CN1372017A - Method for producing and using compound additives used in electric deposition to level and polish metal - Google Patents
Method for producing and using compound additives used in electric deposition to level and polish metal Download PDFInfo
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- 239000000654 additive Substances 0.000 title claims abstract description 60
- 239000002184 metal Substances 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 title abstract description 7
- 230000008021 deposition Effects 0.000 title description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 44
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 108010010803 Gelatin Proteins 0.000 claims abstract description 19
- 229920000159 gelatin Polymers 0.000 claims abstract description 19
- 239000008273 gelatin Substances 0.000 claims abstract description 19
- 235000019322 gelatine Nutrition 0.000 claims abstract description 19
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 19
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 14
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- -1 alkyl sulfate salt Chemical class 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 17
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 238000012797 qualification Methods 0.000 claims 1
- 239000011343 solid material Substances 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 15
- 150000008051 alkyl sulfates Chemical class 0.000 abstract description 10
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 239000010949 copper Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- XXACTDWGHQXLGW-UHFFFAOYSA-M Janus Green B chloride Chemical compound [Cl-].C12=CC(N(CC)CC)=CC=C2N=C2C=CC(\N=N\C=3C=CC(=CC=3)N(C)C)=CC2=[N+]1C1=CC=CC=C1 XXACTDWGHQXLGW-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005363 electrowinning Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 235000020721 horse chestnut extract Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 230000024121 nodulation Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
一种电沉积平整光亮金属的复合添加剂的生产和使用方法,其由聚丙烯酰胺、硼酸盐、烷基含硫酸盐组成。先将烷基含硫酸盐配制成15～35%百分浓度的水溶液,再加入其他一种或两种,即得到该复合添加剂。其与明胶和硫脲配合使用,控制其在电解液中的浓度为2～10mg/L,可获得平整、光亮的阴极沉积金属,并有效的减少了树枝状结晶在阴极上的生长,具有原料廉价,来源可靠,不污染环境等优点,有直接的工业运用价值。A method for producing and using a compound additive for electrodepositing smooth and bright metal, which consists of polyacrylamide, borate, and alkyl sulfate. The compound additive is obtained by first preparing an alkyl sulfate salt into an aqueous solution with a concentration of 15-35%, and then adding one or two other types. It is used in conjunction with gelatin and thiourea, and its concentration in the electrolyte is controlled to be 2-10 mg/L, so that smooth and bright cathode deposited metal can be obtained, and the growth of dendrites on the cathode can be effectively reduced. It has the advantages of low cost, reliable source, no pollution to the environment, etc., and has direct industrial application value.
Description
(一)技术领域：电化学冶金(1) Technical Field: Electrochemical Metallurgy
(二)背景技术：在公知的金属电沉积工艺中，通过外加少量添加剂物质，可以明显改善阴极沉积金属的化学成分和表面结晶质量。(2) Background technology: In the known metal electrodeposition process, the chemical composition and surface crystallization quality of the cathodically deposited metal can be significantly improved by adding a small amount of additives.
控制阴极极化和电解液中悬浮粒子的含量，使晶粒细化和结晶晶体取向，是添加剂的主要目的。但是，阴极在外观上的几何平整与微观上表面的真实平整存在区别；同样，并非所有细化了的晶粒都能达到外观上光亮效果。表面金属光亮的条件是当晶粒小于可见波长(0.4微米)，具有取向晶体结构。Controlling cathodic polarization and the content of suspended particles in the electrolyte, making grain refinement and crystalline crystal orientation are the main purposes of additives. However, there is a difference between the geometric flatness of the cathode and the real flatness of the microscopic surface; similarly, not all the refined grains can achieve the bright effect in appearance. The bright condition of the surface metal is when the crystal grains are smaller than the visible wavelength (0.4 microns) and have an oriented crystal structure.
