH 12) of Na₂SO₄ 0,1N has been investigated, in presence or not of cyclohexylamine, using polarization as well as double layer impedance measurements.The composition of the oxide film and the mechanism of reduction of CuO and Cu₂O are discussed. Some previous results concerning this mechanism are not confirmed. The expected formation of copper-cyclohexylamine complexes does not accelerate the corrosion process of copper: cyclohexylamine can be considered as a copper corrosion inhibitor, making the protective oxide film more stable by formation of a Cu(W NH₂)_x²⁺ complex.     

Adsorbed corrosion inhibitors studied by electron spectroscopy: Benzotriazole on copper and copper alloys

Surface films formed by adsorption of benzotriazole (BTA), on copper and copper alloys have been studied by X-ray photo-electron spectroscopy (XPS). It is found that on both copper and copper-nickel alloys, benzotriazole forms a Cu(I)BTA surface complex. For the copper-nickel alloys the time taken to form the Cu(I)BTA film is dependent on the alloy composition. The Cu(I)BTA films were found to oxidize rapidly to a Cu(II) species on removal from the liquid phase. Surface films formed by BTA on 70 Cu : 30 Zn alloy were found to contain both copper and zinc, the copper again being in the Cu(I) state.A study of the adsorption of BTA on cathodically reduced copper surfaces strongly supports previous suggestions that the presence of Cu₃O facilitates formation of the surface film.     

铜在含氯薄液膜和杂色曲霉作用下的腐蚀行为

目的 研究纯铜在含氯液膜和霉菌共同作用下的腐蚀行为与机理。方法 将海南文昌采集的一株野生杂色曲霉接种到质量分数分别为0.9%和3.5%的NaCl溶液中制成孢子悬浮液,将孢子悬浮液均匀喷洒到铜试样表面后进行恒温恒湿试验,试验不同周期后采用体视学显微镜、扫描电子显微镜观察铜试样的腐蚀形貌,采用X射线光电子能谱仪分析试验14 d的试样表面和氩离子刻蚀15 s后的成分。结果 纯铜在NaCl薄液膜下的腐蚀产物具有明显的双层结构,内层靠近基体的为致密的Cu2O钝化层,外层为疏松的Cu2(OH)2CO3和Cu2(OH)3Cl组成的Cu(II)碱式盐;无菌时,铜表面出现大量蓝绿色的Cu(II)碱式盐,杂色曲霉存在时,铜表面腐蚀产物主要为红棕色的Cu2O钝化膜,仅有少量Cu(II)碱式盐零星分布在Cu2O膜外层;0.9% NaCl薄液膜与霉菌共同作用时,试样表面腐蚀产物主要为Cu2O,当薄液膜中盐的质量分数升高到3.5%时,霉菌数量减少,Cu(II)碱式盐较0.9% NaCl薄液膜组增多。结论 纯铜的腐蚀产物由内层的Cu2O钝化层、外层的Cu2(OH)2CO3和Cu2(OH)3Cl组成双层结构。杂色曲霉通过呼吸作用影响液膜中的O2浓度进而影响铜的腐蚀产物组成,霉菌存在时腐蚀产物中Cu(II)碱式盐显著减少。含氯液膜与霉菌共同作用时,液膜中的NaCl浓度通过影响杂色曲霉的生长活性而影响腐蚀产物组成。     

人血清白蛋白对模拟宫腔液中铜的光电响应特性的影响

用动电位伏安法，动电位光电流测量，表面膜的阴极还原和XRD分析等手段研究了铜在含或不含人血清白蛋白的模拟宫腔液（pH=7)中的电化学和光电化学行为，在不含白蛋白的模拟宫腔液中，铜电极表面生成的Cu2O呈n型光响应；一定量白蛋白存在时使Cu2O的光响应从n型转为p型，Cu2O在模拟宫腔液中呈n型光响应可归因于氯离子对Cu2O的掺杂，白蛋白排斥氯离子对Cu2O的掺杂，使其光响应从n型转为p型。     

涂覆Mannich碱对CU粉抗氧化性能的影响

在酸性溶液中对经一种Mannich碱处理的Cu粉进行了腐蚀实验.热分析结果表明,原始Cu粉在200℃开始氧化,而经处理的Cu粉从300℃开始氧化.X射线光电子能谱分析表明,该Mannich碱与Cu2 形成配位化合物吸附在Cu粉表面,形成Cu/缓蚀膜结构,通过覆盖效应抑制了腐蚀.设计实验分离出该Mannich碱与Cu粉的直接反应产物,并制备了Mannich碱与Cu2 的配合物配合物的红外光谱和紫外可见光谱表明,该Mannich碱是通过分子中的N原子与Cu2 形成配合物而实现保护作用,分子中的O原子未参与配位     

Effect of triethanolamine on deposition rate of electroless copper plating

Abstract

The addition of bis(3-sulphopropyl) disulphide in Cu electroless plating results in Cu superfilling. However, the deposition rate of superfilling copper plating is decreased, which hinders its application for filling Cu into via holes of ultralarge scale integrations. In the present study, the effect of triethanolamine (TEA) on the deposition rate of electroless copper plating was investigated. The deposition rates of electroless plated copper both in traditional and superfilling copper plating were accelerated with an addition of TEA, which was attributed to a decrease in reaction activation energy of a dominant reduction reaction. X-ray diffractometry and atomic force microscopy measurements indicated that with an addition of TEA, the peak intensity ratio /(111)//(200) of electroless plated Cu film was increased and the average surface roughness was decreased.     

