CN105154936A - Rare earth lanthanum-copper-zinc alloy electroplating liquid and electroplating method thereof - Google Patents
Rare earth lanthanum-copper-zinc alloy electroplating liquid and electroplating method thereof Download PDFInfo
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- CN105154936A CN105154936A CN201510516081.5A CN201510516081A CN105154936A CN 105154936 A CN105154936 A CN 105154936A CN 201510516081 A CN201510516081 A CN 201510516081A CN 105154936 A CN105154936 A CN 105154936A
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Abstract
The invention discloses a rare earth lanthanum-copper-zinc alloy electroplating liquid and an electroplating method thereof. The rare earth lanthanum-copper-zinc alloy electroplating liquid comprises 100 g/L-140 g/L of copper sulfate, 40 g/L-60 g/L of zinc sulfate, 0.1 g/L-2 g/L of lanthanum oxide, 4 g/L-20 g/L of formic acid, 40 g/L-80 g/L of sodium pyrosulfite, 1 g/L-8 g/L of formaldehyde and 0.5 g/L-2 g/L of saccharin sodium. A certain amount of rare earth lanthanum is added into the rare earth lanthanum-copper-zinc alloy electroplating liquid, the current efficiency and the disperse capacity can be obviously improved; and a coating obtained through electroplating is compact, uniform, good in combining force and excellent in corrosion resistance.
Description
Technical field
The present invention relates to electroplating technology field, particularly relate to a kind of Rare Earth Lanthanum-copper-zinc alloy electroplate liquid and electro-plating method thereof.
Background technology
The laudatory title that rare earth has " industrial VITAMIN ".Nowadays extremely important strategic resource has been become.Rare earth oxide refers to that period of element atom ordinal number is 15 kinds of lanthanide oxides of 57 to 71, and the oxide compound of the scandium similar to lanthanon chemical property (Sc) and yttrium (Y) totally 17 kinds of elements.Rare earth element is obtained in fields such as oil, chemical industry, metallurgy, weaving, pottery, glass, permanent magnet materials and applies widely, and along with the progress of science and technology and the continuous breakthrough of utilisation technology, the value of rare earth oxide is by increasing.
At present, in order to give brassy metalluster and tone to metal products, plastics, ceramic etc., industrially widely use plating copper-zinc alloy as ornamental plating, but existing copper-zinc alloy erosion resistance is short of to some extent.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of Rare Earth Lanthanum-copper-zinc alloy electroplate liquid, and this Rare Earth Lanthanum-copper-zinc alloy electroplate liquid adds a certain amount of Rare Earth Lanthanum, can significantly improve current efficiency, dispersive ability.
A kind of Rare Earth Lanthanum-copper-zinc alloy electroplate liquid, comprises following component: copper sulfate 100 ~ 140g/L, zinc sulfate 40 ~ 60g/L, lanthanum trioxide 0.1 ~ 2g/L, formic acid 4 ~ 20g/L, Sodium Pyrosulfite 40 ~ 80g/L, formaldehyde 1 ~ 8g/L and sodium benzosulfimide 0.5 ~ 2g/L.
Preferably, following component is comprised: copper sulfate 100 ~ 120g/L, zinc sulfate 50 ~ 60g/L, lanthanum trioxide 0.1 ~ 1g/L, formic acid 4 ~ 20g/L, Sodium Pyrosulfite 60 ~ 80g/L, formaldehyde 1 ~ 4g/L and sodium benzosulfimide 0.5 ~ 0.8g/L.
Preferably, following component is comprised: copper sulfate 110g/L, zinc sulfate 52g/L, lanthanum trioxide 0.5g/L, formic acid 10g/L, Sodium Pyrosulfite 70g/L, formaldehyde 2g/L and sodium benzosulfimide 0.6g/L.
Preferably, described Rare Earth Lanthanum-copper-zinc alloy electroplate liquid pH value is 6 ~ 7.
The present invention provides on the other hand a kind of and uses above-mentioned Rare Earth Lanthanum-copper-zinc alloy electroplate liquid electro-plating method, the coating plated layer compact that this electro-plating method obtains, evenly, the good and excellent corrosion resistance of bonding force.