在一般的工艺条件下，明胶和硫脲能够达到平整和光亮的要求，已经在金属电沉积工业中广泛使用。实践中已经发现，目前的动物胶在高温水溶液中容易降解，特别是在酸性水溶液中的降解速度更快。使用的硫脲会与阴极金属形成络合物，导致阴极铜中硫含量升高。在高电流密度下，如何抑制杂质砷、锑、铋的析出和漂浮阳极泥的机械夹杂行为，获得平整光亮的阴极质量，引起了研究人员和工业部门的关注。Under general process conditions, gelatin and thiourea can meet the requirements of smoothness and brightness, and have been widely used in the metal electrodeposition industry. In practice, it has been found that the current animal glue is easy to degrade in high-temperature aqueous solution, especially in acidic aqueous solution, the degradation rate is faster. The thiourea used will form complexes with the cathode metal, resulting in increased sulfur content in the cathode copper. Under high current density, how to suppress the precipitation of impurities arsenic, antimony and bismuth and the mechanical inclusion behavior of floating anode slime to obtain a smooth and bright cathode quality has attracted the attention of researchers and industrial sectors.
在中国专利“用于铜电解提纯和铜电解冶金的聚丙烯酸添加剂，公告号：“1193053”中指出，聚丙烯酸作为添加剂用于电解冶金浴和电解提纯浴中，可以细化晶粒、减少树枝状晶体和减少电镀中的杂质。In the Chinese patent "Polyacrylic acid additive for copper electrolytic purification and copper electrolytic metallurgy, announcement number: "1193053", it is pointed out that polyacrylic acid is used as an additive in electrolytic metallurgy baths and electrolytic purification baths, which can refine grains and reduce branches shape crystals and reduce impurities in plating.
在美国专利(U S patent 4336114，Mayer et.al 1982)中，提出了适于电子线路基板金属电镀用添加剂，主要成分有含酞化青染料、聚乙烯亚胺烷基化剂，还含有聚醚化合物。In the U.S. patent (U S patent 4336114, Mayer et.al 1982), an additive suitable for metal plating of electronic circuit substrates is proposed. The main components include phthalocyanine dyes, polyethyleneimine alkylating agents, and poly Ether compounds.
在美国哥伦比亚大学的博士论文：“在有复合表面活性剂存在下铜的电沉积”，作者Kelly，James John，哥伦比亚大学，公告号：AAT9916887，1999(Copper Deposition in the Presence of Mixed Surfactants，Kelly，James John，Columbia University，Publication No：AAT9916887，1999)中，针对印刷电路板制造，研究了四种添加剂：氯离子、聚乙烯乙二醇(PEG)，二-(3-亚砜)-二硫化物(SPS)和JGB(Janus Green B)。研究后发现，聚乙二醇加着色剂及某种二硫化物后，可以得到表面质量很好的阴极铜，聚乙二醇加着色剂的作用次之；明胶和硫脲这两种常规添加剂的作用比前两者的作用都差一些；而效果最差的是明胶加磺基脂肪族有机化合物和二硫化物组成的联合添加剂。Doctoral thesis at Columbia University in the United States: "Copper Deposition in the Presence of Mixed Surfactants", author Kelly, James John, Columbia University, announcement number: AAT9916887, 1999 (Copper Deposition in the Presence of Mixed Surfactants, Kelly, James John, Columbia University, Publication No: AAT9916887, 1999), for the manufacture of printed circuit boards, studied four additives: chloride ion, polyethylene glycol (PEG), di-(3-sulfoxide)-disulfide matter (SPS) and JGB (Janus Green B). After research, it was found that after adding polyethylene glycol coloring agent and some kind of disulfide, cathode copper with good surface quality can be obtained, and the effect of polyethylene glycol adding coloring agent is second; gelatin and thiourea, two conventional additives The role of the effect is worse than the former two; and the worst effect is the combined additive of gelatin plus sulfoaliphatic organic compound and disulfide.