Effect of the deposition process on the composition and structure of sputtered lanthanum cuprate films

La-Cu-O thin films were deposited by two different methods. As a first process, the films were deposited by co-sputtering of metallic copper and lanthanum targets in various Ar-O₂ reactive mixtures. The oxygen flow rate introduced into the deposition chamber was optimised to fully oxidise the sputtered atoms. The atomic ratio La/Cu in the film was adjusted by the variation of the pulsed DC current applied to the copper target. Within this process, the experimental window range for successful synthesis of films with the expected La/Cu ratio was found to be very narrow. The second process, namely, reactive sputtering of a composite La-Cu target, showed easier control of the film composition. The La/Cu atomic ratio was strongly dependent on the composite target that evolved during the use of target. Whatever the deposition process, an annealing step in air was necessary to obtain the crystalline La₂CuO₄ phase. To find the temperature of crystallisation, a sample was annealed successively from 100 to 600 °C by step of 100 °C, plus an annealing at 800 °C. The crystalline nature of the sample was ensured by X-ray diffraction measurement after each annealing.     

Effect of Dilute Tellurium and Selenium Additions on the High-Temperature Oxidation Resistance of Copper Alloys

The high-temperature oxidation resistance of Cu–Te–Se alloys and Cu–Se alloys at 300, 400, 500 and 600 °C was studied by measuring weight gain per unit area after fixed oxidation times. The morphologies of the oxide scales formed were observed using a scanning electron microscope, with the distribution of element detected by an energy-dispersive spectrometer, and the phases identified using X-ray diffraction. The focus of this study was to understand the effects of tellurium (Te) and selenium (Se) additions on the high-temperature oxidation resistance of copper alloys. At the dilute levels studied (≤0.5 wt% total), these elements underwent internal oxidation. Meanwhile, new phases formed, which made oxidation films more compact and increased the adherence between the oxide film and the alloy matrix, as well as prevented oxygen diffusing in the copper alloy matrix, so the oxidation resistance of copper alloys was improved.     

Formation of oxides on copper in alkaline solution and their photoelectrochemical properties

The anodic formation of Cu(I) and Cu(II) oxides on polycrystalline copper in a deaerated alkaline solution is studied using the technique of the synchronous recording of transients of the photocurrent and polarization current. The oxide formation in a currentless mode is analyzed via the synchronous recording of photopotential and corrosion potential. It is found that copper is susceptible to corrosion oxidation due to traces of dissolved oxygen with the formation of a Cu(I) oxide. The preliminary formation of the underlayer of anodic Cu(I) oxide on copper hinders its further corrosion oxidation. It is confirmed that copper oxides Cu₂O and CuO, which appear on copper in both anodic and corrosion modes of formation, are p-type semiconductors. The initial stage of anodic oxidation of copper is characterized by the formation of an intermediate compound of Cu(I), possibly CuOH, which exhibits n-type conductivity. A film of Cu(I) oxide is thin and has a band gap of 2.2 eV for indirect optical transitions. Anodic polarization in the range of potentials of CuO formation leads to the formation of a thicker oxide film, which is a mixture of Cu(I) and Cu(II) oxides.     

Thermal performance of sputtered Cu films containing insoluble Zr and Cr for advanced barrierless Cu metallization

Pure Cu films and Cu alloy films containing insoluble substances(Zr and Cr)were deposited on Si(100)substrates,in the presence of interfacial native suboxide(SiOx),by magnetron sputtering.Samples were vacuum annealed between 300℃and 500 ℃to investigate effects of Zr and Cr additions on the thermal performance of Cu films.After annealing,copper silicides were found in the Cu(Zr)films,while no detectable silicides were observed in Cu and Cu(Cr)films.Upon annealing,Zr accelerated the diffusion and reaction between the film and the substrate,and lowered the thermal stability of Cu(Zr)alloy films on Si substrates,which was ascribed to the‘purifying effect’of Zr on the Si substrates.Whereas,Cr prohibited the agglomeration of Cu films at 500℃and decreased the surface roughness.As a result,the diffusion of Cu in Si substrates for Cu(Cr)films was effectively inhibited.In contrast to the high resistivity of Cu(Zr)films,the final resistivity of about 2.76μΩ·cm was achieved for the Cu(Cr)film.These results indicate that Cu(Cr)films have higher thermal stability than Cu(Zr)films on Si substrates and are preferable in the advanced barrierless Cu metallization.     

