碳纤维表面单脉冲电镀铜

采用脉冲电镀法在碳纤维表面镀铜,研究了硫酸铜、硫酸、添加剂、施镀时间、电流密度、占空比等因素的影响,确定了合适的镀液成分和电镀工艺. 采用冷热循环法检测镀层与碳纤维的结合力,采用SEM和XRD考察了铜镀层质量. 结果表明,以130 g/L CuSO4×5H2O, g/L H2SO4 50, 30 g/L KNO3及6 mL/L光亮剂为镀液、室温下电流密度82 mA/mm2、占空比40%、施镀时间6 min为电镀条件,可在碳纤维表面得到表面平整细致、结晶度良好的铜镀层. 镀层结合力由原来的270 kPa提高到450 kPa.     

低锡铜-锡合金无氰电镀工艺

通过赫尔槽试验研究了镀液组成、pH和温度对低锡铜-锡合金镀层外观的影响,并用方槽电镀试验研究了时间和电流密度对低锡铜-锡合金镀层的厚度与组成的影响,得到最佳镀液配方与工艺条件为:Cu2P2O7·3H2O 25 g/L,Sn2P2O7 1.0 g/L,K4P2O7·3H2O 250 g/L,K2HPO4·3H2O 60 ...     

HEDP溶液体系镀铜添加剂的研究

在由160 g/L HEDP、40 g/L CuSO4·5H2O和40 g/L K2CO3组成的基础镀液中,研究了添加剂HES、HEA和HEM对镀铜工艺和镀层性能的影响。结果表明,使用HES或HEA做添加剂时,HEDP溶液体系镀铜的电流密度范围分别拓宽至0.05~10.01 A/dm2和0~8.99 A/dm2,HEM可提高低电流密度区的镀铜层光亮度,HES和HEA都具有细化晶粒和整平的作用。通过正交试验得到的最优复合添加剂为:HEA 1.5 mL/L,HES 3.0 mL/L,HEM 0.5 mL/L,CB-1 0.5 mL/L。采用复配添加剂后,镀速和阴极电流效率提高,可在0.24~6.70 A/dm2电流密度范围内制得全光亮、均匀致密、无微裂纹和结合力较好的铜镀层。     

脉冲电沉积制备低锡铜−锌−锡三元仿金合金

在304不锈钢表面脉冲电镀低锡Cu-Zn-Sn仿金合金,镀液组成为:CuSO4·5H2O 0.18 mol/L,ZnSO4·7H2O 0.06 mol/L,Na2SnO3·3H2O 0.05 mol/L,Na3C6H5O7·2H2O 22.66 g/L,Na2CO325 g/L,羟基乙叉二膦酸(HEDP)100 mL/...     

无氰铜锡合金仿金电镀添加剂的研究

通过赫尔槽试验和方槽试验研究了添加剂H-3、DDS和JZ-1对焦磷酸盐溶液体系电镀仿金铜锡合金性能的影响。基础镀液组成为:K4P2O7·3H2O 240 g/L,Sn2P2O7 2.0 g/L,Cu2P2O7·3H2O 24 g/L,p H 8.7。结果表明,采用焦磷酸盐溶液体系电镀铜锡合金时,只有用到添加剂方可得到仿金镀层。添加剂H-3具有一定的整平、细化晶粒和提高光亮度的作用。H-3的用量为2.8 m L/L时,在黄铜基体上获得仿金镀层的阴极电流密度范围为0.29~2.25 A/cm2。焦磷酸盐溶液体系使用添加剂H-3时,在光亮酸铜、光亮镍、无氰白铜锡中间层上和直接在钢铁基体上进行仿金电镀时,均可获得光亮的仿金镀层。     

添加剂对无氰电镀铜-锡合金(低锡)镀层性能的影响

通过赫尔槽试验与直流电解试验,研究了添加剂在焦磷酸盐溶液体系无氰电镀铜-锡合金(低锡)工艺中的作用。该体系镀液组成与工艺条件为:Cu2P2O7·3H2O25g/L,Sn2P2O71.0g/L,K4P2O7·3H2O250g/L,K2HPO4·3H2O60g/L,温度25℃,pH8.5,电流密度1.0A/dm2。采用扫描电镜(SEM)、X射线衍射(XRD)、能谱(EDS)、中性盐雾试验等方法研究了添加剂对镀层组成结构、外观、耐腐蚀性能及微观形貌的影响。结果表明,焦磷酸盐溶液体系无氰电镀铜-锡合金(低锡)时使用有机胺类添加剂可抑制Sn的析出,使合金镀层致密均匀,耐蚀性能好。镀层结晶主要为Cu13.7Sn结构,镀层中Sn含量为9%～11%。镀液中添加剂的使用量增加,则合金镀层中的Sn含量降低。     