在文献：“一些有机添加剂对从硫酸盐电解液中电解沉积铜的影响”，湿法冶金，2000，54：161-169(The effects of some organic additivsupon copper electrowining from sulphate electrolytes，Hydrometallurgy，2000，54：161-169)中，将HCE(马栗提取物Horse-chestnut extract的缩写)及IT-85(一种乙氧基乙酸乙醇和三乙烷基苯甲基氯化铵的混合物)作为铜电解添加剂进行了研究，并用目测、X-衍射分析阴极铜纯度、X-衍射分析晶粒生长情况等方法进行分析检测后指出，有机添加剂IT-85是一种很好的表面抑制剂，可以获得平整、致密的阴极铜，其作用与硫脲的作用相似。而HCE与动物胶的作用相似，获得的阴极铜有圆形的突起，阴极铜表面质量较差。In the literature: "The effects of some organic additives upon copper electrowinning from sulfate electrolytes", Hydrometallurgy, 2000, 54: 161-169 (The effects of some organic additiv supon copper electrowining from sulfate electrolytes, Hydrometallurgy, 2000, 54 : 161-169), HCE (abbreviation for Horse-chestnut extract) and IT-85 (a mixture of ethoxylated ethanol and triethyl benzyl ammonium chloride) were used as copper electrolytic The additives were studied, and analyzed and detected by visual inspection, X-diffraction analysis of cathode copper purity, X-diffraction analysis of grain growth, etc. It was pointed out that the organic additive IT-85 is a good surface inhibitor, which can obtain flatness , dense cathode copper, its role is similar to that of thiourea. While HCE has a similar effect to animal glue, the obtained cathode copper has round protrusions, and the surface quality of the cathode copper is poor.
至今为止，在众多实际用于铜电解沉积的添加剂中，阿维同—A能显著地改善沉积金属的表面质量，使阴极铜表面光滑、结晶致密，在铜电解精炼工业中得到成功应用。So far, among many additives actually used in copper electrowinning, Aviton-A can significantly improve the surface quality of the deposited metal, make the cathode copper surface smooth and crystallized, and has been successfully applied in the copper electrolytic refining industry.
但是，上述添加剂工艺在不同程度上存在若干限制：原料不容易获得，生产会带来严重的环境污染，工艺流程复杂等。例如，阿维同—A的生产采用氯磺化法(也称Reed法)和磺氧化法(也称I.G.法)，工艺流程复杂，环境污染严重。However, the above-mentioned additive process has some limitations in varying degrees: the raw materials are not easy to obtain, the production will bring serious environmental pollution, and the process is complicated. For example, the production of Aviton-A adopts the chlorosulfonation method (also known as the Reed method) and the sulfonation method (also known as the I.G. method), the process flow is complex, and the environmental pollution is serious.
本发明开发了含聚丙烯酰胺、硼酸盐、烧基含硫酸盐的复合添加剂的生产技术和使用方法。复合添加剂的整体作用机理并不是几个添加剂作用机理的简单迭加，而是几种添加剂的协同作用。该复合添加剂与明胶和硫脲配合使用，生产出的阴极沉积金属致密、平整和光亮，并有效地减少树枝状结晶在阴极的生长。另外，该复合添加剂的平整和光亮的效果类似或优于阿维同—A，原料有可靠的来源，添加剂的生产不会造成环境污染，添加剂的价格不高于目前使用的阿维同—A，具有直接工业应用价值。The invention develops the production technology and application method of the composite additive containing polyacrylamide, borate and alkyl sulfate. The overall action mechanism of the composite additive is not a simple superposition of the action mechanisms of several additives, but a synergistic effect of several additives. The composite additive is used in conjunction with gelatin and thiourea to produce dense, smooth and bright cathode deposited metal, and effectively reduce the growth of dendrites on the cathode. In addition, the leveling and brightening effect of this composite additive is similar to or better than that of Aviton-A, the raw materials have a reliable source, the production of the additive will not cause environmental pollution, and the price of the additive is not higher than that of the currently used Aviton-A , has direct industrial application value.
(三)发明内容：(3) Contents of the invention:
1.发明目的：本发明针对高电流密度和高杂质成分金属电沉积，以及电子线路金属电沉积连接技术的要求，为了使阴极上析出的沉积物表面光亮平整、纯度高、结晶致密，减少电解液中的悬浮物，减少结瘤和枝晶生长所引起的短路，减少阳极泥、电解液机械地粘附在阴极上所引起的污染，研制成功的与明胶和硫脲配合使用时效果显著的复合添加剂技术，可获得致密、平整和光亮的阴极电化学沉积金属。1. Purpose of the invention: the present invention aims at high current density and high impurity composition metal electrodeposition, and the requirements of electronic circuit metal electrodeposition connection technology, in order to make the surface of the deposit precipitated on the cathode bright and smooth, with high purity and compact crystallization, and reduce electrolysis Suspended matter in the liquid, reducing short circuit caused by nodulation and dendrite growth, reducing pollution caused by mechanical adhesion of anode slime and electrolyte to the cathode, successfully developed a compound with remarkable effect when used in conjunction with gelatin and thiourea Additive technology for dense, smooth and bright cathodic electrochemical deposition of metals.