3%NaCl溶液中铜的表面膜及BTA膜的光电化学研究

３％ＮａＣｌ溶液中铜的表面膜及ＢＴＡ膜的光电化学研究任聚杰，杨迈之，童汝亭，蔡生民（河北医学院石家庄０５００１７）（北京大学北京１００８７１）（河北师范大学石家庄０５００１６）１引言人们已经注意到Ｃｌ－对Ｃｕ有腐蚀作用［１，２］，关于ＢＴＡ对Ｃｕ的缓...     

The valence state of copper in anodic films formed on Al-1at.% Cu alloy

During anodising of Al-Cu alloys, copper species are incorporated into the anodic alumina film, where they migrate outward faster than Al³⁺ ions. In the present study of an Al-1at.% Cu alloy, the valence state of the incorporated copper species was investigated by X-ray photoelectron spectroscopy, revealing the presence of Cu²⁺ ions within the amorphous alumina film. However, extended X-ray irradiation led to reduction of units of CuO to Cu₂O, probably due mainly to interactions with electrons from the X-ray window of the instrument and photoelectrons from the specimen. The XPS analysis employed films formed on thin sputtering-deposited alloy/electropolished aluminium specimens. Such an approach enables sufficient concentrations of copper species to be developed in the anodic film for their ready detection.     

Certain characteristics of nickel-containing and copper-containing oxide-phosphate layers on titanium

The oxide-phosphate layers on titanium are formed by plasma-electrolytic oxidation in aqueous electrolytes with polyphosphate complexes of Ni(II) and Cu(II). The obtained coatings are investigated by X-ray photoelectron spectroscopy and X-ray spectral analysis. A nonuniform distribution of elements over the thickness of coatings is established; they are characterized by an insignificant titanium content on the surface, concentrated copper in the surface layer, and the presence of carbon. It is shown that the ob CO₂ tained compositions film/Ti manifest a certain catalytic activity in the oxidation of CO to CO₂.     

Mott–Schottky analysis of passive films on Cu containing Fe–20Cr–xCu (x = 0, 4) alloys

Effect of copper on the defect density of Fe–20Cr–xCu (x?=?0, 4) stainless steel alloys was investigated in deaerated pH 8·5 borate buffer solution at room temperature using Mott–Schottky analysis. Mott–Schottky analysis revealed that the addition of copper increased the acceptor density (N_A, V_Cr^?3), i.e. decreased the Cr⁺³ content of the passive film. Also the donor densities, shallow donor (N_D1, V_O⁺²) and deep donor (N_D2, V_Cr⁺⁶), of the passive films formed were increased. XPS analysis confirmed the decrease in Cr content and enrichment of copper in the passive film of Cu containing alloys, which ultimately dictated their lower corrosion resistance, i.e. decreased film protectiveness and stability.     

Preparation of micron-sized flake copper powder for base-metal-electrode multi-layer ceramic capacitor

The preparation of flake micron-sized copper powders with the chemical–mechanical method was investigated. Reaction of [Cu(NH₃)₄]²⁺ complex with hydrazine hydrate at 85 °C produced monodispersed fine spherical copper powders, which were used as precursor to synthesize flake copper powders by the ball milling process. The flake copper powders having an excellent dispersibility and a uniform size of 9 ± 2 μm could be achieved. Thermogravimetry (TG), differential thermogravimetry (DTG) and differential thermal analysis (DTA) of the flake copper were investigated with thermal analyzer. The results showed that the oxidizing temperature increased with a decreasing specific area. The flake copper powder particles were employed as functional conductive materials in copper thick film paste for base-metal-electrode multi-layer ceramic capacitors (BME-MLCCs). Excellent connection between internal and terminal electrode and even distribution of glass in copper thick film can be observed by polarized light photograph. The dense thick films were also found by scanning electron microscopy (SEM) analysis, and the high densification of the fired films could be attributed to the “framework” effects.     

Electroless plating of palladium and copper on polypyrrole films

A novel process for the metallization of polypyrrole (PPY) film surface through consecutive electroless plating of palladium and copper in the complete absence of the SnCl₂ sensitization step was demonstrated. X-ray photoelectron spectroscopy (XPS) technique was used to characterize the polymer surface at each stage of the metallization process. It was found that only the fully reduced PPY film could reduce palladium ions to palladium metal (Pd(0)) in substantial amounts from either the Pd(NO₃)₂ or PdCl₂ acid solution. The palladium metal was necessary for catalyzing the subsequent electroless plating of copper. The reduction of Pd(II) ions in acid solution to Pd(0) on the film surface was accompanied by a simultaneous increase in intrinsic oxidation state and doping level of the film. The copper plating process after the palladium uptake step was highly dependent on the [Pd]/[N] ratio on the film. Through XPS and Auger photoeletron spectroscopy measurements, it was postulated that during the electroless copper plating process, the Cu(II) ions were first reduced to Cu(I) on the PPY film surface before complete reduction to copper metal.