氧化铝陶瓷基板化学镀铜工艺优化

目的化学镀铜是氧化铝陶瓷基板金属化的一种重要手段,为了进一步优化氧化铝陶瓷基板化学镀铜工艺,研究了化学镀铜液配比(尤其是镀液中铜离子和甲醛含量)对氧化铝陶瓷覆铜板微结构和导电性的影响。方法在对氧化铝陶瓷基板经过前期处理后,采用化学镀铜法在基板上镀铜。采用X射线衍射仪、光学显微镜对氧化铝基板上的化学镀铜层物相和形貌进行观察。采用覆层测厚仪、四探针测试仪对化学铜镀层的膜厚和方阻进行测量。结果 XRD结果表明,不同配比镀液得到的化学镀铜层均具有较好的晶化程度,镀液中甲醛和铜含量较低的镀液可制备出晶粒更为细小的化学镀铜层。甲醛和铜离子含量均较高时,沉积速度过快,使镀铜层的均匀性和致密性不佳。但当甲醛含量较高、铜离子含量较低时,沉积速度适中,从而获得了均匀性和致密性较好的镀铜层,同时这种镀层具有良好的导电性。结论采用表面活性化学镀铜工艺,当镀液中甲醛浓度为0.25 mol/L和硫酸铜质量浓度为1.2 g/L时,无需高温热处理,即获得了均匀性和致密性俱佳的铜镀层,可满足覆铜板的使用要求。     

Effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores

The effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores was carried out by phase analysis means of XRD, optical microscopy and SEM−EDS. The results indicated that at ambient temperature, the easily leached copper oxide minerals were completely dissolved, while the bonded copper minerals were insoluble. At lukewarm temperature of 40 °C, it was mainly the dissolution of copper in isomorphism state. With increasing temperature to 60 °C, the copper leaching rate in the adsorbed state was significantly accelerated. In addition, when the temperature increased to 80 °C, the isomorphic copper was completely leached, leaving 11.2% adsorbed copper un-leached. However, the copper in feldspar−quartz−copper−iron colloid state was not dissolved throughout the leaching process. Overall, the leaching rates of copper in different copper minerals decreased in the order: malachite, pseudo-malachite > chrysocolla > copper-bearing chlorite > copper-bearing muscovite > copper-bearing biotite > copper-bearing limonite > feldspar−quartz−copper−iron colloid.     

Corrosion-induced copper runoff from naturally and pre-patinated copper in a marine environment

Corrosion-induced copper runoff has been monitored for copper sheet, naturally patinated copper and pre-patinated copper, with and without surface treatments, in a marine environment during one year. The study comprises solution measurements on total copper runoff rates, sulphates and chlorides released from the patina, and parallel surface analytical studies on patina formation, combined with electrochemical impedance measurements on changes in barrier properties during exposure. Bioassay tests and model predictions were applied to elucidate copper bioavailability at the immediate release situation. The runoff rate of copper was significantly lower compared to the corrosion rate throughout the exposure period. At comparable rain quantities, copper runoff rates were significantly lower at the marine site compared to similar data obtained in an urban environment. The bioavailable concentration of released copper was significantly lower compared to the total copper concentration.     

国内铜板带生产技术与加工装备现状

重点介绍了中色科技所研制开发的铜板带热轧机、铜带坯水平连铸机、铜带粗轧机、铜带精轧机、铜带拉弯矫直机、铜带（酸洗）脱脂清洗机等铜加工设备的技术特点、装机水平及其加工工艺。     

CAUSE OF FORMATION OF NODULAR COPPER PARTICLES ON ELECTROREFINED COPPER SUBSTRATE

ＣＡＵＳＥＯＦＦＯＲＭＡＴＩＯＮＯＦＮＯＤＵＬＡＲＣＯＰＰＥＲＰＡＲＴＩＣＬＥＳＯＮＥＬＥＣＴＲＯＲＥＦＩＮＥＤＣＯＰＰＥＲＳＵＢＳＴＲＡＴＥ￥Ｌｉｎ，Ｊｉａｎｘｉｎ；Ｌｉ，Ｘｕｅｌｉａｎｇ；Ｃｈｅｎ，Ｈａｎｈｅ；Ｈｅ，Ｊｉａｎｂｏ（ＨｅｆｅｉＰｏｌ...     