2.复合添加剂的生产方法2. Production method of composite additives
1)原料及所占重量百分比：烷基含硫酸盐85～100％；硼酸盐0～10％；聚丙烯酰胺0～15％。1) Raw materials and their percentage by weight: 85-100% of alkyl sulfate; 0-10% of borate; 0-15% of polyacrylamide.
2)配方2) Recipe
复合添加剂1：烷基含硫酸盐90％；聚丙烯酰胺5％；硼酸盐占5％Composite additive 1: alkyl sulfate 90%; polyacrylamide 5%; borate 5%
复合添加剂2：烷基含硫酸盐95％；聚丙烯酰胺5％；硼酸盐0％；Composite additive 2: alkyl sulfate 95%; polyacrylamide 5%; borate 0%;
复合添加剂3：烷基含硫酸盐100％；聚丙烯酰胺0％；硼酸盐0％；Composite additive 3: alkyl sulfate 100%; polyacrylamide 0%; borate 0%;
复合添加剂4：烷基含硫酸盐88％；聚丙烯酰胺8％；硼酸盐4％；Composite additive 4: alkyl sulfate 88%; polyacrylamide 8%; borate 4%;
复合添加剂5：烷基含硫酸盐90％；聚丙烯酰胺10％；硼酸盐0％；Composite additive 5: alkyl sulfate 90%; polyacrylamide 10%; borate 0%;
3)技术条件3) Technical conditions
(1)先将上述三种固体原料磨细至-20目粉末；(1) First grind the above three solid raw materials to -20 mesh powder;
(2)烷基含硫酸盐按配方中的数量称量放入水中，配制成15-35％(重量百分浓度)的水溶液，再将配方中的另外一种或两种粉末加入上述水溶液中，搅拌至完全溶解，即得该复合添加剂。(2) Alkyl sulfate is weighed according to the quantity in the formula and put into water to prepare a 15-35% (weight percent concentration) aqueous solution, and then add one or two other powders in the formula to the above aqueous solution , and stir until completely dissolved to obtain the composite additive.
3.复合添加剂的使用方法3. How to use compound additives
1)控制复合添加剂在电解液中的重量百分浓度为2～10毫克/升·电解液，(加入量由电解液的总量控制)；1) Control the weight percent concentration of the composite additive in the electrolyte to be 2 to 10 mg/liter electrolyte, (the amount added is controlled by the total amount of the electrolyte);
2)与明胶、硫脲配合使用，先将三种添加剂加水稀释配制成重量百分浓度为复合添加剂0.2～10克/升·水，明胶1-15克/升·水，硫脲0.5～15克/升·水的稀释液，在生产过程中连续均匀的滴入电解液中；2) Used in conjunction with gelatin and thiourea, first dilute the three additives with water to prepare a weight percent concentration of 0.2-10 g/L water for the composite additive, 1-15 g/L water for gelatin, and 0.5-15% thiourea The diluent of g/L·water is continuously and uniformly dropped into the electrolyte solution during the production process;
3)复合添加剂可单独加入电解液，也可与明胶、硫脲混合一起加入电解液。3) The composite additive can be added to the electrolyte alone or mixed with gelatin and thiourea.
4.与公知技术相比本发明具备的优点及积极效果：复合添加剂与现有明胶和硫脲配合，平整和光亮效果类似或优于阿维同—A，能够应用于各种电化学金属沉积过程。添加剂的生产原料有廉价和可靠的来源保证，生产不会造成环境污染，价格不高于现使用的阿维同—A，具有直接的工业应用价值。4. Compared with the known technology, the present invention has the advantages and positive effects: the composite additive is combined with the existing gelatin and thiourea, and the smoothing and brightening effects are similar to or better than Avitam-A, and can be applied to various electrochemical metal deposition process. The production raw materials of the additives are guaranteed by cheap and reliable sources, the production will not cause environmental pollution, the price is not higher than that of the currently used Aviton-A, and it has direct industrial application value.
