CN107829116A - Cyanide-free alkaline copper plating electroplate liquid - Google Patents
Cyanide-free alkaline copper plating electroplate liquid Download PDFInfo
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- CN107829116A CN107829116A CN201711340361.0A CN201711340361A CN107829116A CN 107829116 A CN107829116 A CN 107829116A CN 201711340361 A CN201711340361 A CN 201711340361A CN 107829116 A CN107829116 A CN 107829116A
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- 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
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Abstract
A kind of cyanide-free alkaline copper plating electroplate liquid, is mainly mixed by the component of following concentration：(2 hydroxypropyl) the N' AEEAs of N, N, N' tri- 1g/L~60g/L；0~8g/L of tetrahydroxypropyl ethylenediamine；DMH 0g/L~the 0.6g/L of 1,3 dibromo 5,5；Citrate and/or tartrate 25g/L~45g/L；Mantoquita 20g/L~50g/L；Inorganic base 50g/L~70g/L；Conducting salt 20g/L~120g/L；Water surplus；Selected at least from the DMH of 1,3 dibromo 5,5 and tetrahydroxypropyl ethylenediamine a kind of.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 liquid.
Background technology
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 extensively should 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, but cyanide
It is extremely toxic substance, its lethal dose is only 5mg, and it not only has potential safety hazard in use, and 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 systems are without cyanogen alkali copper etc..But these are without cyanogen alkali
The dispersibility of copper is poor, has a strong impact on the uniformity of coating.Particularly there is the device of deep chamber shape, such as：With rectangular
The wave filter of shape or the deep chamber shape of square, its depth reach 3-5cm, and the thickness difference of whole workpiece highest region and lowest region can not
More than 3 times, some workpiece can not even be more than 2 times.It can be seen that traditional no cyanogen alkali copper electrolyte due to device Shang Gao areas with it is low
The thickness difference in area is too big, can not meet demand.Need to research and develop a kind of cyanide-free alkaline copper plating electroplate liquid having compared with high dispersive ability.
The content of the invention
The problem of dispersibility for how to increase cyanide-free alkaline copper plating electroplate liquid, the present invention provide 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：
Selected at least from the bromo- 5,5- DMHs of the 1,3- bis- and tetrahydroxypropyl ethylenediamine a kind of.
Above-mentioned cyanide-free alkaline copper plating electroplate liquid, using N, N, N'- tri- (2- hydroxypropyls)-N'- AEEAs are as master
Complexant is coordinated with copper ion, it is possible to additionally incorporate bromo- 5, the 5- DMHs of 1,3- bis- and/or tetrahydroxypropyl ethylenediamine, citric acid
Salt and/or tartrate strengthen 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 strengthen the scattered energy of plating solution
Power.In addition, adding inorganic base, the pH of plating solution is maintained in certain scope, ensure the coordination form of complexant and copper ion,
Increase the polarization of negative electrode, and then strengthen the dispersibility of plating solution.In addition, certain density conducting salt is additionally added, with increase
Conductance, make cathode surface electric current distribution more uniform, be advantageous to obtain coating in uniform thickness, in addition, the conducting salt
Addition can also decline tank voltage, make the covering power of plating solution be improved, so as to further improve the scattered of plating solution
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- hydroxypropyls)-N '-AEEA conduct
Main complexant, N, (2- hydroxypropyls)-the N '-AEEA of N, N'- tri- and/or bromo- 5, the 5- diformazans of 1,3- bis- are additionally added in addition
Base glycolylurea, citrate and/or tartrate strengthen its coordination ability, the complexant is formed highly stable match somebody with somebody with copper ion
Position ion, to be effectively reduced the deposition potential of copper, is allowed to the deposition potential near or above parent metal, restrained effectively
Reaction between copper electroplating liquid and matrix, therefore can ensure that coating and matrix have good adhesion.
