CN110158129A - Pre- bleeding agent composition, pre- bleeding agent, copper facing preprocess method and cyanide-free copper electroplating method - Google Patents
Pre- bleeding agent composition, pre- bleeding agent, copper facing preprocess method and cyanide-free copper electroplating method Download PDFInfo
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- CN110158129A CN110158129A CN201910445567.2A CN201910445567A CN110158129A CN 110158129 A CN110158129 A CN 110158129A CN 201910445567 A CN201910445567 A CN 201910445567A CN 110158129 A CN110158129 A CN 110158129A
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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
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
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Abstract
The present invention relates to a kind of pre- bleeding agent composition, pre- bleeding agent, copper facing preprocess method and cyanide-free copper electroplating method, which includes the first complexing agent, the second complexing agent and third complexing agent；Wherein, first complexing agent is succinate, and second complexing agent is selected from least one of tartrate and gluconate, and second complexing agent is selected from least one of ethylenediamine and glycerol；The w/v of first complexing agent, second complexing agent and the third complexing agent is (15~30) g:(10~35) g:(1~4.5) mL.The present invention carries out dipping pretreatment using pre- bleeding agent composition, penetrate into complexing agent in the hole and crackle of workpiece surface, to being capable of complex copper ion well during subsequent cyanide-free copper electroplating, copper coating is covered in the sightless tiny bubble of workpiece surface to be plated naked eyes, crackle, pin hole the defects of, it can solve the bubble problem due to caused by workpiece surface hole, improve the binding force of non-cyanide plating layers of copper and alloy substrate.
Description
Technical field
The present invention relates to electroplating technologies, locate in advance more particularly to a kind of pre- bleeding agent composition, pre- bleeding agent, copper facing
Reason method and cyanide-free copper electroplating method.
Background technique
Kirsite has good casting character, is excellent casting alloy, for casting complex-shaped, high-precision work
Part Shi Gengyou superiority.In traditional Zinc alloy electroplating technique, cyanide electroplating is as strike copper plating technique, technically, has
Binding force is good, dispersibility is good, crystallization is careful, porosity is low, bath stability and maintenance it is simple the advantages that.But cyanide is
Severe poisonous chemicals, it is only 0.005g to the lethal dose of people, and cyanide electroplating liquid can release hypertoxic cyaniding in the plating process
Object, big to the health hazard of electroplater, there are huge security risks, and in view of the hypertoxic character of cyanide, cyanide electroplating is
It is listed in backward production technology, will be gradually eliminated.
For a long time, people have carried out unremitting effort to substitute cyanide copper plating process.So far, cyanide-free alkaline copper plating work
Skill huge number, have pyrophosphate copper plating, ethylenediamine copper facing, citrate copper-plating, tartrate copper facing, triethanolamine copper facing,
EDTA copper facing, gluconate copper facing, borofluoride copper facing, sulfamate copper facing also mix the copper facing of complexing agent system,
Such as: citric acid-tartrate copper facing, EDTA- citric acid-tartrate copper facing have been reported that.However, the above system without cyanogen
The problems such as generally existing deposition rate of alkaline copper plating technique is low, binding force is poor, cannot be complete in the plating of zinc alloy diecasting
Coating blisters after solving the problems, such as baking, is unable to the substitution cyanide electroplating of generality so far.HEDP (1-hydroxy ethylidene-1,1-diphosphonic acid) body
The cyanide-free alkaline copper plating of system, it has been proved by practice that it can obtain preferable binding force on Al-alloy parts and ironware, in kirsite
In terms of die casting, plating solution operating temperature is reduced if reduced copper content concentration in plating solution by process modification, charges lower slot, lower slot
Copper replacement proble is solved with modes such as strong-current electroplatings in latter short time, so that coating performance reaches cyanide electroplating water
Flat, still, this technique also may be only available for the high-quality zinc alloy diecasting of sub-fraction die casting, and die casting quality depends on mould
Has the reasonability of design, proportion and content, the operating condition of press casting procedure of impurity of metal component etc. in kirsite, big portion's zinc
The quality of alloy pressuring casting is general, is especially mixed with the zinc alloy diecasting of a certain amount of reclaimed materials, still using cyanide-free alkaline copper plating
Cyanide electroplating can not so be substituted.
Therefore, cyanide electroplating still largely exists in Electroplating on Zinc Die Castings technique, especially medium-sized and small enterprises more
Generally, the technique of the cyanide-free alkaline copper plating solution electroplating zinc alloy of cyanide electroplating can be substituted it is urgent to provide one kind.
