CN103806063A - Method for electroplating silver on molybdenum foil surface - Google Patents
Method for electroplating silver on molybdenum foil surface Download PDFInfo
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- CN103806063A CN103806063A CN201210444359.9A CN201210444359A CN103806063A CN 103806063 A CN103806063 A CN 103806063A CN 201210444359 A CN201210444359 A CN 201210444359A CN 103806063 A CN103806063 A CN 103806063A
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Abstract
The present invention relates to a method for electroplating silver on a molybdenum foil surface. The method is characterized in that Ag ions with a certain dose are injected into a molybdenum foil, and cyanide-free silver electroplating is performed on the surface. According to the present invention, the metal plasma injection modification technology is adopted to directly inject the Ag ions into molybdenum so as to obtain the Ag-modified layer with characteristics of no significant interface and high bonding strength, ion beam bombardment is adopted to remove natural oxides and improve the surface conductivity, and then electroplating is performed on the molybdenum, such that the obtained Ag electroplating layer has characteristics of good quality and high bonding strength.
Description
Technical field
The present invention relates to a kind of method of electrosilvering, be specifically related to a kind of silver-plated method of molybdenum foil surface electrical.
Background technology
Molybdenum and molybdenum alloy belong to high temperature material, at high temperature can keep higher intensity, also there is high thermal conductivity and low thermal expansivity simultaneously, good thermal shock resistance, electroconductibility and wear resistance, be widely used in aerospace field, comprising the molybdenum foil for spacecraft solar array sheet of interconnect.But the weldability of molybdenum is relatively poor, and can strong oxidation when high temperature, this oxide film has no protective effect, therefore need electroplate modification on molybdenum surface.Because silver has good brazing property, conventionally silver-plated to improve solderability in molybdenum surface electrical, and reduce or prevent the oxidation of molybdenum.But because molybdenum surface often exists native oxide (MoO3), can disturb the absorption of coating, between molybdenum and silver, form alloy (sosoloid) very difficult in addition, therefore, larger in the silver-plated difficulty of molybdenum surface electrical, directly silver-plated often adhesion is not firm, and quality of coating is poor.It is generally to adopt preplating or strike plating first to plate the thin metal of one deck (as chromium, nickel, gold, rhodium, platinum etc.) on surface that solution molybdenum is electroplated difficult way, continues to electroplate after high-temperature heat treatment again, and technique is comparatively loaded down with trivial details.Meanwhile, nickel preplating causes disadvantageous effect to conductivity, and gold, rhodium, platinum also can strengthen cost.
Summary of the invention
For the deficiencies in the prior art, it is a kind of in the silver-plated method of molybdenum foil surface electrical that one of object of the present invention is to provide, and it can effectively improve the bonding force of silvered film and molybdenum foil and technique is simple, cost is lower.
Present inventor finds through a large amount of test and studies, adopt metal plasma to inject modification technology directly by ion implantation Ag molybdenum, can obtain without sharp interface, there is the very Ag modified layer of high bond strength, and utilize the bombardment of ionic fluid to remove native oxide, improve its surperficial electroconductibility, molybdenum is electroplated, the Ag electrolytic coating quality of acquisition is better, bonding strength is high again.Thereby realize the present invention.
Of the present invention in the silver-plated method of molybdenum foil surface electrical, comprise in ion implantation the Ag of doses molybdenum foil, then carry out non-cyanide silver electroplating on its surface.
Wherein, the technique that described silver ions injection molybdenum foil adopts is: silver more than employing purity 99.8wt% is as metallic cathode, and Implantation Energy is 95-115keV, and dosage is (0.1-5) × 10
17ions/cm
2, line is controlled at 2.5-4mA left and right.
To achieve these goals, technical scheme of the present invention has adopted a kind of described non-cyanide silver coating electroplate liquid, formulated by following composition: Silver Nitrate 40～45g/L, Sulfothiorine 200～250g/L, potassium pyrosulfite 40～45g/L, ammonium acetate 20～30g/L, thiosemicarbazide 0.6～0.8g/L, pH remains on 5～6.