工艺参数对电镀镍铜合金镀层成分及相结构的影响

采用由200 g/L NiSO4·6H2O、10 g/L CuSO4·5H2O、80 g/L Na3C6H5O7·2H2O、0.2 g/L C12H25SO4Na和0.5 g/L糖精钠组成的镀液,在10~60 mA/cm2、pH=2.5~5.0和25~50°C条件下电沉积制备了NiCu合金镀层。探讨了镀液pH、电流密度、温度等工艺参数对镍铜合金镀层相结构和组成的影响。结果表明,NiCu合金镀层的铜含量随电流密度或温度升高而增大。但随pH增大,镀层铜含量降低,pH小于4.0时,NiCu合金镀层中含有单质铜。     

镀锡铁基体的化学镀铜

为了提高铁的耐蚀性,在镀锡铁基体上进行了化学镀铜的研究。系统地研究了柠檬酸-酒石酸二元配位体化学镀铜体系中各因素对镀速的影响。结果表明,柠檬酸-酒石酸二元配位体系的镀速大于柠檬酸单配位体系的镀速。随着CuSO4.5H2O、柠檬酸、酒石酸、次磷酸钠浓度的增大,以及随着pH和温度的升高,镀速均先升高后降低。化学镀铜液的最佳组成为：CuSO4.5H2O 12 g/L,柠檬酸40 g/L,酒石酸40 g/L,次磷酸钠20 g/L,抗氧化剂1 g/L,硼酸10 g/L,表面活性剂0.1 g/L。最佳温度为55～60℃、pH为1.25～1.76。在最佳条件下,铜的镀速为5.06μm/h,获得的镀层表面光亮平滑,结晶致密,耐蚀性良好。铜锡镀层之间、锡镀层与铁基体之间的结合力优良。     

EDTA在化学镀铜中的应用

以EDTA为配体,CuSO4·5H2O为主盐,次磷酸钠为还原剂,对铸铁基体表面化学快速镀铜进行了研究,确定的镀液的组成为:7.5g/L CuSO4.5H2O,20 g/L EDTA,38 g/L次磷酸钠,37 g/L四硼酸钠,15g/L柠檬酸三钠,0.5g/L硫酸镍,0.2mg/L硫脲,0.05g/L脂肪醇聚氧乙烯醚(O-20)。最佳工艺条件θ为65℃,pH=8.3,t为40min。结果表明,在上述条件下铸铁基体表面形成的铜镀层光亮度良好,镀层均一,纯度高,显著提高了镀层质量。     

钢铁基体上HEDP体系无氰滚镀铜工艺

探讨了HEDP(羟基乙叉二膦酸)溶液体系滚镀铜工艺的可行性。通过正交试验和单因素实验研究了配位剂含量、主盐含量、电流、温度、装载量和施镀时间对滚镀铜的影响,得到最佳配方和工艺条件为:HEDP 120 g/L,Cu SO4·5H2O 16 g/L,K2CO3 60 g/L,p H 9.5,温度50°C,阴极电流2.0 A,滚筒转速15 r/min,装载量50 g/筒。在该条件下滚镀1 h,可获得高、低电流密度区平均厚度分别为7.39μm和1.60μm,与钢铁基体结合良好的半光亮铜镀层。该滚镀铜工艺基本满足预镀铜的要求,但对有光亮度要求的产品,需要往镀液中加入适量添加剂HEAS。     

铜及铜合金着色

简述了铜及铜合金着色的原理.总结了铜及铜合金着黑色、褐色、绿色、蓝色的工艺配方及操作条件,介绍了手工点涂铜绿(铜锈)、双色点蚀(先着黑色再点蚀铜绿)、套色、着土黄铜绿色等多种特殊的着色工艺.     

Electrocatalytic oxidation of ethanol at copper bromide modified copper electrode in comparison to bare and copper chloride modified copper electrodes

Copper bromide modified copper electrode was prepared and used to electrocatalytic oxidation of ethanol. Scanning electron microscopy and energy dispersive x-ray experiments suggested the formation of thin layer of copper bromide on the copper surface. The j₀ for copper bromide modified copper and copper chloride modified copper electrodes are 9.8 and 5.7 folds respectively higher than for that of bare copper electrode. For copper bromide modified copper electrode, the charge transfer coefficient (α) and the number of electrons involved in the rate determining step (n_α) were calculated as 0.44 and 1 respectively.     

