CN107829116B - Cyanide-free alkaline copper plating electroplate liquid - Google Patents
Cyanide-free alkaline copper plating electroplate liquid Download PDFInfo
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- CN107829116B CN107829116B CN201711340361.0A CN201711340361A CN107829116B CN 107829116 B CN107829116 B CN 107829116B CN 201711340361 A CN201711340361 A CN 201711340361A CN 107829116 B CN107829116 B CN 107829116B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Abstract
A kind of cyanide-free alkaline copper plating electroplate liquid, is mainly mixed by the component of following concentration: (2- the hydroxypropyl)-N'- hydroxyethyl ethylenediamine of N, N, N'- tri- 1g/L~60g/L；0~8g/L of tetrahydroxypropyl ethylenediamine；1,3- bis- bromo- 5,5- Dimethyl Hydan 0g/L~0.6g/L；Citrate and/or tartrate 25g/L~45g/L；Mantoquita 20g/L~50g/L；Inorganic base 50g/L~70g/L；Conductive salt 20g/L~120g/L；Water surplus；At least one kind is selected from the bromo- 5,5- Dimethyl Hydan of the 1,3- bis- and tetrahydroxypropyl ethylenediamine.Above-mentioned cyanide-free alkaline copper plating electroplate liquid has stronger dispersibility.
Description
Technical field
The present invention relates to electroplating technology more particularly to cyanide-free alkaline copper plating electroplate liquids.
Background technique
In electroplating industry, alkaline copper plating is mainly used in the matrixes such as ironware, zinc alloy piece, Al-alloy parts, brass part
Bottoming coating.The complexing agent of traditional alkaline copper plating solution all uses cyanide, and is answered extensively after the World War I
With so far.Cyanide copper plating superior performance, porosity is low, dispersibility is good, covering power is good, bath stability, however cyanide
It is extremely toxic substance, lethal dose is only 5mg, not only there is security risk in use, but also waste water post-processes
It is extremely complex, huge economic pressures are also brought to enterprise.Therefore need to research and develop cyanide-free copper electroplating technique.
Traditionally, no cyanogen alkali copper mainly has: pyrophosphate copper plating, HEDP system are without cyanogen alkali copper etc..But these are without cyanogen alkali
The dispersibility of copper is poor, seriously affects the uniformity of coating.Especially there is the device of deep chamber shape, such as: have rectangular
The filter of shape or the deep chamber shape of square, depth reach 3-5cm, and the thickness difference of entire workpiece highest region and lowest region cannot
Greater than 3 times, some workpiece cannot even be greater than 2 times.As it can be seen that traditional no cyanogen alkali copper electrolyte due to the area device Shang Gao with it is low
The thickness difference in area is too big, is unable to satisfy demand.Need to research and develop a kind of cyanide-free alkaline copper plating electroplate liquid with compared with high dispersive ability.
Summary of the invention
Aiming at the problem that how to increase the dispersibility of cyanide-free alkaline copper plating electroplate liquid, the present invention provides a kind of non-cyanide alkali
Plating solution for copper-plating used.
A kind of cyanide-free alkaline copper plating electroplate liquid, is mixed by the component of following concentration:
At least one kind is selected from the bromo- 5,5- Dimethyl Hydan of the 1,3- bis- and tetrahydroxypropyl ethylenediamine.
Above-mentioned cyanide-free alkaline copper plating electroplate liquid, using N, (2- the hydroxypropyl)-N'- hydroxyethyl ethylenediamine of N, N'- tri- is as master
Complexant and copper ion are coordinated, and additionally incorporate bromo- 5, the 5- Dimethyl Hydan of 1,3- bis- and/or tetrahydroxypropyl ethylenediamine, citric acid
Salt and/or tartrate enhance the coordination of each complexant and copper ion, and reasonably select the concentration of mantoquita, make copper ion with
The concentration ratio of each complexant is maintained within a certain range, so that coating crystallization is careful, greatly strengthens the dispersion energy of plating solution
Power.In addition, inorganic base is added, the pH of plating solution is made to maintain in a certain range, to guarantee the coordination form of complexant and copper ion,
Increase the polarization of cathode, and then enhances the dispersibility of plating solution.In addition, certain density conductive salt is additionally added, to increase
Conductivity keeps the distribution of cathode surface current density more uniform, coating in homogeneous thickness is help to obtain, in addition, the conductive salt
Addition tank voltage can also be made to decline, improve the covering power of plating solution, thus further improve plating solution dispersion
Ability.Therefore, above-mentioned cyanide-free alkaline copper plating electroplate liquid has stronger dispersibility.