(四)附图说明：图1是本发明的工艺流程图。(4) Description of drawings: Fig. 1 is a process flow diagram of the present invention.
(五)具体实施方式(5) Specific implementation methods
[实施例1]电解液的组成(g/L)：Cu 48；H2SO4 180；Cl 0.04；Ni 12；As 5；Sb 0.5；Bi 0.3；悬浮物≤0.07。[Example 1] The composition of the electrolyte (g/L): Cu 48; H 2 SO 4 180; Cl 0.04; Ni 12; As 5; Sb 0.5; Bi 0.3;
电解液温度60～65℃；Electrolyte temperature 60～65℃;
电流密度270～300A/m2 Current density 270～300A/m 2
电解液循环量25～35L/min.槽；Electrolyte circulation volume 25～35L/min. tank;
取复合添加剂1，其中烷基含硫酸盐采用烷基磺酸钠、其配比为：烷基磺酸钠90％，聚丙烯酰胺5％，硼酸盐5％；取所需之复合添加剂量(由电解过程中电解液的总量来限定)，用水稀释至浓度为～5g/L再与稀释好的明胶和硫脲混匀后，在连续均匀的滴入电解液中，并保持电解液中含复合添加剂2～10mg/L，明胶3～10mg/L，硫脲2～8mg/L产出致密，平整、光亮的阴极铜。Take composite additive 1, wherein the alkyl sulfate is sodium alkylsulfonate, and its proportioning ratio is: sodium alkylsulfonate 90%, polyacrylamide 5%, borate 5%; take the required composite additive amount (limited by the total amount of electrolyte solution in the electrolysis process), dilute it with water to a concentration of ~5g/L and mix it with diluted gelatin and thiourea, then drop it into the electrolyte solution continuously and uniformly, and keep the electrolyte solution Contains 2-10mg/L of compound additives, 3-10mg/L of gelatin, and 2-8mg/L of thiourea to produce dense, smooth and bright cathode copper.
[实施例2]电解液的组成(g/L)：Cu 49；H2SO4200；Cl 0.04；Ni 8；As 5；Sb 0.5；Bi 0.3；悬浮物≤0.07。[Example 2] Composition (g/L) of the electrolyte: Cu 49; H 2 SO 4 200; Cl 0.04; Ni 8; As 5; Sb 0.5; Bi 0.3;
电解液温度60～65℃；Electrolyte temperature 60～65℃;
电流密度270～300A/m2 Current density 270～300A/m 2
电解液循环量25～35L/min槽；Electrolyte circulation volume 25 ~ 35L/min tank;
明胶稀释液浓度为～4.5g/L；The gelatin dilution concentration is ~4.5g/L;
硫脲稀释液浓度为～2g/L；The concentration of thiourea diluent is ~2g/L;
复合添加剂3 配比：烷基硫酸钠100％稀释液浓度为～1.5g/L；Compound additive 3 Proportion: The concentration of 100% diluent of alkyl sodium sulfate is ~1.5g/L;
添加剂的配制和加入方法与[实施例1]相同。并保持电解液中含有复合添加剂2～8mg/L，明胶3～9mg/L，硫脲2～7mg/L可产出致密、平整、光亮的阴极铜。The preparation and adding method of additives are the same as [Example 1]. And keeping the composite additive in the electrolyte 2-8mg/L, gelatin 3-9mg/L, thiourea 2-7mg/L can produce dense, smooth and bright cathode copper.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100540748C (en) * | 2006-06-15 | 2009-09-16 | 云南冶金集团总公司 | Assembled gelatin additive |
| CN115449850A (en) * | 2022-09-16 | 2022-12-09 | 珠海市建泰环保工业园有限公司 | Method and system for recycling acidic etching waste liquid and extracting copper |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100540748C (en) * | 2006-06-15 | 2009-09-16 | 云南冶金集团总公司 | Assembled gelatin additive |
| CN115449850A (en) * | 2022-09-16 | 2022-12-09 | 珠海市建泰环保工业园有限公司 | Method and system for recycling acidic etching waste liquid and extracting copper |
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