It can be seen that above-mentioned cyanide-free alkaline copper plating electroplate liquid may be used also while ensureing that coating has good adhesion with matrix
To ensure that coating has higher uniformity.Therefore electricity can be carried out to the matrix with irregular shape using the electroplate liquid
Plating, can equally obtain electrodeposited coating in uniform thickness, meet demand.
In a wherein embodiment, the cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration：
In a wherein embodiment, the cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration：
In a wherein embodiment, the cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration：
The mixture of the bromo- 5,5- DMHs of 1,3- bis- and tetrahydroxypropyl ethylenediamine composition has stronger with copper ion
Coordination ability, it can further strengthen the dispersibility of plating solution together with citrate or tartrate.
In a wherein embodiment, the conducting salt includes the first conducting salt and the second conducting salt；First conducting salt
To be one or more in potassium nitrate, potassium sulfate, sodium sulphate, potassium chloride or sodium chloride, second conducting salt be potassium carbonate and/or
Sodium carbonate, the concentration of first conducting salt is 40g/L~60g/L, and the concentration of second conducting salt is 40g/L~70g/L.
First conducting salt can strengthen the electric conductivity of plating solution, can also increase negative electrode unit area current density.
In addition, the second conducting salt is added on the basis of the first conducting salt can stablize bath pH value, ensure the stability of plating solution, also may be used
To improve the depth capability of plating solution, so as to further improve the dispersibility of plating solution.
In a wherein embodiment, the mantoquita is selected from：Copper sulphate or basic copper carbonate；The inorganic base is hydroxide
Potassium；Second conducting salt is selected from：Potassium sulfate and/or potassium carbonate.
Selection copper sulphate or basic copper carbonate have more preferable 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, crystallization is more careful, therefore the dispersiveness of plating solution is also more superior.Such difference be probably because
Sodium, the atom peripheral electron configuration of potassium are different.Similarly, sylvite is selected as conducting salt.
In a wherein embodiment, the mantoquita is selected from：Copper sulphate, basic copper carbonate, copper acetate, copper nitrate, copper chloride
Or its mixture；The inorganic base is potassium hydroxide or sodium hydroxide.
In a wherein 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, electroplated using above-mentioned cyanide-free alkaline copper plating electroplate liquid.
There is higher dispersibility by above-mentioned cyanide-free alkaline copper plating electroplate liquid, therefore the electrodeposited coating obtained by its plating has
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 has higher dispersibility, is suitable in the plating of aluminium alloy device.
In a wherein embodiment, the aluminium alloy device is the aluminium alloy device for having deep chamber shape.
Because above-mentioned cyanide-free alkaline copper plating electroplate liquid has higher dispersibility, for the device with deep chamber shape
Coating in uniform thickness can be obtained, therefore in the plating for being suitable for there is the aluminium alloy device of deep chamber shape.
In one embodiment, the aluminium alloy device is aluminium alloy wave filter.
A kind of aluminium alloy wave filter, including electrodeposited coating, the electrodeposited coating are electroplated by above-mentioned cyanide-free alkaline copper plating electroplate liquid
Form.
Above-mentioned aluminium alloy wave filter has imporosity rate, is well combined and thickness uniformly-coating layer, can be with meet demand.
Brief description of the drawings
Fig. 1 is the schematic diagram of the negative electrode iron plate of an embodiment.
Embodiment
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention
The implication that technical staff is generally understood that is identical.Term used in the description of the invention herein 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
The arbitrary and all combination of the Listed Items of pass.
In addition, in the present invention, EDTO refers to N, and N, N'- tri- (2- hydroxypropyls)-N'- AEEAs, the two can be mutual
Change use；EDTP refers to tetrahydroxypropyl ethylenediamine, and the two is interchangeable；C5H6Br2N2O2 and bromo- 5, the 5- dimethyl of 1,3- bis-
Glycolylurea refers to identical material, is interchangeable.