And the electroplate liquid uses the N with strong coordination ability, N, N'- tri- (2- hydroxypropyl)-N '-hydroxyethyl ethylenediamine conduct
In addition main complexant is additionally added tetrahydroxypropyl ethylenediamine and/or 1, bromo- 5, the 5- Dimethyl Hydan of 3- bis-, citrate and/or wine
Stone hydrochlorate enhances its coordination ability, so that complexant and copper ion is formed highly stable coordination ion, to be effectively reduced copper
Deposition potential, be allowed to the deposition potential near or above parent metal, restrained effectively between copper electroplating liquid and matrix
Reaction, therefore can guarantee that coating and matrix have good binding force.
It can be seen that above-mentioned cyanide-free alkaline copper plating electroplate liquid may be used also while guaranteeing that coating and matrix have good binding force
To guarantee coating uniformity with higher.Therefore electricity can be carried out to the matrix with irregular shape using the electroplate liquid
Plating, same available electroplated layer in homogeneous thickness, meet demand.
In one embodiment, the cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration:
In one embodiment, the cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration:
In one embodiment, the cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration:
The mixture of the bromo- 5,5- Dimethyl Hydan of 1,3- bis- and tetrahydroxypropyl ethylenediamine composition has stronger with copper ion
Coordination ability can further strengthen the dispersibility of plating solution together with citrate or tartrate.
In one embodiment, the conductive salt includes the first conductive salt and the second conductive salt；First conductive salt
To be one or more in potassium nitrate, potassium sulfate, sodium sulphate, potassium chloride or sodium chloride, second conductive salt be potassium carbonate and/or
Sodium carbonate, the concentration of first conductive salt are 40g/L~60g/L, and the concentration of second conductive salt is 40g/L~70g/L.
The electric conductivity of plating solution can be enhanced in first conductive salt, can also increase cathode unit area current density.
In addition, the second conductive salt is added on the basis of the first conductive salt can stablize bath pH value, guarantee the stability of plating solution, it can also
To improve the depth capability of plating solution, to further improve the dispersibility of plating solution.
In one embodiment, the mantoquita is selected from: copper sulphate or basic copper carbonate；The inorganic base is hydroxide
Potassium；Second conductive salt is selected from: potassium sulfate and/or potassium carbonate.
Select copper sulphate or basic copper carbonate that there is better electroplating effect as the electroplate liquid of mantoquita.
Select potassium hydroxide better than selection sodium hydroxide as the electroplating effect of inorganic base.Potassium hydroxide makes as inorganic base
It is more preferable to obtain plating solution electric conductivity, it is more careful to crystallize, therefore the dispersibility of plating solution is also more superior.Such difference may be because
Sodium, the atom peripheral electron configuration of potassium are different.Similarly, select sylvite as conductive salt.
In one embodiment, the mantoquita is selected from: copper sulphate, basic copper carbonate, copper acetate, copper nitrate, copper chloride
Or mixtures thereof；The inorganic base is potassium hydroxide or sodium hydroxide.
In one embodiment, the cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration:
The electroplate liquid that the component of above-mentioned concentration mixes has higher dispersibility.
A kind of method of cyanide-free alkaline copper plating is electroplated using above-mentioned cyanide-free alkaline copper plating electroplate liquid.