Summary of the invention
Based on this, it is necessary to a kind of pre- bleeding agent composition is provided, can be improved the binding force of copper coating and alloy substrate,
So as to realize the cyanide-free copper electroplating of industrialization.
A kind of pre- bleeding agent composition, including the first complexing agent, the second complexing agent and third complexing agent；
Wherein, first complexing agent is succinate, and second complexing agent is selected from tartrate and gluconate
At least one of, second complexing agent is selected from least one of ethylenediamine and glycerol；
The w/v of first complexing agent, second complexing agent and the third complexing agent is (15~30) g:
(10~35) g:(1~4.5) mL.
Above-mentioned pre- bleeding agent composition makes by selecting specific complexing agent component, and by the collocation of a variety of complexing agents
, when carrying out infiltration processing to workpiece to be plated, it is sightless that complexing agent molecule can penetrate sufficiently into workpiece surface naked eyes for it
In the defects of tiny bubble, crackle, pin hole, so that complexing agent can be well during subsequent cyanide-free copper electroplating
The copper ion in plating solution is complexed, is covered on copper ion sufficiently in the crackle and hole of workpiece surface to be plated and forms copper coating, and
The binding force of copper coating and workpiece substrate to be plated is improved, realizes that industrialization provides foundation stone for cyanide-free copper electroplating.
Second complexing agent is the mixture of tartrate and gluconate in one of the embodiments, described
The weight ratio of tartrate and the gluconate is (5~20): (5~25).
The present invention also provides a kind of pre- bleeding agents, including the first complexing agent of 15g/L~30g/L, 10g/L~35g/L second
Complexing agent and 1mL/L~4.5mL/L third complexing agent；
First complexing agent be succinate, second complexing agent in tartrate and gluconate extremely
Few one kind, the third complexing agent are selected from least one of ethylenediamine and glycerol.
In one of the embodiments, in the pre- bleeding agent, the concentration of the tartrate is 10g/L~20g/L,
The concentration of the gluconate is 0~25g/L.
In one of the embodiments, in the pre- bleeding agent composition, the concentration of the tartrate be 10g/L~
20g/L, the concentration of the gluconate are 0g/L~25g/L.
In one of the embodiments, in the pre- bleeding agent composition, the concentration of the tartrate is 0~20g/
L, the concentration of the gluconate are 10g/L~25g/L.
In one of the embodiments, in the pre- bleeding agent composition, the concentration of the tartrate be 5g/L~
20g/L, the concentration of the gluconate are 5g/L~25g/L.
In one of the embodiments, in the pre- bleeding agent, the concentration of the third complexing agent be 1mL/L~
3.5mL/L。
In one of the embodiments, in the pre- bleeding agent, the concentration of the ethylenediamine is 0~2.5mL/L, described
The concentration of glycerol be 0~2mL/L, and the content of the ethylenediamine and the glycerol at least one be not zero.
The pH value of the pre- bleeding agent is 8~14 in one of the embodiments,.
The pH adjusting agent is selected from least one of dipotassium hydrogen phosphate and potassium carbonate in one of the embodiments,.
Yet another object of that present invention is to provide a kind of copper facing preprocess method, comprising the following steps:
Workpiece to be plated is subjected to immersion treatment using above-mentioned pre- bleeding agent.
The temperature of the immersion treatment is 30 DEG C~40 DEG C in one of the embodiments, and the time is 5min~20min.
In this way, being 30 DEG C~40 DEG C by maintaining the temperature of immersion treatment, complexing agent can be promoted to enter workpiece table to be plated
In the hole in face, to can achieve good osmotic effect in 5min~20min.
The immersion treatment carries out under ultrasound condition in one of the embodiments, and the sound intensity of the ultrasound is 200w/
m2~300w/m2。
The workpiece to be plated is kirsite workpiece to be plated in one of the embodiments,.
Another object of the present invention provides a kind of cyanide-free copper electroplating method, comprising the following steps:
Workpiece to be plated is subjected to immersion treatment using above-mentioned pre- bleeding agent；
Copper facing is carried out using non-cyanide plating copper liquid to the workpiece to be plated Jing Guo the immersion treatment.
The present invention compares traditional copper-plating technique, increases pre-treatment step before carrying out copper facing to workpiece to be plated, treats
It plates workpiece and immersion treatment is carried out using pre- bleeding agent of the invention, so that complexing agent is penetrated into workpiece surface naked eyes to be plated sightless
In the defects of tiny bubble, crackle, pin hole, thus during subsequent cyanide-free copper electroplating can complex copper ion well,
Copper coating is covered in the hole, crackle of workpiece surface to be plated, can solve zinc alloy diecasting due to caused by surface pore
Bubble problem improves the binding force of non-cyanide plating layers of copper and kirsite matrix, meets the plating requirement of cyanide-free copper electroplating.Moreover, this hair
It avoids meeting environmental protection and sustainable production requirement using copper plating bath containing cyanogen, environment capable of being reduced in bright above-mentioned cyanide-free copper electroplating method
Pollution.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
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.