A kind of cyanide-free alkaline copper plating electroplate liquid, is mixed by the component of following concentration：N, N, N'- tri- (2- hydroxypropyls)-
Bromo- 5, the 5- DMHs of N'- AEEAs 1g/L~60g/L, tetrahydroxypropyl ethylenediamine 0g/L~8g/L, 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, conducting salt 20g/L~120g/L, water surplus；At least from bromo- 5, the 5- DMHs of 1, the 3- bis- and four hydroxypropyls
Selected in ethylenediamine a kind of.
Above-mentioned cyanide-free alkaline copper plating electroplate liquid has stronger dispersibility.So-called dispersibility refers to that electroplating liquid energy makes plating
For the thickness of layer in the equally distributed ability in surface of plated part, dispersibility is also covering power.That is, from scattered energy
The 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 copper ion, can be divided
The stronger electroplate liquid of scattered 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 ingredients 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 somebody with somebody 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 by：(2- the hydroxypropyls)-N'- ethoxys of N, N, N'- tri- second two
Amine, tetrahydroxypropyl ethylenediamine, citrate and/or tartrate, mantoquita, inorganic base, conducting salt and water composition.
In one embodiment, cyanide-free alkaline copper plating electroplate liquid by：(2- the hydroxypropyls)-N'- ethoxys of N, N, N'- tri- second two
Amine, 1,3- bis- bromo- 5,5- DMHs, citrate and/or tartrate, mantoquita, inorganic base, conducting salt and water group
Into.
In one embodiment, cyanide-free alkaline copper plating electroplate liquid by：(2- the hydroxypropyls)-N'- ethoxys of N, N, N'- tri- second two
Amine, tetrahydroxypropyl ethylenediamine, 1,3- bis- bromo- 5,5- DMHs, citrate and/or tartrate, mantoquita, inorganic base,
Conducting salt and water composition.
In one embodiment, with N, the concentration of (2- the hydroxypropyls)-N'- AEEAs of N, N'- tri- (EDTO) is 10g/L
~60g/L；In one embodiment, EDTO concentration is 20g/L~60g/L；In one embodiment, EDTO concentration is 20g/L
~50g/L；In one embodiment, EDTO concentration is 20g/L~45g/L.
In one embodiment, the concentration of bromo- 5, the 5- DMHs (C5H6Br2N2O2) of 1,3- bis- is 0.01g/L~0.6g/
L；In one embodiment, the concentration of bromo- 5, the 5- DMHs of 1,3- bis- is 0.2g/L~0.5g/L；In one embodiment, 1,
The concentration of bromo- 5, the 5- DMHs 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：(the 2- of N, N, N'- tri-
Hydroxypropyl) bromo- 5, the 5- DMHs 0.2g/L~0.4g/L of-N'- AEEAs 20g/L~50g/L, 1,3- bis-, lemon
Lemon hydrochlorate and/or tartrate 25g/L~45g/L, mantoquita 20g/L~50g/L, inorganic base 50g/L~70g/L, conducting 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 group 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：(the 2- of N, N, N'- tri-
Hydroxypropyl)-N'- AEEAs 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, conducting salt 20g/L~130g/L, water
Surplus.
In one embodiment, the concentration of bromo- 5, the 5- DMHs (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- DMHs
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- DMHs 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：(the 2- of N, N, N'- tri-
Hydroxypropyl)-N'- AEEAs 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, conducting salt 20g/L~130g/L, water surplus.
Citrate and tartrate can strengthen complexing power of the plating solution to copper, reduce the drop out point position 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, its concentration are 30g/L~40g/L；In one embodiment, potassium tartrate and the/concentration of potassium citrate for 32g/L~
37g/L；In one embodiment, the concentration of potassium tartrate and/potassium citrate is 35g/L.
In addition, above-mentioned complexant can form highly stable coordination ion with copper ion, the analysis of copper is significantly reduced
Go out current potential, be allowed to the deposition potential near or above parent metal, restrained effectively the reaction between copper electrolyte and matrix, because
This can ensure that coating and matrix have good adhesion.