By above-mentioned cyanide-free alkaline copper plating electroplate liquid dispersibility with higher, therefore had by the electroplated layer that its plating obtains
Uniform thickness.Purposes of the above-mentioned cyanide-free alkaline copper plating electroplate liquid in Electroplating Aluminum alloy component.
Above-mentioned cyanide-free alkaline copper plating electroplate liquid dispersibility with higher, is suitable in the plating of aluminium alloy device.
In one embodiment, the aluminium alloy device is the aluminium alloy device with deep chamber shape.
Due to above-mentioned cyanide-free alkaline copper plating electroplate liquid dispersibility with higher, for having the device of deep chamber shape
Coating in homogeneous thickness can be obtained, therefore is suitable in the plating of the aluminium alloy device with deep chamber shape.
In one embodiment, the aluminium alloy device is aluminium alloy filter.
A kind of aluminium alloy filter, including electroplated layer, the electroplated layer are electroplated by above-mentioned cyanide-free alkaline copper plating electroplate liquid
It forms.
Above-mentioned aluminium alloy filter has imporosity rate, is well combined and thickness uniformly-coating layer, can satisfy demand.
Detailed description of the invention
Fig. 1 is the schematic diagram of the cathode iron plate of an embodiment.
Specific embodiment
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
In addition, EDTO refers to N, and N, N'- tri- (2- hydroxypropyl)-N'- hydroxyethyl ethylenediamine, the two can be mutual in the present invention
Change use；EDTP refers to tetrahydroxypropyl ethylenediamine, and the two may be used interchangeably；C5H6Br2N2O2 and 1, bromo- 5, the 5- dimethyl of 3- bis-
Glycolylurea refers to identical substance, may be used interchangeably.
A kind of cyanide-free alkaline copper plating electroplate liquid, is mixed by the component of following concentration: N, N, N'- tri- (2- hydroxypropyl)-
N'- hydroxyethyl ethylenediamine 1g/L~60g/L, tetrahydroxypropyl ethylenediamine 0g/L~8g/L, bromo- 5, the 5- Dimethyl Hydan of 1,3- bis-
0g/L~0.6g/L, citrate and/or tartrate 25g/L~45g/L, mantoquita 20g/L~50g/L, inorganic base 50g/L~
70g/L, conductive salt 20g/L~120g/L, water surplus；At least from bromo- 5, the 5- Dimethyl Hydan of 1, the 3- bis- and four hydroxypropyls
One kind is selected in ethylenediamine.
Above-mentioned cyanide-free alkaline copper plating electroplate liquid has stronger dispersibility.So-called dispersibility refers to that electroplate liquid can make to plate
The thickness of layer is also covering power in the equally distributed ability in surface for being plated part, dispersibility.That is, from dispersion energy
Thickness of coating obtained in the good plating solution of power is all uniform at each position.
Above-mentioned cyanide-free alkaline copper plating electroplate liquid selects several complexant mixing to be coordinated to copper ion, and available point
Dissipate the stronger electroplate liquid of ability.Due to the stability influence electroplate liquid of the valence state and cooperation ion of complexant and copper ion coordination
Dispersibility, it is therefore desirable to suitably selected.
It should be noted that other function component can also be added in above-mentioned electroplate liquid as needed, as long as not to this
Each component in electroplate liquid has an impact.Furthermore it is also possible to add other known complexants, match to increase with copper ion
Capability, as long as not had an impact to each component in the electroplate liquid.
In one embodiment, cyanide-free alkaline copper plating electroplate liquid is by (2- the hydroxypropyl)-N'- ethoxy of N, N, N'- tri- second two
Amine, tetrahydroxypropyl ethylenediamine, citrate and/or tartrate, mantoquita, inorganic base, conductive salt and water composition.
In one embodiment, cyanide-free alkaline copper plating electroplate liquid is by (2- the hydroxypropyl)-N'- ethoxy of N, N, N'- tri- second two
Amine, bromo- 5, the 5- Dimethyl Hydan of 1,3- bis-, citrate and/or tartrate, mantoquita, inorganic base, conductive salt and water group
At.