Kirsite matrix is made of the metals such as zinc, aluminium and a small amount of copper, magnesium, in press casting procedure, becomes solid-state from molten state
When, since cooled and solidified point is different, causes surface to be also easy to produce composition segregation phenomena, be more especially mixed with the kirsite of reclaimed materials
Die casting exacerbates the adult segregation phenomena of workpiece surface, and in die cast, there are the sightless tiny gas of naked eyes for matrix
The defects of bubble, crackle, pin hole, so that die casting surface is mostly the structure of hole.After workpiece is polished, buffing wax is easy to be embedded in this
It is difficult to remove in a little tiny holes, after pre-treatment, pre-treatment working solution penetrates into hole, or because of surface tension original
Cause makes hole mouth gassing, these prevent electric current from importing hole.Cyanide electroplating liquid is mainly by copper cyano complex and certain
The free cyanide composition of amount, since cyanide ion is smaller and has very strong penetrating power and complexing power, so copper cyanogen network
Conjunction object, which can be entered in the hole of workpiece surface and be formed wherein, covers copper coating, ensure that after subsequent plating, baking
The binding force of coating.And the complexing agent molecule in current cyanide-free alkaline copper plating solution is big compared with cyanide ion, since volume steric hindrance is imitated
The penetrating power of copper with product after complexing agent complexing should be reduced, so that copper coating can not be penetrated into these holes and be formed,
On the contrary, forming coating at these tiny hole mouths and covering hole mouth, after leading to plating, baking, in the position of these holes
It sets and foaming phenomena occurs, to not be able to satisfy the needs of plating production, cannot achieve industrialization.
In view of the above-mentioned problems, the application hair people is bright by numerous studies, a kind of pre- bleeding agent composition is provided, for treating
It plates workpiece and carries out copper facing pretreatment, can be improved the penetrating power of non-cyanide plating copper liquid, improve the combination of copper coating and alloy substrate
Power can be realized the zinc alloy cyanide-free copper electroplating method of industrialization.
A kind of pre- bleeding agent composition, including the first complexing agent, the second complexing agent and third complexing agent；
Wherein, the first complexing agent be succinate, the second complexing agent in tartrate and gluconate at least
One kind, the second complexing agent are selected from least one of ethylenediamine and glycerol；First complexing agent, second complexing agent and described
The w/v of three complexing agents is (15~30) g:(10~35) g:(1~4.5) mL.
Specifically, succinate can be potassium succinate and sodium succinate etc.；Tartrate can be sodium potassium tartrate tetrahydrate, wine
Stone acid potassium or sodium tartrate etc.；Gluconate can be sodium gluconate or K-IAO etc..
In one embodiment, the second complexing agent is the mixture of tartrate and gluconate.
In one embodiment, the weight ratio of tartrate and gluconate is (5~20): (5~25).
Another embodiment of the present invention provides a kind of pre- bleeding agent, including the first complexing agent of 15g/L~30g/L, 10g/L~
The second complexing agent of 35g/L and 1mL/L~4.5mL/L third complexing agent；
Wherein, the first complexing agent be succinate, the second complexing agent in tartrate and gluconate at least
One kind, third complexing agent are selected from least one of ethylenediamine and glycerol.
It is worth noting that each component concentration is to be seeped in advance using pre- bleeding agent to workpiece to be plated in above-mentioned pre- bleeding agent
Final concentration is used when processing thoroughly, similarly hereinafter.
Specific product form may include that diversified forms exist, for example the first complexing agent, the second complexing agent and third are complexed
Pre- bleeding agent composition, is then dissolved in water when in use, obtains final concentration existing for reset condition of the agent with raw material
The pre- bleeding agent met the requirements；Or the first complexing agent, the second complexing agent, third complexing agent are dissolved in water, obtain a certain concentration
Concentrate, then diluted when in use, obtain the pre- bleeding agent composition solution that final concentration is met the requirements.
For example, in pre- bleeding agent include 30g/L~60g/L potassium succinate, 20g/L~40g/L sodium potassium tartrate tetrahydrate, 0~
50g/L sodium gluconate and 2.5mL/L~7mL/L third complexing agent, in use, diluted 2 times, obtain include 15g/L~
30g/L potassium succinate, 10g/L~20g/L sodium potassium tartrate tetrahydrate, 0~25g/L sodium gluconate and 1mL/L~4.5mL/L third network
The pre- osmotic agent solution of mixture.