Use an electro-plating method for above-mentioned electroplate liquid, comprise the following steps:
(1) Sodium Pyrosulfite 40 ~ 80g and sodium benzosulfimide 0.5 ~ 2g is inserted in deionized water to dissolve and form solution, formic acid 1 ~ 8g, copper sulfate 100 ~ 140g and zinc sulfate 40 ~ 60g is added in this solution, heated and stirred is dissolved and is made mixed solution, continue to add lanthanum trioxide 0.1 ~ 2g and formaldehyde 1 ~ 8g in this mixed solution, stirring and dissolving, the deionized water adding surplus is 1L to cumulative volume, obtains Rare Earth Lanthanum-copper-zinc alloy electroplate liquid;
(2) do anode with carbon dioxide process carbon electrode, workpiece does negative pole, electroplates, and namely obtains Rare Earth Lanthanum-copper-zinc alloy coating.
Preferably, Rare Earth Lanthanum-copper-zinc alloy electroplate liquid pH value to 6 ~ 7 are regulated with dilute hydrochloric acid or dilute sulphuric acid in step (1).
Preferably, step (2) electroplating process is 40 ~ 50 DEG C in temperature, and current density is 60 ~ 80mA/cm
2under carry out, the area ratio of negative electrode and positive electrode is (1/2 ~ 2): 1.
Preferably, step (2) electroplating process is 45 DEG C in temperature, and current density is 80mA/cm
2under carry out, the area ratio of negative electrode and positive electrode is 1:1.
Preferably, in step (2), workpiece carries out polishing, degreasing, diluted acid dip treating in early stage.
Compared with prior art, beneficial effect of the present invention: Rare Earth Lanthanum provided by the invention-copper-zinc alloy electroplate liquid comprises following component: copper sulfate 100 ~ 140g/L, zinc sulfate 40 ~ 60g/L, lanthanum trioxide 0.1 ~ 2g/L, formic acid 4 ~ 20g/L, Sodium Pyrosulfite 40 ~ 80g/L, formaldehyde 1 ~ 8g/L and sodium benzosulfimide 0.5 ~ 2g/L.Rare Earth Lanthanum of the present invention-copper-zinc alloy electroplate liquid adds a certain amount of Rare Earth Lanthanum, can significantly improve current efficiency, dispersive ability; Electroplate obtain plated layer compact, evenly, the good and excellent corrosion resistance of bonding force.
Embodiment
Come that the invention will be further described below respectively in conjunction with specific embodiments.
Raw material involved in following examples is commercially available.
Embodiment 1: the Rare Earth Lanthanum-copper-zinc alloy electroplate liquid of the present embodiment comprises following component:
Use this Rare Earth Lanthanum-copper-zinc alloy electroplate liquid electro-plating method as follows:
Sodium Pyrosulfite 40g and sodium benzosulfimide 0.5g is inserted in deionized water to dissolve and form solution, formic acid 1g, copper sulfate 100g and zinc sulfate 40g is added in this solution, heated and stirred is dissolved and is made mixed solution, continue to add lanthanum trioxide 0.1g and formaldehyde 1g in this mixed solution, stirring and dissolving, the deionized water adding surplus is 1L to cumulative volume, obtains Rare Earth Lanthanum-copper-zinc alloy electroplate liquid, regulates pH value to 6 with dilute hydrochloric acid;
Do anode with carbon dioxide process carbon electrode, workpiece is done negative pole through polishing, degreasing, diluted acid dipping behind place, the area ratio of negative electrode and positive electrode is 1:1, Rare Earth Lanthanum-copper-zinc alloy temperature of electroplating solution be 45 DEG C, current density is 80mA/cm
2electroplate under condition, obtain Rare Earth Lanthanum-copper-zinc alloy coating.