In one embodiment, cyanide-free alkaline copper plating electroplate liquid is by (2- the hydroxypropyl)-N'- ethoxy of N, N, N'- tri- second two
Amine, tetrahydroxypropyl ethylenediamine, bromo- 5, the 5- Dimethyl Hydan of 1,3- bis-, citrate and/or tartrate, mantoquita, inorganic base,
Conductive salt and water composition.
In one embodiment, with N, the concentration of (2- the hydroxypropyl)-N'- hydroxyethyl ethylenediamine of N, N'- tri- (EDTO) is 10g/L
~60g/L；In one embodiment, the concentration of EDTO is 20g/L~60g/L；In one embodiment, the concentration of EDTO is 20g/L
~50g/L；In one embodiment, the concentration of EDTO is 20g/L~45g/L.
In one embodiment, the concentration of bromo- 5, the 5- Dimethyl Hydan (C5H6Br2N2O2) of 1,3- bis- is 0.01g/L~0.6g/
L；In one embodiment, the concentration of bromo- 5, the 5- Dimethyl Hydan of 1,3- bis- is 0.2g/L~0.5g/L；In one embodiment, 1,
The concentration of bromo- 5, the 5- Dimethyl Hydan of 3- bis- is 0.2g/L~0.4g/L；In one embodiment, bromo- 5, the 5- dimethyl of 1,3- bis-
The concentration of glycolylurea is 0.25g/L~0.3g/L.
In one embodiment, cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration: tri- (2- of N, N, N'-
Hydroxypropyl)-N'- hydroxyethyl ethylenediamine 20g/L~50g/L, bromo- 5, the 5- Dimethyl Hydan 0.2g/L~0.4g/L of 1,3- bis-, lemon
Lemon hydrochlorate and/or tartrate 25g/L~45g/L, mantoquita 20g/L~50g/L, inorganic base 50g/L~70g/L, conductive salt
20g/L~130g/L, water surplus.
In one embodiment, the concentration of tetrahydroxypropyl ethylenediamine (EDTP) is 1g/L~8g/L；In one embodiment, four hydroxyl
The concentration of propyl ethylenediamine is 1g/L~7g/L；In one embodiment, the concentration of tetrahydroxypropyl ethylenediamine is 3g/L~8g/L；?
In one embodiment, the concentration of tetrahydroxypropyl ethylenediamine is 3g/L~6g/L.
In one embodiment, cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration: tri- (2- of N, N, N'-
Hydroxypropyl)-N'- hydroxyethyl ethylenediamine 20g/L~50g/L, tetrahydroxypropyl ethylenediamine 3g/L~8g/L, citrate and/or wine
Stone hydrochlorate 25g/L~45g/L, mantoquita 20g/L~50g/L, inorganic base 50g/L~70g/L, conductive salt 20g/L~130g/L, water
Surplus.
In one embodiment, the concentration of bromo- 5, the 5- Dimethyl Hydan (C5H6Br2N2O2) of 1,3- bis- is 0.01g/L~0.6g/
L, and the concentration of tetrahydroxypropyl ethylenediamine is 0.1g/L~8g/L；In one embodiment, 1,3- bis- bromo- 5,5- Dimethyl Hydan
Concentration is 0.1g/L~0.6g/L, and the concentration of tetrahydroxypropyl ethylenediamine is 3g/L~8g/L；In one embodiment, 1,3- bis-
The concentration of bromo- 5,5- Dimethyl Hydan is 0.2g/L~0.4g/L, and the concentration of tetrahydroxypropyl ethylenediamine is 3g/L~8g/L.
In one embodiment, cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration: tri- (2- of N, N, N'-
Hydroxypropyl)-N'- hydroxyethyl ethylenediamine 10g/L~60g/L, tetrahydroxypropyl ethylenediamine 3g/L~8g/L, bromo- 5, the 5- bis- of 1,3- bis-
Methyl hydantoin 0.1g/L~0.6g/L, citrate and/or tartrate 25g/L~45g/L, mantoquita 20g/L~50g/L, nothing
Machine alkali 50g/L~70g/L, conductive salt 20g/L~130g/L, water surplus.
