基于超临界水技术处理含铜蚀刻废液制备纳米铜的技术经济性评估

通过对比分析多种含铜蚀刻废液处理方法的优缺点,提出了优化的"酸碱蚀刻废液自中和-酸溶解-还原超临界水热合成"组合工艺方案,将废液中铜离子制备为纳米铜粉。首先将酸性、碱性蚀刻废液按一定比例混合发生中和反应生成沉淀,再采用硫酸溶解沉淀生成硫酸铜溶液,最后采用该硫酸铜溶液进行还原超临界水热合成反应制备纳米铜终产物。该工艺方案具有流程简单、易大规模应用、可实现废液零排放和纳米铜粉制备效率高等技术优势;处理废液的运行费用约为3500元/t,制备的纳米铜粉可获得极高的经济收益,在蚀刻废液的无害化处理及资源化利用领域中具有广阔的发展前景。     

硝磷酸氨法净化生产磷酸二氢铵工艺研究

针对硫酸法湿法磷酸生产磷酸二氢铵副产磷石膏的问题，基于硝酸法冷冻母液深度脱硝后的净化液，采用氨中和工艺生产工业级磷酸二氢铵，系统研究了反应温度、磷酸浓度、反应时间、搅拌速率、pH、杂质离子浓度等因素对于氨中和工艺的影响。结果表明，氨中和过程中杂质离子生成磷酸盐沉淀影响磷收率，且杂质离子之间主要以形成复盐沉淀互相影响。通过对比氨中和后滤液的成分可得出最佳工艺条件：P₂O₅质量分数为15%、反应温度为85℃、搅拌速率为250 r/min、反应时间为40 min、pH为4.3，最后以最佳工艺条件制备的磷酸二氢铵产品达到一级产品标准要求。     

由线路板碱性废蚀刻液回收硫酸铜

由线路板碱性废蚀刻液回收硫酸铜使用碱性蚀刻液进行线路板加工后的废蚀刻液其含铜量可达１０～１５％。主要以硫酸铜氨络合物形式存于溶液中，用它来生产硫酸铜可获得良好的经济效益，并且有积极的环保意义。１原理２工艺流程３工艺流程依据：３．１配制６０％的Ｈ２ＳＯ...     

从酸性氯化铜蚀刻废液中回收氧化亚铜和氯化钠

以某PCB(印制线路板)厂的酸性CuCl_2蚀刻废液为原料,采用液相法制备Cu_2O,并对其中的NaCl进行回收。研究了水合肼与废液中Cu~(2+)的浓度比、pH、反应温度、时间等参数对Cu_2O纯度的影响,得到最佳工艺条件为:先在水合肼与Cu~(2+)的浓度比为0.2625、pH=4~5和室温之下沉淀和还原,再在pH=12、100 ℃之下取代和脱水反应1 h。所得Cu_2O的纯度达98.4%,铜杂质含量小于0.07%,满足HG/T 2961–2010中优等品的要求。回收的NaCl纯度高于97.5%,符合GB/T 5462–2015中二级精制工业盐的要求。     

碱性蚀刻废液的综合利用-水合肼还原回收铜

研究了以水合肼为还原剂,回收碱性蚀刻废液中铜的方法。试验结果表明,最佳工艺条件为：水台肼用量3.5mL,反应时间40min,0．05mL催化剂LA和1．5mL催化剂LB,铜的收率为68．6％。回收锕后的碱性蚀刻废液可重复利用,用于配制新的蚀刻液,基本实现零排放,实现清洁生产。     

铜蚀刻废液制备氧化铜

采用沉淀法分别以酸性蚀刻废液、酸性和碱性混合蚀刻废液制取氧化铜，并优化了工艺条件。结果表明，酸性蚀刻废液和混合蚀刻废液中铜离子沉淀的最佳pH值分别为9和4．3，氢氧化铜沉淀的最佳分解温度和时间分别为500℃和30rain，采用自来水洗3次、纯净水洗3次的洗涤方式，可有效去除沉淀中的杂质氯离子和铵离子。     

化学还原法处理酸性镀铜废水

含铜废水的处理常用的有离子交换法、槽边电解法和氢氧化物沉淀法。国外曾有报导用甲醛作还原剂还原沉淀铜的方法。本文提出用连二亚硫酸钠作还原剂,投放在酸性镀铜废水中,使铜离子还原成金属铜沉淀,再经过滤回收。滤液中尚含有过量的连二亚硫酸钠及亚硫酸,可作还原剂使用,适用于处理六价铬废水,达到了废物利用的目的。本工艺对30g/L以下的含铜废水有效,投药比按铜离子算为1:3.9,按硫酸铜算为1:1。滤液中残余的铜离子量为1mg/L以下,符合排放标准的规定。本方法设备简便,管理方便,为处理含铜废水提出了一个新的途径。     

印刷线路板废液的综合利用

<正> 印刷线路板的腐蚀废液中含有氯化亚铁、氯化铁及氯化铜等,如直接排放,污染环境,且浪费有用金属。为此,我们试验成功了由废液中回收两种金属盐的方法。硫酸铜的制备废液中加入理论量115％的铁屑,析出沉淀,为铜铁混合物。过滤,滤液供回收铁盐用。沉淀物与理论量120～125％的浓盐酸在搅拌下反应,pH保持1～2。反应完毕后,静置2小时,过滤,滤液与上述滤液合并,沉淀用倾注法洗涤,得粗海绵铜。再依次与计量的6N硝酸及6N硫酸反应,反应结束后过滤,滤液蒸发浓缩至49～     

硝酸铵氧化法制备氯化亚铜技术研究

介绍了硝酸铵氧化分解海绵铜生产氯化亚铜的方法。工艺过程：将海绵铜加入硝酸铵和硫酸的混合液中,海绵铜中的铜溶解得到硫酸铜溶液;向硫酸铜溶液中加入亚硫酸铵和氯化铵,亚硫酸铵将硫酸铜还原为硫酸亚铜,氯化铵将硫酸亚铜氯化沉淀为氯化亚铜;氯化亚铜经酸洗、醇洗、烘干得到成品;滤液经蒸发浓缩得到硫酸铵副产品。最佳制备条件：（1）海绵铜溶解过程,反应温度为60 ℃,硫酸浓度为0.2~0.3 mol/L,硝酸铵用量为过量10%~20%;（2）沉淀氯化亚铜过程,亚硫酸铵与硫酸铜的物质的量比为0.6,氯化铵与硫酸铜的物质的量比为1.0~1.1; （3）沉淀氯化亚铜用质量分数为2%的硫酸水溶液洗涤,再用质量分数为95%的乙醇洗涤,再经烘干得到氯化亚铜产品,所得产品质量符合GB/T 27562-2011《工业氯化亚铜》要求。     

原子荧光法测定食品添加剂硫酸铜中痕量砷

原子荧光法测定食品添加剂硫酸铜中痕量砷,铜与硫脲和硼氢化钾反应均发生沉淀,影响测量结果。样品溶液先用碘化钾将溶液中的铜还原为碘化亚铜,然后加入硫氰酸盐,将溶液中游离的亚铜离子以硫氰化亚铜的形式沉淀下来,过滤定容后测定样品溶液中的砷,回算出样品中的砷含量。该方法条件下加标回收实验结果符合相关要求。     

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.