Embodiment 2: the Rare Earth Lanthanum-copper-zinc alloy electroplate liquid of the present embodiment comprises following component:
Use this Rare Earth Lanthanum-copper-zinc alloy electroplate liquid electro-plating method as follows:
Sodium Pyrosulfite 60g and sodium benzosulfimide 0.8g is inserted in deionized water to dissolve and form solution, formic acid 1g, copper sulfate 120g and zinc sulfate 50g is added in this solution, heated and stirred is dissolved and is made mixed solution, continue to add lanthanum trioxide 0.1g and formaldehyde 1g in this mixed solution, stirring and dissolving, the deionized water adding surplus is 1L to cumulative volume, obtains Rare Earth Lanthanum-copper-zinc alloy electroplate liquid, regulates pH value to 6 with dilute hydrochloric acid;
Do anode with carbon dioxide process carbon electrode, workpiece is done negative pole through polishing, degreasing, diluted acid dipping behind place, the area ratio of negative electrode and positive electrode is 2:1, Rare Earth Lanthanum-copper-zinc alloy temperature of electroplating solution be 50 DEG C, current density is 80mA/cm
2electroplate under condition, obtain Rare Earth Lanthanum-copper-zinc alloy coating.
Embodiment 3: the Rare Earth Lanthanum-copper-zinc alloy electroplate liquid of the present embodiment comprises following component:
Use this Rare Earth Lanthanum-copper-zinc alloy electroplate liquid electro-plating method as follows:
Sodium Pyrosulfite 70g and sodium benzosulfimide 0.6g is inserted in deionized water to dissolve and form solution, formic acid 10g, copper sulfate 110g and zinc sulfate 52g is added in this solution, heated and stirred is dissolved and is made mixed solution, continue to add lanthanum trioxide 0.5g and formaldehyde 2g in this mixed solution, stirring and dissolving, the deionized water adding surplus is 1L to cumulative volume, obtains Rare Earth Lanthanum-copper-zinc alloy electroplate liquid, regulates pH value to 6 with dilute hydrochloric acid;
Do anode with carbon dioxide process carbon electrode, workpiece is done negative pole through polishing, degreasing, diluted acid dipping behind place, the area ratio of negative electrode and positive electrode is 2:1, Rare Earth Lanthanum-copper-zinc alloy temperature of electroplating solution be 50 DEG C, current density is 80mA/cm
2electroplate under condition, obtain Rare Earth Lanthanum-copper-zinc alloy coating.
Comparative example: the present embodiment alloy plating liquid is not except containing except component lanthanum trioxide, and other are identical with embodiment 1.
The electroplate liquid of testing method known in the field to embodiment 1 ~ 3 and comparative example is adopted to carry out cathode efficiency test, 5%NaCl soaks coating to be observed with or without rust spot for 200 hours, the coating obtained is carried out salt-fog test to measure solidity to corrosion, coating is carried out hot mist experimental observation coating with or without foaming, obscission to measure bonding force, test result is as following table.
Can find out that Rare Earth Lanthanum of the present invention-copper-zinc alloy coating can significantly improve current efficiency by upper table; Electroplate the good and excellent corrosion resistance of the binding force of cladding material that obtains.
Rare Earth Lanthanum of the present invention-copper-zinc alloy electroplate liquid adds a certain amount of Rare Earth Lanthanum, can significantly improve current efficiency, dispersive ability; Electroplate obtain plated layer compact, evenly, the good and excellent corrosion resistance of bonding force.
It should be noted that and understand, when not departing from the spirit and scope of accompanying claim the present invention for required protection, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (9)
1. Rare Earth Lanthanum-copper-zinc alloy electroplate liquid; it is characterized in that, comprise following component: copper sulfate 100 ~ 140g/L, zinc sulfate 40 ~ 60g/L, lanthanum trioxide 0.1 ~ 2g/L, formic acid 4 ~ 20g/L, Sodium Pyrosulfite 40 ~ 80g/L, formaldehyde 1 ~ 8g/L and sodium benzosulfimide 0.5 ~ 2g/L.