Plating solution can be enhanced to the complexing power of copper in citrate and tartrate, reduces the precipitation point of copper, Jin Ergai
The dispersibility of kind plating solution.Citrate can be selected from potassium citrate, sodium citrate or ammonium citrate, and tartrate can be selected from
Potassium tartrate, sodium tartrate or ammonium tartrate.
In addition, the dispersibility of the electroplate liquid containing sylvite is better than sodium salt, in one embodiment, potassium tartrate and/lemon are selected
Lemon acid potassium, concentration are 30g/L~40g/L；In one embodiment, potassium tartrate and the/concentration of potassium citrate be 32g/L~
37g/L；In one embodiment, the concentration of potassium tartrate and/potassium citrate is 35g/L.
In addition, above-mentioned complexant and copper ion can form highly stable coordination ion, the analysis of copper is significantly reduced
Current potential out is allowed to the deposition potential near or above parent metal, restrained effectively reacting between copper electrolyte and matrix, because
This can guarantee that coating and matrix have good binding force.
Selected mantoquita can be the inorganic salts for being capable of providing copper ion, which can be selected from: copper sulphate, alkali formula carbon
Or mixtures thereof sour copper, copper acetate, copper nitrate, copper chloride.In one embodiment, mantoquita is basic copper carbonate, due to the alkali formula
Copper carbonate will not introduce anionic impurity to plating solution, and in the presence of an inorganic base, carbonate can improve the crystal knot of coating
Structure improves dispersibility.In one embodiment, mantoquita is copper sulphate, due to copper sulphate introduce sulfate radical on plating solution influence compared with
It is small.
In addition, inorganic base is added in the plating solution to adjust the pH of plating solution, it is made to be maintained within a certain range.Because of plating solution
PH be one of the key factor for influencing quality of coating, it influences the coordination form of complexant and copper ion, complexant and copper from
The state of son is different with pH variation.PH is too low, and the stability of ion is cooperated to reduce, and the dispersibility of plating solution reduces, and is also easy to produce
Replace copper, make coating with matrix in conjunction with loosely, pH is excessively high, tint dimness.In the present embodiment, the concentration of inorganic base is
50g/L~70g/L.
Inorganic base can be potassium hydroxide or sodium hydroxide.Select potassium hydroxide as the dispersion effect of inorganic base than selection
Sodium hydroxide is good.Potassium hydroxide is more preferable as the plating solution electric conductivity of inorganic base, and it is more careful to crystallize, therefore the dispersibility of plating solution
It is more superior.Such difference may be because the atom peripheral electron configuration of sodium, potassium is different.
In one embodiment, inorganic base is potassium hydroxide.
It should be noted that the additional amount of inorganic base needs to carry out adjusting appropriate according to conductive salt, and such as: work as conductive salt
When for alkaline conductive salt, the additional amount of inorganic base can be suitably reduced.
In addition, the addition of conductive salt can increase conductivity, keeps the distribution of cathode surface current density more uniform, be conducive to
Coating in homogeneous thickness is obtained, in addition, the addition of the conductive salt can also be such that tank voltage declines, obtains the covering power of plating solution
Improve, to further improve the dispersibility of plating solution.
In one embodiment, conductive salt includes the first conductive salt and the second conductive salt potassium nitrate, potassium sulfate, sodium sulphate, chlorine
Change one or more in potassium or sodium chloride；Second conductive salt is potassium carbonate and/or sodium carbonate, and the concentration of the first conductive salt is 40g/
L~60g/L, the concentration of the second conductive salt are 40g/L~70g/L.
The electric conductivity of plating solution can be enhanced in first conductive salt, can also increase cathode unit area current density.In addition,
The second conductive salt is added on the basis of the first conductive salt can stablize bath pH value, guarantee the stability of plating solution, can also change
The depth capability of kind plating solution, to further improve the dispersibility of plating solution.
