Summary of the invention
In view of this, the present invention proposes a kind of copper electroplating liquid and electroplating technology thereof, be a kind of Alkali CyanideFree Copper Electroplating Technology, be applied in the electro-coppering production, copper layer and basal body binding force well can reach the requirement of production technique cleaning, environmental protection, can substitute traditional cyanide copper plating technique, solve the prior art environmental pollution and to direct labor's health threat problem.
Technical scheme of the present invention is achieved in that a kind of copper electroplating liquid, and described electroplate liquid mainly comprises complexing agent, main salt, conducting salt, brightening agent, wherein:
Complexing agent content is 100 ~ 200 grams per liters;
Main salts contg is 30 ~ 100 grams per liters;
Conducting salt content is 20 ~ 50 grams per liters;
Brightening agent content is 10 ~ 100 mg/litre;
The pH value of electroplate liquid is 9.0 ~ 11.0; Solvent is water.
Described complexing agent is by one or more the combination in Trisodium Citrate, thionamic acid sodium, Sunmorl N 60S, the disodium ethylene diamine tetraacetate.
Described complexing agent is disodium ethylene diamine tetraacetate and Trisodium Citrate.
Described main salt is by in copper sulfate, the ventilation breather one or both.
Described main salt is ventilation breather, and its content is 50 ~ 80 grams per liters.
Described conducting salt is one or both in vitriolate of tartar, the saltpetre.
Described brightening agent is one or more the combination in Sulfothiorine, potassium sulfocyanate, the furans.
Described pH value is with ammoniacal liquor or sulfuric acid adjustment.
The electroplating technology of a kind of copper electroplating liquid of the present invention is characterized in that: may further comprise the steps:
(1) metallic copper is put into above-mentioned copper electroplating solution, as anode;
(2) workpiece is put into above-mentioned copper electroplating solution, as negative electrode;
(3) pass into direct supply, 0.5 ~ 3 ampere/square decimeter of cathode current density, 40 ~ 55 ℃ of temperature of electroplating solution, electroplating time 2 ~ 8 minutes.
Cathode current density is 1.0 ~ 2.0 amperes/square decimeter in the described step (3); Temperature of electroplating solution is 45 ~ 50 ℃; Electroplating time is 4 ~ 6 minutes.
Compared with prior art, electroplate liquid of the present invention adopts New Chelating Agents to replace the prussiate complexing agent, and the beneficial effect that has is:
1) electroplate liquid does not contain prussiate, reaches the requirement of environment-protecting clean production technique, can direct labor's health problem not threatened.
2) coating and basal body binding force are good, reach the technical requirements of electrolytic coating bonding force.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment, but any limitation of the invention that does not consist of.
Embodiment 1
A kind of copper electroplating liquid, described electroplate liquid mainly comprise complexing agent, main salt, conducting salt, brightening agent, wherein:
The pH value is 10.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 50 C, galvanic current are 1.0 amperes, electroplated 5 minutes, and anode uses copper coin, obtains test piece A1.
Electroplating effect is estimated: observe test piece A1 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571(Usa Metals coating adhesive power qualitative test) standard, test piece A1 is heated to 240 ~ 260 ℃ in stove, then take out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 2
Electroplating bath components:
The pH value is 10.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 50 C, galvanic current are 1.0 amperes, electroplated 8 minutes, and anode uses copper coin, obtains test piece A2.
Electroplating effect is estimated: observe test piece A2 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A2 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 3
Electroplating bath components:
The pH value is 11.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 50 C, galvanic current are 1.0 amperes, electroplated 6 minutes, and anode uses copper coin, obtains test piece A3.
Electroplating effect is estimated: observe test piece A3 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A3 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 4
Electroplating bath components:
The pH value is 9.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: 55 ℃ of temperature, galvanic current are 0.5 ampere, electroplated 8 minutes, and anode uses copper coin, obtains test piece A4.
Electroplating effect is estimated: observe test piece A4 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A4 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 5
Electroplating bath components:
The pH value is 10.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: 40 ℃ of temperature, galvanic current are 0.5 ampere, electroplated 8 minutes, and anode uses copper coin, obtains test piece A5.
Electroplating effect is estimated: observe test piece A5 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A5 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 6
Electroplating bath components:
The pH value is 10.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: 55 ℃ of temperature, galvanic current are 1.5 amperes, electroplated 4 minutes, and anode uses copper coin, obtains test piece A6.
Electroplating effect is estimated: observe test piece A6 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A6 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 7
Electroplating bath components:
The pH value is 10.5, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 50 C, galvanic current are 1.0 amperes, electroplated 5 minutes, and anode uses copper coin, obtains test piece A7.
Electroplating effect is estimated: observe test piece A7 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A7 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Embodiment 8
Electroplating bath components:
The pH value is 11.0, with ammoniacal liquor or sulfuric acid adjustment.
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 45 C, galvanic current are 0.5 ampere, electroplated 3 minutes, and anode uses copper coin, obtains test piece A8.
Electroplating effect is estimated: observe test piece A8 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece A8 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Comparative Examples 1
Electroplating bath components: do not add inferior sodium phosphate;
Electro-plating method: adopt rectangle iron plate 70 * 100mm, electroplate test in the Hull Cell of 267ml, condition is: temperature 50 C, galvanic current are 1.0 amperes, electroplated 5 minutes, and anode uses copper coin, obtains test piece B1.
Electroplating effect is estimated: observe test piece B1 outward appearance, light evenly, crystallization is careful for coating.
Coat binding strength is estimated: according to ASTM B571 standard, test piece B1 is heated to 240 ~ 260 ℃ in stove, then takes out the water of putting into room temperature and cool off, observe whether bubbling or come off of coating.If the copper layer has bubbling or comes off, then copper layer and substrate combinating strength are defective; If the copper layer does not have bubbling or comes off, then copper layer and substrate combinating strength are qualified.
Copper facing test piece obtained above, Deposit appearance effect and bonding strength such as table 1.
Table 1: electroplating effect evaluation table
Numbering |
The plating bath numbering |
Deposit appearance |
Coat binding strength |
Embodiment 1 |
A1 |
Light is even, crystallization is careful |
Qualified |
Embodiment 2 |
A2 |
Light is even, crystallization is careful |
Qualified |
Embodiment 3 |
A3 |
Light is even, crystallization is careful |
Qualified |
Embodiment 4 |
A4 |
Light is even, crystallization is careful |
Qualified |
Embodiment 5 |
A5 |
Light is even, crystallization is careful |
Qualified |
Embodiment 6 |
A6 |
Light is even, crystallization is careful |
Qualified |
Embodiment 7 |
A7 |
Light is even, crystallization is careful |
Qualified |
Embodiment 8 |
A8 |
Light is even, crystallization is careful |
Qualified |
Comparative Examples 1 |
B1 |
Light is even, crystallization is careful |
Qualified |
Do not contain prussiate in the embodiment 1-8 plating bath, the plating bath of Comparative Examples 1 contains prussiate, and the test piece outward appearance copper layer light of embodiment 1-8 and Comparative Examples 1 is even, crystallization is careful, and is good with substrate combinating strength.In sum, a kind of Alkali CyanideFree Copper Electroplating Technology provided by the invention, electroplate liquid does not contain prussiate, and the copper electroplating layer light is even, careful, good with the substrate combinating strength advantage of crystallization.
The above embodiments only are the preferred embodiments of the present invention, can not limit interest field of the present invention with this, and therefore, the equivalent variations according to the present patent application claim is done still belongs to the scope that the present invention is contained.