2. Rare Earth Lanthanum according to claim 1-copper-zinc alloy electroplate liquid; it is characterized in that, comprise following component: copper sulfate 100 ~ 120g/L, zinc sulfate 50 ~ 60g/L, lanthanum trioxide 0.1 ~ 1g/L, formic acid 4 ~ 20g/L, Sodium Pyrosulfite 60 ~ 80g/L, formaldehyde 1 ~ 4g/L and sodium benzosulfimide 0.5 ~ 0.8g/L.
3. Rare Earth Lanthanum according to claim 1-copper-zinc alloy electroplate liquid; it is characterized in that, comprise following component: copper sulfate 110g/L, zinc sulfate 52g/L, lanthanum trioxide 0.5g/L, formic acid 10g/L, Sodium Pyrosulfite 70g/L, formaldehyde 2g/L and sodium benzosulfimide 0.6g/L.
4. Rare Earth Lanthanum according to claim 1-copper-zinc alloy electroplate liquid, is characterized in that, described Rare Earth Lanthanum-copper-zinc alloy electroplate liquid pH value is 6 ~ 7.
5. use an electroplate liquid electro-plating method described in claim 1, it is characterized in that, comprise the following steps:
(1) Sodium Pyrosulfite 40 ~ 80g and sodium benzosulfimide 0.5 ~ 2g is inserted in deionized water to dissolve and form solution, formic acid 1 ~ 8g, copper sulfate 100 ~ 140g and zinc sulfate 40 ~ 60g is added in this solution, heated and stirred is dissolved and is made mixed solution, continue to add lanthanum trioxide 0.1 ~ 2g and formaldehyde 1 ~ 8g in this mixed solution, stirring and dissolving, the deionized water adding surplus is 1L to cumulative volume, obtains Rare Earth Lanthanum-copper-zinc alloy electroplate liquid;
(2) do anode with carbon dioxide process carbon electrode, workpiece does negative pole, electroplates, and namely obtains Rare Earth Lanthanum-copper-zinc alloy coating.
6. electro-plating method according to claim 5, is characterized in that, regulates Rare Earth Lanthanum-copper-zinc alloy electroplate liquid pH value to 6 ~ 7 in step (1) with dilute hydrochloric acid or dilute sulphuric acid.
7. electro-plating method according to claim 5, is characterized in that, step (2) electroplating process is 40 ~ 50 DEG C in temperature, and current density is 60 ~ 80mA/cm
2under carry out, the area ratio of negative electrode and positive electrode is (1/2 ~ 2): 1.
8. electro-plating method according to claim 7, is characterized in that, step (2) electroplating process is 45 DEG C in temperature, and current density is 80mA/cm
2under carry out, the area ratio of negative electrode and positive electrode is 1:1.
9. electro-plating method according to claim 5, is characterized in that, in step (2), workpiece carries out polishing, degreasing, diluted acid dip treating in early stage.
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Citations (3)
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| CN101302635A (en) * | 2008-01-18 | 2008-11-12 | 梁国柱 | Steel member acidic electroplating additive for copper pre-plating and pre-plating process |
| JP2010059508A (en) * | 2008-09-04 | 2010-03-18 | Bridgestone Corp | Copper-zinc alloy electroplating bath |
| CN102787338A (en) * | 2011-04-19 | 2012-11-21 | 罗门哈斯电子材料有限公司 | Plating of copper on semiconductors |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302635A (en) * | 2008-01-18 | 2008-11-12 | 梁国柱 | Steel member acidic electroplating additive for copper pre-plating and pre-plating process |
| JP2010059508A (en) * | 2008-09-04 | 2010-03-18 | Bridgestone Corp | Copper-zinc alloy electroplating bath |
| CN102787338A (en) * | 2011-04-19 | 2012-11-21 | 罗门哈斯电子材料有限公司 | Plating of copper on semiconductors |
Non-Patent Citations (3)
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| 卢月红: "《实施创新驱动，发展生态建设》", 31 December 2013, 中国环境出版社 * |
| 杨胜奇: ""电镀仿金稀土添加剂的研制"", 《电镀与环保》 * |
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Application publication date: 20151216 |