Microstructure and Nano-hardness of Pure Copper and ODS Copper Alloy under Au Ions Irradiation at Room Temperature

The microstructure and nano-hardness of the pure copper and oxide dispersion-strengthened(ODS) copper alloy subjected to 1.4 Me V Au ions irradiation at room temperature were investigated. After irradiation, dislocation-loops form in both materials, while voids can only be generated in the pure copper. Compared with the irradiated pure copper, larger average diameter and lower number density of irradiation-induced dislocation-loops were detected in the ODS copper alloy, revealing that high-density dislocation and large volume of Al_2O_3 particles existing in the ODS copper alloy can act as effective sinks for the irradiation-induced defects. It was also detected that irradiation hardening in the ODS copper alloy is lower than that in the pure copper. The microstructure and nano-hardness results reveal that the ODS copper alloy has a better irradiation tolerance than the pure copper. In addition, the average diameter of the Al_2O_3 particles in the ODS copper alloy decreases after irradiation, because the Al–O chemical bonds are decomposed and the atoms are redistributed in the matrix during the irradiation process. This work reveals that the irradiation tolerance of the copper can be effectively enhanced by adding nano-sized Al_2O_3 particles into the matrix.     

铜基复合材料中短碳纤维增强体表面镀铜的研究现状

短碳纤维增强铜基复合材料是一种极具发展前景的金属基复合材料。但是碳纤维和铜的浸润性很差,一般须对短碳纤维进行表面镀铜处理。主要介绍了短碳纤维表面电镀铜和化学镀铜工艺,从工艺流程等方面分析其优缺点,并探讨了短碳纤维化学镀铜未来的研究方向。以甲醛为还原剂得到的镀层铜纯度接近100%,以此制成的铜基复合材料的导电性也较优异,但甲醛对人体有害和污染环境。次磷酸钠还原体系的化学镀铜工艺无毒无害,但需对碳纤维进行敏化活化处理。如何简化次磷酸钠还原体系化学镀铜工艺,提高镀铜层的纯度将是今后研究发展的重点。     

Influence of organic matter on orthophosphate corrosion inhibition for copper pipe in soft water

The adverse effects of organic matter on orthophosphate corrosion inhibition for copper pipe in simulated soft water were investigated. Sodium alginate and fulvic acid were selected to simulate extracellular polymeric substance produced by bacteria and natural organic matter in potable water. The results showed that the doses of organic matters, pH values and stagnation times had significantly affected on the function of orthophosphate corrosion inhibition for copper pipe in soft water. More soluble copper release was observed in low levels for sodium alginate (1 mg/l as TOC) and in high concentration for fulvic acid (16 mg/l as TOC). When the concentration of fulvic acid was high, the 2-week aged copper pipe released more soluble copper than the 6 and 12-month aged copper pipe. The soluble copper release increased with the reduction of initial pH value. Effect of stagnation time on soluble copper release from different aged copper pipe in soft water was highly variable. Compared to the system of no organic matters, organic matters markedly decreased the efficiency of orthophosphate corrosion inhibition for copper pipe in soft water.     

Simulated small-scale pilot heap leaching of low-grade copper sulfide ore with selective extraction of copper

The bioleaching of low-grade copper sulfide ore and the selective extraction of copper were investigated. Lix984 dissolved in kerosene was used as extractant. The results show that it is possible to selectively leach copper from the ores by heap leaching. The copper concentration of leaching liquor after 250 d is 2.17 g/L, and the copper concentration is 0.27 g/L after solvent extraction. The leach liquor was subjected to solvent extraction, scrubbing and selective stripping for the enrichment of copper and the removal of impurities. The pregnant copper sulfate solution produced from the stripping cycle is suitable for copper electro-winning.     