The preparation method of described electroplate liquid is first dissolved in the Sulfothiorine of calculated amount in distilled water, stirs it is all dissolved; Then the Silver Nitrate of calculated amount and potassium pyrosulfite are dissolved with distilled water respectively, and under agitation pyrosulphite potassium solution is poured in silver nitrate solution, generate after pyrosulphite silver turbid solution, immediately solution is added in hypo solution slowly, generate micro-yellow clear liquor; Again the ammonium acetate of calculated amount is added in solution, after the solution left standstill preparing, then add the thiosemicarbazide of calculated amount, it is all dissolved, finally fixed molten with distilled water.
Described temperature when silver-plated is 15 ℃～30 ℃; Ratio of cathodic to anodic area is 0.7～1: 1.5～2, and anode adopts the fine silver plate of 99.99wt.%.
Advantage of the present invention is: (1) plating solution toxicity is extremely low or nontoxic, has reduced to a greater degree the harm to environment and operator, bath stability and dispersed good; (2) silver coating can reach nano level, and is combined with matrix well, surfacing, densification, and luminance brightness is good, and anti-tarnishing ability is strong; (3) the silver-plated rust cleaning and silver-plated in advance before of present method, technique is simple, easy to operate, with low cost, can meet the needs of production field.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
The formula of the electroplate liquid of the non-cyanide silver coating of the present embodiment and preparation method are
The formula of electroplate liquid is: Silver Nitrate 40g/L, and Sulfothiorine 200g/L, potassium pyrosulfite 40g/L, ammonium acetate 20g/L, thiosemicarbazide 0.6g/L, pH remains on 5～6.
The preparation method of electroplate liquid: first the Sulfothiorine of 200g is dissolved in the distilled water of 300ml, stirs it is all dissolved; Then the potassium pyrosulfite of the Silver Nitrate of 40g and 40g is dissolved with the distilled water of 250ml respectively, and under agitation pyrosulphite potassium solution is poured in silver nitrate solution, generate after pyrosulphite silver turbid solution, immediately solution is added in hypo solution slowly, make silver ions and Sulfothiorine complexing, generate micro-yellow clear liquor; Again the ammonium acetate of 20g is added in solution, after the solution left standstill preparing, then add the thiosemicarbazide of 0.6g, it is all dissolved, be finally dissolved to 1L with distilled water.
Embodiment 2
The formula of the electroplate liquid of the non-cyanide silver coating of the present embodiment and preparation method are
The formula of electroplate liquid is: Silver Nitrate 43g/L, and Sulfothiorine 230g/L, potassium pyrosulfite 43g/L, ammonium acetate 25g/L, thiosemicarbazide 0.7g/L, pH remains on 5～6.
The preparation method of electroplate liquid: preparation method, with embodiment 1, just requires the add-on of each composition to be adjusted accordingly according to formula.
Embodiment 3
The formula of the electroplate liquid of the non-cyanide silver coating of the present embodiment and preparation method are
The formula of electroplate liquid is: Silver Nitrate 45g/L, and Sulfothiorine 250g/L, potassium pyrosulfite 45g/L, ammonium acetate 30g/L, thiosemicarbazide 0.8g/L, pH remains on 5～6.
The preparation method of electroplate liquid: preparation method, with embodiment 1, just requires the add-on of each composition to be adjusted accordingly according to formula.
Embodiment 4
The non-cyanide silver coating method of the present embodiment mainly comprises the following steps:
(1) silver-plated front ion implantation silver: silver more than employing purity 99.8wt% is as metallic cathode, and Implantation Energy is 95keV, and dosage is 0.1 × 10
17ions/cm
2, line is controlled at 4mA left and right;
(2) DC electrodeposition is silver-plated: pretreated plating piece is carried out to DC electrodeposition silver-plated, the current density when silver-plated is 0.1A/dm2, and temperature is 15 ℃; Ratio of cathodic to anodic area is 0.7: 2, and anode adopts the fine silver plate of 99.99wt.%; Wherein electroplate liquid uses the plating solution of preparing in embodiment 1.