Selected mantoquita can be the inorganic salts that can provide copper ion, and the mantoquita can be selected from：Copper sulphate, alkali formula carbon
Sour copper, copper acetate, copper nitrate, copper chloride or its mixture.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, improve 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, adding inorganic base in the plating solution to adjust the pH of plating solution, it is set to be maintained within a certain range.Because plating solution
PH be one of the key factor for influenceing 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 changes.PH is too low, coordinates the stability of ion to reduce, and the dispersibility of plating solution reduces, and is also easy to produce
Copper is replaced, coating is combined with matrix loosely, pH is too high, and tint is dim.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 crystallization is more careful, therefore the dispersiveness of plating solution
It is more superior.Such difference is probably because sodium, the atom peripheral electron configuration of potassium are different.
In one embodiment, inorganic base is potassium hydroxide.
It should be noted that the addition of inorganic base needs to carry out appropriate regulation according to conducting salt, such as：Work as conducting salt
For alkaline conducting salt when, can suitably reduce the addition of inorganic base.
In addition, the addition of conducting salt can increase conductance, make cathode surface electric current distribution more uniform, be advantageous to
Coating in uniform thickness is obtained, in addition, the addition of the conducting salt can also decline tank voltage, obtains the covering power of plating solution
Improve, so as to further improve the dispersibility of plating solution.
In one embodiment, conducting salt includes the first conducting salt and the second conducting salt potassium nitrate, potassium sulfate, sodium sulphate, chlorine
Change one or more in potassium or sodium chloride；Second conducting salt is potassium carbonate and/or sodium carbonate, and the concentration of the first conducting salt is 40g/
L~60g/L, the concentration of the second conducting salt is 40g/L~70g/L.
First conducting salt can strengthen the electric conductivity of plating solution, can also increase negative electrode unit area current density.In addition,
The second conducting salt is added on the basis of the first conducting salt can stablize bath pH value, ensure the stability of plating solution, can also change
The depth capability of kind plating solution, so as to further improve the dispersibility of plating solution.
It should be noted that can be only selected from a kind of inorganic salts as conducting salt.
In one embodiment, the first conducting salt is potassium nitrate, and the second conducting salt is potassium carbonate.
In one embodiment, cyanide-free alkaline copper plating electroplate liquid is mixed by the component of following concentration：(the 2- of N, N, N'- tri-
Hydroxypropyl) the bromo- 5,5- DMHs 0.2g/L~0.4g/L of-N '-AEEA 20g/L~45g/L, 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 kind of method for preparing above-mentioned cyanide-free alkaline copper plating electroplate liquid, comprises the following steps：By above-mentioned each complexant, copper
Salt, conducting salt and inorganic base are dissolved in water, and are uniformly mixed and are produced 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 compound method is not particularly limited, only final solution need to be mixed
Close uniform.
A kind of method of cyanide-free alkaline copper plating, electroplated using above-mentioned cyanide-free alkaline copper plating electroplate liquid.
There is higher dispersibility by above-mentioned cyanide-free alkaline copper plating electroplate liquid, therefore the electrodeposited coating obtained by its plating has
Uniform thickness.Purposes of the above-mentioned cyanide-free alkaline copper plating electroplate liquid in Electroplating Aluminum alloy component.
There is higher dispersibility by above-mentioned cyanide-free alkaline copper plating electroplate liquid, therefore the electrodeposited coating obtained by its plating has
Uniform thickness.Purposes of the above-mentioned cyanide-free alkaline copper plating electroplate liquid in Electroplating Aluminum alloy component.
Further, since above-mentioned plating solution has higher dispersibility, coating in uniform thickness, therefore suitable use can be obtained
In the device of plating irregular shape, particularly suitable for the wave filter with rectangle or the deep chamber shape of square, above-mentioned plating
Liquid can cause the high area of the wave filter and low area all to have the coating of uniform thickness, disclosure satisfy that demand.