某含银高硫铜矿的综合回收试验

某含银高硫铜矿含铜0.76%、硫24.35%及银34.92 g/t,有价矿物种类多、矿石性质复杂,采用抑硫优先浮选铜-活化浮选硫的原则工艺流程进行试验,配合石灰作为硫化铁矿物抑制剂以及筛选出丁基黄药+酯-105作为硫化铜矿物的组合捕收剂,强化了银在铜精矿中的富集。在选定工艺条件下,可获得铜品位21.60%、银品位602.84 g/t的铜精矿(铜和银回收率分别为89.30%和54.39%),硫品位45.60%、银21.55 g/t的硫精矿(硫和银回收率分别为89.79%和29.59%),实现了铜、硫和银的综合回收利用。     

三维封装铜柱应力及结构优化分析

文中利用有限元模拟软件ANSYS对三维立体封装芯片发热过程中整体应力及局部铜柱的应力情况进行了分析,并对三维封装的结构进行了优化设计.结果表明,最大应力分布在铜柱层,铜柱的应力最大点出现在铜柱外侧拐角与底部接触位置.以铜柱处最大应力作为响应,进行了结构参数优化,采用三因素三水平正交试验方法,分别使用铜柱直径、铜柱高度、铜柱间距三个影响因素作为变化的结构参数.结果表明,铜柱直径的变化对等效应力影响最大,铜柱间距次之,铜柱高度影响最小.且发现随着铜柱高度、铜柱间距、铜柱直径的不断增大其铜柱外侧拐角与底部接触位置的最大等效应力不断减小.     

电子束辐照下铜超微粒子氧化与还原过程的高分辨电子显微镜观察

利用电子显微镜中的电子束对铜超微粒子进行了连续地照射和跟踪观察，结果表明电子束使Ｃｕ与镜筒中的低氧压气氛发生了反应，电子束的辐照使纳米量级的Ｃｕ粒子发生了氧化并被消耗，首先生成一种类非晶膜，然后生成Ｃｕ的晶态氧化物，新生成的Ｃｕ的晶态氧化物，在电子束的进一步照射下，又发生了还原反应，不断地还原为铜     

Synthesis of Commercial Products from Copper Wire-Drawing Waste

Copper powder and copper sulfate pentahydrate were obtained from copper wire-drawing scale. The hydrometallurgical recycling process proposed in this article yields a high-purity copper powder and analytical grade copper sulfate pentahydrate. In the first stage of this process, the copper is dissolved in sulfuric acid media via dismutation of the scale. In the second stage, copper sulfate pentahydrate is precipitated using ethanol. Effects such as pH, reaction times, stirring speed, initial copper concentration, and ethanol/solution volume ratio were studied during the precipitation from solution reaction. The proposed method is technically straightforward and provides efficient recovery of Cu from wire-drawing scale.     

涡流贫化法回收铜渣中的金、银、铜

采用熔融铜渣为原料,经过涡流贫化过程,回收铜渣中的金、银、铜,贫化渣进一步升温还原得到含铜铁水,最终可制备成耐磨铸铁。结果表明,通过涡流贫化,铜渣中的Fe_3O_4被还原为FeO,然后FeO与SiO_2结合,生成Fe_2SiO_4。经过涡流贫化后,金、银、铜的回收率分别达到了99.44%、93.97%和93.14%。贫化渣中Fe_3O_4和铜的含量分别为1.53%和0.61%(质量分数)。贫化渣涡流还原后得到的含铜铁水制备的耐磨铸铁成分满足高铬耐磨铸铁国标要求。     

The Dissolution of a Copper Cathode in Acidic Chloride Solutions

The dissolution of cathodically polarized copper under various conditions is definitely measured. The process is most substantially affected by the concentration of dissolved oxygen, while the effect of hydrogen ions is small. Stirring the solution produces a noticeable effect at high cathodic potentials. On the surface of a copper electrode, two opposite processes proceed, namely, the ionization of copper and the deposition of copper ions. A technique for estimating the true rate of the anomalous copper dissolution when the deposition of the dissolution products is minimal is proposed. These dissolution rates of copper substantially exceed the values evaluated from the analysis of the working solution. The integral dissolution of copper is considered in terms of the chemical conjugation of the copper ionization and oxygen reduction. The hydrogen evolution is thought of as also probable.     