Embodiment 5
The non-cyanide silver coating method of the present embodiment mainly comprises the following steps:
(1) silver-plated front ion implantation silver: silver more than employing purity 99.8wt% is as metallic cathode, and Implantation Energy is 115keV, and dosage is 5 × 10
17ions/cm
2, line is controlled at 2.5mA left and right.
(2) DC electrodeposition is silver-plated: pretreated plating piece is carried out to DC electrodeposition silver-plated, the current density when silver-plated is 0.2A/dm
2, temperature is 25 ℃; Ratio of cathodic to anodic area is 1: 2, and anode adopts the fine silver plate of 99.99wt.%; Wherein electroplate liquid uses the plating solution of preparing in embodiment 2.
Embodiment 6
The non-cyanide silver coating method of the present embodiment mainly comprises the following steps
(1) silver-plated front ion implantation silver: silver more than employing purity 99.8wt% is as metallic cathode, and Implantation Energy is 105keV, and dosage is 1 × 10
17ions/cm
2, line is controlled at 3mA left and right;
(2) DC electrodeposition is silver-plated: pretreated plating piece is carried out to DC electrodeposition silver-plated, the current density when silver-plated is 0.3A/dm
2, temperature is 30 ℃; Ratio of cathodic to anodic area is 2: 3, and anode adopts the fine silver plate of 99.99wt.%; Wherein electroplate liquid uses the plating solution of preparing in embodiment 3.
Use aforesaid method, the silver coating covering power obtaining under DC electrodeposition effect is good, can reach nano level, and is combined with matrix well, surfacing, densification, and luminance brightness is good, and anti-tarnishing ability is strong.
Applicant's statement, 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, 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, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (4)
1. the method that molybdenum foil surface electrical is silver-plated, it is characterized in that, by in ion implantation the Ag of doses molybdenum foil, then carry out non-cyanide silver electroplating on its surface, wherein, the technique that described silver ions injection molybdenum foil adopts is: silver more than employing purity 99.8wt% is as metallic cathode, and Implantation Energy is 95-115keV, and dosage is (0.1-5) × 10
17ions/cm
2, line is controlled at 2.5-4mA left and right.
2. according to the method for claim 1, it is characterized in that: described electroplate liquid is formulated by following composition: Silver Nitrate 40～45g/L, Sulfothiorine 200～250g/L, potassium pyrosulfite 40～45g/L, ammonium acetate 20～30g/L, thiosemicarbazide 0.6～0.8g/L.
3. method according to claim 2, is characterized in that: the temperature when silver-plated is 15 ℃～30 ℃.
4. method according to claim 2, is characterized in that: in described step (2), adopt the fine silver plate of 99.99wt.% for silver-plated anode, ratio of cathodic to anodic area is 0.7～1: 1.5～2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210444359.9A CN103806063A (en) | 2012-11-08 | 2012-11-08 | Method for electroplating silver on molybdenum foil surface |
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| CN201210444359.9A CN103806063A (en) | 2012-11-08 | 2012-11-08 | Method for electroplating silver on molybdenum foil surface |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105112952A (en) * | 2015-09-21 | 2015-12-02 | 无锡清杨机械制造有限公司 | Electroplating solution for non-cyanide silver electrodeposition, and electroplating method |
| CN107254696A (en) * | 2017-06-08 | 2017-10-17 | 广东电网有限责任公司电力科学研究院 | Silver/graphite alkene composite silver plating liquor and preparation method thereof and electrodeposition technology |
| CN109280895A (en) * | 2017-07-20 | 2019-01-29 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion |
-
2012
- 2012-11-08 CN CN201210444359.9A patent/CN103806063A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105112952A (en) * | 2015-09-21 | 2015-12-02 | 无锡清杨机械制造有限公司 | Electroplating solution for non-cyanide silver electrodeposition, and electroplating method |
| CN107254696A (en) * | 2017-06-08 | 2017-10-17 | 广东电网有限责任公司电力科学研究院 | Silver/graphite alkene composite silver plating liquor and preparation method thereof and electrodeposition technology |
| CN109280895A (en) * | 2017-07-20 | 2019-01-29 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the Mo/Ag laminar composite of high-densit, high interface cohesion |
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