A kind of aluminium alloy wave filter, including electrodeposited coating, the electrodeposited coating by above-mentioned cyanide-free alkaline copper plating electroplate liquid plating and
Into.
Aluminium alloy wave filter is that a rectangle or the deep chamber shape of square, its depth reach 3cm-5cm, have several points on bottom surface
Separate the small deep chamber and up to 3cm-5cm projections pillar come, and wave filter is high to copper electroplating layer requirement, not only need coating without
Porosity, adhesion are good, and require whole workpiece thickness of coated copper layer requirement control in 3-7cm, and workpiece highest region and most
The thickness difference in low area can not be more than 3 times, and some workpiece can not even be more than 2 times.Due to low in deep chamber workpiece without cyanogen alkali copper coating
Area's sedimentation rate is less than cyanide electroplating, so as to cause the high area of workpiece and low area's thickness difference to meet that very much wave filter plating will greatly
Ask.Traditional non-cyanide plating solution for copper-plating used can not meet the demand, and use above-mentioned cyanide-free alkaline copper plating electroplate liquid to aluminium alloy
Wave filter is electroplated, resulting electrodeposited coating not only imporosity rate, be well combined but also thickness is uniform, can be with meet demand.
Invention is illustrated with reference to specific embodiment.
It should be noted that the reagent or instrument in the unreceipted specific source of the present invention, conventional reagent for market purchase or
Instrument.
Embodiment one
Component and concentration configuration cyanide-free alkaline copper plating electroplate liquid, the concentration of the electroplate liquid are as shown in Tables 1 and 2
1000ml/L, then electroplated using the electroplate liquid by existing method.
(1) compound method of cyanide-free alkaline copper plating electroplate liquid (embodiment 1- embodiments 8)：
By the component and its concentration in Tables 1 and 2, each complexant, mantoquita, conducting salt and inorganic base are dissolved in water
In, it is uniformly mixed and produces cyanide-free alkaline copper plating electroplate liquid.
The cyanide-free alkaline copper plating electroplate liquid of comparative example 1 is prepared by the component in comparative example 1 and its concentration.
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), and it is currently used no cyanogen alkali
Property plating solution for copper-plating used.
(2) bending cathode method measure solution dispersibility
Test flume size is 160mm × 180mm × 120mm.Anode material is anaerobic electrolytic copper plate, size be 150mm ×
50mm × 5mm, the area for immersing solution are 0.55dm2(it is 110mm to immerse solution height equivalent to anode).Cathode material is iron
Piece, each edge lengths are 29mm, thickness 0.2mm, and the area for immersing solution two sides is 1dm2, the back side is on-insulated, such as Fig. 1 institutes
Show.Electroplating current is 1A/dm2, electroplating time 10min.After plating, using coulomb tester, (Wuhan Kang Jie developments in science and technology have
Limit company, KJ-4000 coulombs calibrator) test each face central part of negative electrode style A, B, D, E thickness (A, B, D, E four sides position
Put as shown in Figure 1), then according to the dispersibility of calculation formula calculating plating solution.
Calculation formula：
Wherein δA、δB、δD、δEFor the thickness of each face central portion position of bending cathode A, B, D, E.
Test result such as table 3：
From table 3 it can be seen that above-mentioned cyanide-free alkaline copper plating electroplate liquid have relative to the dispersibility of comparative example 1 it is larger
Improve.In addition, comparative example 1-3 and embodiment 4-8 is understood, when bromo- 5, the 5- DMHs of 1,3- bis- and four hydroxypropyl second
When diamines mixes, the dispersibility of its electroplate liquid is higher.
Embodiment two
Aluminium alloy wave 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) heavy zinc：25 DEG C 55 seconds
(5) zinc is moved back：Normal temperature 60 seconds
(6) heavy zinc：25 DEG C 40 seconds
(7) 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) it is silver-plated：28 DEG C 4 minutes
(10) silver protection：45 DEG C of 4-5 minutes
(11) dry
(12) storage is examined
The each face of wave filter obtained as stated above is respectively provided with uniform thickness.The high area of workpiece and low area's thickness of coating are poor
Less than 3 times, electroplate 40 minutes, workpiece lowest region thickness is not less than 3 microns, and plated layer compact, adhesion is good, can meet wave filter
Performance requirement.