It should be noted that can be only selected from a kind of inorganic salts as conductive salt.
In one embodiment, the first conductive salt is potassium nitrate, and the second conductive salt is potassium carbonate.
In one embodiment, cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration: tri- (2- of N, N, N'-
Hydroxypropyl)-N '-hydroxyethyl ethylenediamine 20g/L~45g/L, the bromo- 5,5- Dimethyl Hydan 0.2g/L~0.4g/L of 1,3- bis-, four
Hydroxypropylethylendiamine diamine 3g/L~8g/L, copper sulphate 30g/L~40g/L, potassium citrate 25g/L~45g/L, potassium hydroxide 50g/L
~70g/L, 40~60g/L of potassium nitrate, 40~70g/L of potassium carbonate, water surplus.
The electroplate liquid that the component of above-mentioned concentration mixes has higher dispersibility.
A method of preparing above-mentioned cyanide-free alkaline copper plating electroplate liquid, comprising the following steps: by above-mentioned each complexant, copper
Salt, conductive salt and inorganic base are dissolved in water, and are uniformly mixed up to cyanide-free alkaline copper plating electroplate liquid.
This method is simple, convenient and raw material is commercial reagent, simple and easy to get.
It should be noted that the material order of addition of above-mentioned preparation method is not particularly limited, only need so that final solution is mixed
It closes uniform.
A kind of method of cyanide-free alkaline copper plating is electroplated using above-mentioned cyanide-free alkaline copper plating electroplate liquid.
By above-mentioned cyanide-free alkaline copper plating electroplate liquid dispersibility with higher, therefore had by the electroplated layer that its plating obtains
Uniform thickness.Purposes of the above-mentioned cyanide-free alkaline copper plating electroplate liquid in Electroplating Aluminum alloy component.
By above-mentioned cyanide-free alkaline copper plating electroplate liquid dispersibility with higher, therefore had by the electroplated layer that its plating obtains
Uniform thickness.Purposes of the above-mentioned cyanide-free alkaline copper plating electroplate liquid in Electroplating Aluminum alloy component.
In addition, due to above-mentioned plating solution dispersibility with higher, available coating in homogeneous thickness, therefore be suitable for using
In the device of plating irregular shape, particularly suitable for the filter with rectangle or the deep chamber shape of square, above-mentioned plating
Liquid can make the high area of the filter and low area all have the coating of uniform thickness, can satisfy demand.
A kind of aluminium alloy filter, including electroplated layer, the electroplated layer by above-mentioned cyanide-free alkaline copper plating electroplate liquid plating and
At.
Aluminium alloy filter is that a rectangle or the deep chamber shape of square, depth reach 3cm-5cm, have several points on bottom surface
Separate the small deep chamber come and up to 3cm-5cm protrusion pillar, and filter is high to copper electroplating layer requirement, not only need coating without
Porosity, binding force are good, and require entire workpiece thickness of coated copper layer requirement control in 3-7cm, and workpiece highest region and most
The thickness difference in low area cannot be greater than 3 times, and some workpiece cannot even be greater than 2 times.Since no cyanogen alkali copper coating is low in deep chamber workpiece
Area's deposition rate is lower than cyanide electroplating, is very much not able to satisfy very much filter plating with low area's thickness difference so as to cause the high area of workpiece and wants
It asks.Traditional non-cyanide plating solution for copper-plating used is unable to satisfy the demand, and uses above-mentioned cyanide-free alkaline copper plating electroplate liquid to aluminium alloy
Filter is electroplated, obtained electroplated layer not only imporosity rate, be well combined but also thickness is uniform, can satisfy demand.
Invention is illustrated combined with specific embodiments below.
It should be noted that the reagent or instrument in specific source is not specified in the present invention, for market purchase conventional reagent or
Instrument.
Embodiment one
Cyanide-free alkaline copper plating electroplate liquid is configured by component shown in Tables 1 and 2 and concentration, the concentration of the electroplate liquid is
Then 1000ml/L is electroplated according to the existing method using the electroplate liquid.