Dissolution from electrodeposited copper–cobalt–copper sandwiches

The electrochemical behaviour of electrodeposited Co–Cu/Cu multilayers from citrate electrolytes was investigated using cyclic voltammetry and stripping techniques at a rotating ring disc electrode. Copper and cobalt–copper alloy sandwiches were deposited from an electrolyte containing 0.0125 M CuSO₄, 0.250 M CoSO₄ and 0.265 M trisodium citrate at two different pHs, 1.7 and 6.0. The Cu/Co–Cu/Cu sandwich is representative of a single layer in a Co–Cu/Cu multilayer deposit, which is known to exhibit unusual physical and magnetic properties. Results from cyclic voltammetry and detection of dissolving species at the ring showed that cobalt is stripped from a Cu/Co–Cu/Cu sandwich even when a copper layer as thick as 600 nm covers the Co–Cu alloy. Scanning electron microscopy showed that cobalt can dissolve from the deposit easily because the copper layer covering the Co–Cu alloy is porous. A separate series of experiments with Cu/Co–Ni–Cu/Cu sandwich showed that cobalt does not dissolve from these deposits because the addition of nickel stabilises cobalt in the Co–Ni–Cu alloy.     

新型铜及铜合金光亮酸洗工艺

介绍了一种铜及铜合金无硝酸、无铬光亮酸洗工艺,其主要工序包括化学除油、盐酸漂洗和化学出光。通过正交试验对化学出光溶液组成进行优化,得到最优配方为:H2SO415%,H3PO420%,出光剂A(含氧化剂、缓蚀剂及表面活性剂)20%。该新型抛光剂适用于多种铜及铜合金,工件的光泽与传统混酸洗工艺相当,在自动线上必要的38s内不会对工件产生过腐蚀。     

萃取光度法测定微量铜

以三氯甲烷作萃取剂，PAN作显色剂，通过光度法测定镀铜废水中的微量铜，选择了适合的测量波长，讨论了酸度，萃取剂用量及振荡时间对萃取率的影响，分析了干扰元素的影响及消除，该方法准确度高，可测量0．01－1．00μg/mL的微量铜。     

Recovery of copper from copper concentrator tailings by leaching

Tailings from a chalcopyrite beneficiation plant (concentrator) have been leached with dilute ferric chloride in a packed bed. The effect of leaching time and packed bed height on the conversion of cuprous sulphide (present in tailings) has been determined. For predicting the conversion, an expression based on the shrinking core model has been derived and compared with the experimental data. At low conversion, the agreement is good, but at intermediate and high conversion the deviation is considerable.     

Oxidation of the copper alloy with pure copper plating

The oxidation failure of a copper alloy lead frame with/without a copper plating layer was investigated. The oxidation rate and adhesion strength of oxide films on copper alloy substrates were studied by measuring the thickness and by carrying out peel tests. The adhesion strength of the oxide film was mainly influenced by the composition but not the thickness of the oxide film. The highest adhesion strength was obtained when the oxide film was composed mainly of Cu₂O. When the thickness of the copper preplated layer was over 0.165?μm, the Cu atoms of the preplated copper were available for oxidation. Thus the oxidation process was within the copper preplated layer, and the main product of the oxidation was Cu₂O. It was found that the large column grain of the oxide film on the copper alloy with a copper plated layer, favored the diffusion of copper or oxygen atoms that led to the formation of Cu₂O, and lead to higher adhesion strength. This indicated that the oxidation resistance of a copper alloy lead frame can be effectively improved by electroplating copper.     

两种含铜杀菌剂中铜含量分析方法的研究

利用氧化还原滴定法测定86.2%氧化亚铜可湿性粉剂、铜甲七十二中氧化亚铜的含量,分析了影响氧化亚铜测定的因素。设备简单,方法快速、准确。方法的变异系数分别为0.31%和0.51%,回收率分别为99.5%和99.6%。分析方法精密度好,准确度高。     

A comparison of the rate of copper deposition at mercury,copper amalgam and copper metal

The rate of reduction of Cu²⁺ ions is slower on solid copper than on mercury. The reason probably lies the adsorption of Cu²⁺ ions on mercury.     

Integration of thin electroless copper films in copper interconnect metallization

Deposition of a thin electroless copper films on PVD copper seed layers in interconnect metallization was investigated for formation of a composite seed layer. Issues such as film stress, adhesion, electrical reliability, and hydrogen incorporation were addressed to determine feasibility of the process for the fabrication of real device structures. The formation of blisters between the copper films and underlying barrier layer were observed due to hydrogen incorporation and high level of compressive stress as a result of the electroless deposition process. Optimization of the electroless copper bath and process flow were investigated to minimize blister formation and improve fill enhancement effectiveness. Low temperature postelectroless anneal was found to remove incorporated hydrogen but also decreased overall fill effectiveness. Post-CMP electrical reliability of thin PVD/electroless/copper fill process was found to be equivalent to thick PVD/copper fill process. Potential reliability issues with electroless deposition on poorly seeded features were suggested by via yield degradation following final anneal.