Embodiment three
(1) thermal shock is tested
The wave filter obtained in embodiment two is placed under conditions of 220 DEG C and toasted, takes out after 60 minutes, throws immediately
Enter in cold water, after 10 minutes, take out observation, phenomenon of the part without foaming, decortication.
(2) file is tested
Direction of the edge of the wave filter obtained using four cun of files in embodiment two along metallic matrix to sedimentary with
Coating frustrates sedimentary in 45° angle, observation, and sedimentary and metallic matrix are without separating.
Show that above-mentioned electroplate liquid not only has higher dispersibility, and coating has higher adhesion with matrix.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply 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, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
- A kind of 1. cyanide-free alkaline copper plating electroplate liquid, it is characterised in that the cyanide-free alkaline copper plating electroplate liquid by following concentration group Divide and mix：Selected at least from bromo- 5, the 5- DMHs of 1, the 3- bis- and the tetrahydroxypropyl ethylenediamine a kind of.
- 2. cyanide-free alkaline copper plating electroplate liquid according to claim 1, it is characterised in that the cyanide-free alkaline copper plating electroplate liquid Mixed by the component of following concentration：
- 3. cyanide-free alkaline copper plating electroplate liquid according to claim 1, it is characterised in that the cyanide-free alkaline copper plating electroplate liquid Mixed by the component of following concentration：
- 4. cyanide-free alkaline copper plating electroplate liquid according to claim 1, it is characterised in that the cyanide-free alkaline copper plating electroplate liquid Mixed by the component of following concentration：
- 5. according to the cyanide-free alkaline copper plating electroplate liquid described in claim any one of 1-4, it is characterised in that the conducting salt includes First conducting salt and the second conducting salt；First conducting salt is in potassium nitrate, potassium sulfate, sodium sulphate, potassium chloride or sodium chloride It is one or more；Second conducting salt is potassium carbonate and/or sodium carbonate；The concentration of first conducting salt be 40g/L~ 60g/L, the concentration of second conducting salt is 40g/L~70g/L；The mantoquita is selected from：Copper sulphate, basic copper carbonate, copper acetate, copper nitrate, copper chloride or its mixture；The inorganic base For potassium hydroxide or sodium hydroxide.
- 6. cyanide-free alkaline copper plating electroplate liquid according to claim 5, it is characterised in that the cyanide-free alkaline copper plating electroplate liquid Mixed by the component of following concentration：
- A kind of 7. method of cyanide-free alkaline copper plating, it is characterised in that plated using the non-cyanide alkali described in claim any one of 1-6 Copper electroplating liquid is electroplated.
- 8. purposes of the cyanide-free alkaline copper plating electroplate liquid described in claim any one of 1-6 in Electroplating Aluminum alloy component.
- 9. purposes according to claim 8, it is characterised in that the aluminium alloy device is aluminium alloy wave filter.