A comparison between the corrosion behavior of nanostructured copper thin films deposited on oxidized silicon and copper sheet in alkaline media

Copper thin films were deposited on oxidized silicon at a substrate temperature of 70 °C and 150 °C using EB-PVD technique. The morphology and crystal orientation of the deposited film were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. Corrosion behavior of films was studied through electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, immersion test, and cathodic chronopotentiography. Additionally, the crystalline structure of corroded samples immediately after polarization was examined by XRD. Corrosion current density for copper deposits was higher than copper sheet by polarization tests, while the data obtained by the EIS technique emphasized higher corrosion current density for copper sheet. However there was a conflict between polarization and EIS data, the other results obtained by immersion and cathodic chronopotentiography tests proved that the corrosion resistance of copper deposits was higher than copper sheet in the same alkaline media, which can be attributed to chemical composition and higher thickness of the passive layer formed on copper deposits. On the other hand, breakdown potential (E_bp) for copper sheet was about 0.3 V_SCE, while a distinct E_bp was not found for copper deposits. This was a sign of higher stability of the passive layer formed on copper deposits. The XRD patterns of samples immediately after polarization showed a higher content of Cu(OH)₂ on copper deposits in comparison with copper sheet. The stable morphology formed on the surface of copper after polarization was monoclinic CuO, which is assumed to have a significant effect on copper protection in alkaline media. This morphology was more compact on copper deposits in comparison with copper sheet. This was due to higher ability of deposits to react with hydroxyl ions.     

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     

化学镀镍作为钢酸性镀铜前处理工艺的应用研究

为了防止钢表面酸性电镀铜出现置换铜,采取在电镀铜前增加化学镀镍工序,研究了化学镀镍工艺对酸性电镀铜的影响。结果表明,化学镀镍时间超过6 min时(镍层厚度>2.5～3μm),工件在酸性镀铜液中浸泡10 min,无置换铜出现。化学镀镍层对后续的酸性镀铜层的表面形貌和附着力均无明显影响,表明化学镀镍可作为钢酸性镀铜的底层。     

无铅易切削铜合金的研究进展

综述了Pb在铜合金中的易切削机理和无Pb易切削铜合金的国内外研究进展,重点评述了铋易切削铜合金的可行性及存在的主要问题,同时介绍了所研制的无Pb易切削镁锑黄铜合金的组织和切削试验结果。对无Pb易切削铜合金的研究进行了展望,提出要加大对复合加入(以两种或两种以上元素)在代Pb方面的研究力度。     

The kinetics of copper corrosion in nitric acid

The strategy for the permanent disposal of high-level nuclear waste in Canada involves sealing it in a copper-coated steel container and burying it in a deep geologic repository. During the early emplacement period, the container could be exposed to warm humid air, which could result in the condensation of nitric acid, produced by the radiolysis of the humid air, on the copper surface. Previous studies have suggested that both nitrate and oxygen reduction will drive copper corrosion, with the nitrate reduction kinetics being dependent on the concentration of soluble copper(I) produced by the anodic dissolution of copper in the reaction with oxygen. This study focused on determining the kinetics of nitrate and oxygen reduction and elucidating the synergistic relationship between the two processes. This was investigated using corrosion potential and polarization measurements in conjunction with scanning electron microscopy and X-ray photoelectron spectroscopy. Oxygen reduction was shown to be the dominant cathodic reaction with the oxidation of copper(I) to copper(II) by nitrate, promoting the catalytic cycle involving the reaction of copper(II) with copper to reproduce copper(I).