(1) preparation method of cyanide-free alkaline copper plating electroplate liquid (embodiment 1- embodiment 8):
By the component and its concentration in Tables 1 and 2, each complexant, mantoquita, conductive salt and inorganic base are dissolved in water
In, it is uniformly mixed up to cyanide-free alkaline copper plating electroplate liquid.
By the cyanide-free alkaline copper plating electroplate liquid of component and its concentration preparation comparative example 1 in comparative example 1.
Table 1
Table 2
Comparative example 1: 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) 80g/L, potassium citrate 35g/L, copper sulphate 38.5g/L, potassium carbonate
40g/L, potassium hydroxide 40g/L
Complexant used in the comparative example 1 is 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), is currently used no cyanogen alkali
Property plating solution for copper-plating used.
(2) bending cathode method measures solution dispersibility
Test flume is having a size of 160mm × 180mm × 120mm.Anode material is anaerobic electrolytic copper plate, having a size of 150mm ×
50mm × 5mm, the area for immersing solution is 0.55dm2(being equivalent to anode to immerse solution height is 110mm).Cathode material is iron
Piece, each edge lengths are 29mm, and with a thickness of 0.2mm, the area for immersing solution two sides is 1dm2, the back side is on-insulated, such as Fig. 1 institute
Show.Electroplating current is 1A/dm2, electroplating time 10min.After plating, using coulomb tester, (Wuhan Kang Jie development in science and technology has
Limit company, KJ-4000 coulombs of calibrators) test each face central part of cathode style A, B, D, E the thickness (four sides A, B, D, E position
Set as shown in Figure 1), the dispersibility of plating solution is then calculated according to calculation formula.
Calculation formula:
Wherein δA、δB、δD、δEFor the thickness of each face central portion of bending cathode A, B, D, E position.
Test result such as table 3:
From table 3 it can be seen that above-mentioned cyanide-free alkaline copper plating electroplate liquid relative to comparative example 1 dispersibility have it is biggish
It improves.In addition, comparative example 1-3 and embodiment 4-8 is it is found that when bromo- 5, the 5- Dimethyl Hydan of 1,3- bis- and four hydroxypropyl second
When diamines mixes, the dispersibility of electroplate liquid is higher.
Embodiment two
Aluminium alloy filter can be electroplated in the steps below using existing method.
(1) oil removing: 55 DEG C 5 minutes
(2) alkaline etching: 50 DEG C 30 seconds
(3) scale removal: 25 DEG C 90 seconds
(4) sink zinc: 25 DEG C 55 seconds
(5) zinc is moved back: room temperature 60 seconds
(6) sink zinc: 25 DEG C 40 seconds
(7) it is electroplated using the cyanide-free alkaline copper plating electroplate liquid of embodiment 4: 55 DEG C of 40 minutes 1.5A/dm2
(8) burnt copper: 55 DEG C 20 minutes
(9) silver-plated: 28 DEG C 4 minutes
(10) silver protection: 45 DEG C 4-5 minutes
(11) it dries
(12) storage is examined
The each face of the filter obtained according to the above method all has uniform thickness.The high area of workpiece and low area's thickness of coating are poor
It lower than 3 times, is electroplated 40 minutes, workpiece lowest region thickness is not less than 3 microns, and plated layer compact, binding force is good, can satisfy filter
Performance requirement.
Embodiment three
(1) thermal shock is tested
Filter obtained in embodiment two is placed under conditions of 220 DEG C and is toasted, is taken out after sixty minutes, is thrown immediately
Enter in cold water, after ten minutes, take out observation, the part without blistering, decortication the phenomenon that.
(2) file is tested
The edge of the filter obtained in example 2 using four cun of files along direction from metallic matrix to sedimentary with
Coating frustrates sedimentary in 45° angle, observes, and sedimentary and metallic matrix are without separating.