- 10. a kind of aluminium alloy wave filter, it is characterised in that including electrodeposited coating, the electrodeposited coating is by any one of claim 1-6 institutes The cyanide-free alkaline copper plating electroplate liquid plating stated forms.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109487309A (en) * | 2018-09-26 | 2019-03-19 | 武汉奥克特种化学有限公司 | A kind of new non-cyanide bright alkaline copper plating complexing agent |
| 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 |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS230197B1 (en) * | 1983-01-28 | 1984-07-16 | Zuzana Cifkova | Copper bath for non-electric chemical coppering |
| US5646236A (en) * | 1994-07-01 | 1997-07-08 | Hoechst Aktiengesellschaft | Polyesters and their use as additives in coating compositions |
| CN101275255A (en) * | 2007-12-20 | 2008-10-01 | 广州市二轻工业科学技术研究所 | Maintenance method for alkaline non-cyanide plating copper |
| US20100243461A1 (en) * | 2009-03-31 | 2010-09-30 | Fujifilm Corporation | Method of fabricating circuit board |
| CN101952487A (en) * | 2007-08-07 | 2011-01-19 | 摩西湖工业公司 | Electroplating aqueous solution and preparation thereof and using method |
| CN102943289A (en) * | 2012-10-25 | 2013-02-27 | 南京大地冷冻食品有限公司 | Complete-displacement cyanide-free alkaline copper |
| CN105274589A (en) * | 2014-05-28 | 2016-01-27 | 无锡永发电镀有限公司 | Alkaline cyanogen-free copper plating electroplating liquid and electroplating method thereof |
| EP3023515A2 (en) * | 2014-11-24 | 2016-05-25 | Rohm and Haas Electronic Materials LLC | Formaldehyde-free electroless metal plating compositions and methods |
| CN105671600A (en) * | 2016-03-16 | 2016-06-15 | 武汉奥邦表面技术有限公司 | Cyanogen-free alkaline copper electroplating solution |
| CN106086836A (en) * | 2016-08-18 | 2016-11-09 | 东莞市印和新材料科技有限公司 | A kind of high Speed Electroless Copper Plating Solution and copper-plating technique thereof |
-
2017
- 2017-12-14 CN CN201711340361.0A patent/CN107829116B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CS230197B1 (en) * | 1983-01-28 | 1984-07-16 | Zuzana Cifkova | Copper bath for non-electric chemical coppering |
| US5646236A (en) * | 1994-07-01 | 1997-07-08 | Hoechst Aktiengesellschaft | Polyesters and their use as additives in coating compositions |
| CN101952487A (en) * | 2007-08-07 | 2011-01-19 | 摩西湖工业公司 | Electroplating aqueous solution and preparation thereof and using method |
| CN101275255A (en) * | 2007-12-20 | 2008-10-01 | 广州市二轻工业科学技术研究所 | Maintenance method for alkaline non-cyanide plating copper |
| US20100243461A1 (en) * | 2009-03-31 | 2010-09-30 | Fujifilm Corporation | Method of fabricating circuit board |
| CN102943289A (en) * | 2012-10-25 | 2013-02-27 | 南京大地冷冻食品有限公司 | Complete-displacement cyanide-free alkaline copper |
| CN105274589A (en) * | 2014-05-28 | 2016-01-27 | 无锡永发电镀有限公司 | Alkaline cyanogen-free copper plating electroplating liquid and electroplating method thereof |
| EP3023515A2 (en) * | 2014-11-24 | 2016-05-25 | Rohm and Haas Electronic Materials LLC | Formaldehyde-free electroless metal plating compositions and methods |
| CN105671600A (en) * | 2016-03-16 | 2016-06-15 | 武汉奥邦表面技术有限公司 | Cyanogen-free alkaline copper electroplating solution |
| CN106086836A (en) * | 2016-08-18 | 2016-11-09 | 东莞市印和新材料科技有限公司 | A kind of high Speed Electroless Copper Plating Solution and copper-plating technique thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109487309A (en) * | 2018-09-26 | 2019-03-19 | 武汉奥克特种化学有限公司 | A kind of new non-cyanide bright alkaline copper plating complexing agent |
| 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 |
| CN110923757A (en) * | 2019-12-27 | 2020-03-27 | 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 |
| CN110983389A (en) * | 2019-12-31 | 2020-04-10 | 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 |
| 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 |
| CN111155153A (en) * | 2020-02-19 | 2020-05-15 | 广州三孚新材料科技股份有限公司 | Copper electroplating solution and copper electroplating method |
| CN114003009A (en) * | 2021-10-29 | 2022-02-01 | 中国联合网络通信集团有限公司 | Copper deposition control method, and training method and device of copper deposition control model |
| 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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