Show above-mentioned electroplate liquid not only dispersibility with higher, but also coating and matrix binding force with higher.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of cyanide-free alkaline copper plating electroplate liquid, which is characterized in that the cyanide-free alkaline copper plating electroplate liquid by following concentration group
Divide and mix:
At least one kind is selected from bromo- 5, the 5- Dimethyl Hydan of 1, the 3- bis- and the tetrahydroxypropyl ethylenediamine.
2. cyanide-free alkaline copper plating electroplate liquid according to claim 1, which is characterized in that the cyanide-free alkaline copper plating electroplate liquid
It is mixed by the component of following concentration:
3. cyanide-free alkaline copper plating electroplate liquid according to claim 1, which is characterized in that the cyanide-free alkaline copper plating electroplate liquid
It is mixed by the component of following concentration:
4. cyanide-free alkaline copper plating electroplate liquid according to claim 1, which is characterized in that the cyanide-free alkaline copper plating electroplate liquid
It is mixed by the component of following concentration:
5. cyanide-free alkaline copper plating electroplate liquid according to claim 1-4, which is characterized in that the conductive salt includes
First conductive salt and the second conductive salt；First conductive salt is in potassium nitrate, potassium sulfate, sodium sulphate, potassium chloride or sodium chloride
It is one or more；Second conductive salt is potassium carbonate and/or sodium carbonate；The concentration of first conductive salt be 40g/L~
60g/L, the concentration of second conductive salt are 40g/L~70g/L；
The mantoquita is selected from: or mixtures thereof copper sulphate, basic copper carbonate, copper acetate, copper nitrate, copper chloride；The inorganic base
For potassium hydroxide or sodium hydroxide.
6. cyanide-free alkaline copper plating electroplate liquid according to claim 5, which is characterized in that the cyanide-free alkaline copper plating electroplate liquid
It is mixed by the component of following concentration:
7. a kind of method of cyanide-free alkaline copper plating, which is characterized in that plated using non-cyanide alkali described in any one of claims 1-6
Copper electroplating liquid is electroplated.
8. purposes of the cyanide-free alkaline copper plating electroplate liquid described in any one of claims 1-6 in Electroplating Aluminum alloy component.
9. purposes according to claim 8, which is characterized in that the aluminium alloy device is aluminium alloy filter.
10. a kind of aluminium alloy filter, which is characterized in that including electroplated layer, the electroplated layer is by any one of claim 1-6 institute
The cyanide-free alkaline copper plating electroplate liquid stated is electroplated.
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| CN109868492A (en) * | 2018-05-18 | 2019-06-11 | 临海市伟星电镀有限公司 | A kind of no cyanogen alkali copper electroplating liquid and preparation method thereof |
| CN109487309B (en) * | 2018-09-26 | 2021-03-23 | 武汉奥克特种化学有限公司 | Novel cyanide-free bright alkaline copper plating complexing agent |
| CN109355686A (en) * | 2018-12-12 | 2019-02-19 | 东莞市同欣表面处理科技有限公司 | A kind of alkali copper electrolyte using HEDP as main complexing agent and preparation method thereof and electroplating technology |
| CN110402015A (en) * | 2019-07-24 | 2019-11-01 | 景旺电子科技(龙川)有限公司 | A kind of production method of direct heat-radiating aluminum printed board |
| CN110923757B (en) * | 2019-12-27 | 2021-04-06 | 广州三孚新材料科技股份有限公司 | Cyanide-free alkali copper electroplating solution and use method thereof |
| CN110983389B (en) * | 2019-12-31 | 2020-11-13 | 广州三孚新材料科技股份有限公司 | Cyanide-free alkaline copper electroplating solution for steel parts and preparation method thereof |
| CN111155153B (en) * | 2020-02-19 | 2021-06-08 | 广州三孚新材料科技股份有限公司 | Copper electroplating solution and copper electroplating method |
| CN114003009B (en) * | 2021-10-29 | 2024-01-12 | 中国联合网络通信集团有限公司 | Copper deposition control method, training method and device of copper deposition control model |
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