In pre- bleeding agent include 150g/L~300g/L potassium succinate, 50g/L~200g/L sodium potassium tartrate tetrahydrate, 50~
250g/L sodium gluconate and 12.5mL/L~35mL/L third complexing agent, in use, 100 times are diluted, including
15g/L~30g/L potassium succinate, 5g/L~20g/L sodium potassium tartrate tetrahydrate, 5g/L~25g/L sodium gluconate and 1mL/L~
The pre- osmotic agent solution of 4.5mL/L third complexing agent.
In one embodiment, in pre- bleeding agent, the concentration of tartrate is 10g/L~20g/L, gluconate
Concentration is 0g/L~25g/L.
In one embodiment, in pre- bleeding agent, the concentration of tartrate is 0~20g/L, the concentration of gluconate
For 10g/L~25g/L.
In one embodiment, in pre- bleeding agent, the concentration of tartrate is 5g/L~20g/L, gluconate
Concentration is 5g/L~25g/L.
In one embodiment, in pre- bleeding agent, the concentration of third complexing agent is 1mL/L~3.5mL/L.
In one embodiment, in pre- bleeding agent, the concentration of ethylenediamine is 0~2.5mL/L, the concentration of glycerol is 0~
2mL/L, and the content of ethylenediamine and glycerol at least one be not zero.
In one embodiment, the pH value of pre- bleeding agent is 8~14.
In one embodiment, pH adjusting agent is selected from least one of dipotassium hydrogen phosphate and potassium carbonate.
In one embodiment, in pre- bleeding agent, the concentration of dipotassium hydrogen phosphate is 2g/L~7.8g/L, potassium carbonate it is dense
Degree is 0.25g/L~2.5g/L.
A further embodiment of this invention is to provide a kind of copper facing preprocess method, comprising the following steps:
Workpiece to be plated is subjected to immersion treatment using above-mentioned pre- bleeding agent.
In one embodiment, the temperature of immersion treatment is 30 DEG C~40 DEG C, and the time is 5min~20min.
In one embodiment, immersion treatment carries out under ultrasound condition, and the ultrasonic sound intensity is 200w/m2~300w/m2。
In one embodiment, workpiece to be plated is kirsite workpiece to be plated.
In one embodiment, to workpiece to be plated carry out immersion treatment the step of before, further include to workpiece to be plated into
Row paraffin removal, oil removing and activation processing.
Further, hot dipping or/and ultrasonic wave paraffin removal can be used；Using hot dipping or/and ultrasonic oil removal.
A further embodiment of this invention is to provide a kind of cyanide-free copper electroplating method, comprising the following steps:
Workpiece to be plated is subjected to immersion treatment using above-mentioned pre- bleeding agent；
Copper facing is carried out to the workpiece to be plated Jing Guo immersion treatment with non-cyanide plating copper liquid.
In one embodiment, non-cyanide plating copper liquid is cyanide-free alkaline copper plating solution.
In one embodiment, with non-cyanide plating copper liquid to the workpiece to be plated Jing Guo immersion treatment carry out copper coating step it
It afterwards, further include the processing such as electric coke-plated copper, plating semi-gloss nickel, Bright Nickel Electroplating, electrodeposited chromium and drying.
The following are specific embodiments
1, according to the dosage of each raw material component in the pre- bleeding agent composition of the following table 1, prepare each raw material component, then by each original
Material component is added in pure water, dissolves and physics mixes, be settled to 1L, obtain pre- bleeding agent.
Table 1
2, cyanideless electro-plating processing is carried out to kirsite workpiece to be plated, the process flow of processing is as follows:
Zinc alloy diecasting blank → hot dipping paraffin removal → ultrasonic wave paraffin removal → hot dipping oil removing → ultrasonic oil removal → catholyte
Cyanide-free alkaline copper plating → electricity coke-plated copper → electroplating acid copper → electricity is electroplated in oil removing → activation → ultrasonic wave infiltration in advance → hot pure water is washed →
Plate semi-gloss nickel → Bright Nickel Electroplating → electrodeposited chromium → drying.
In the pre- impregnation step of ultrasonic wave, pre- bleeding agent that will be prepared in above-described embodiment 1~7 and comparative example 1~3 respectively
It is diluted to the pre- osmotic agent solution of 1000ml/L, pH value is 8~14, then will be soaked by the zinc alloy diecasting blank being activated
Bubble is permeated in pre- osmotic agent solution, and being aided with the sound intensity is 200w/m2~300w/m2Ultrasonication, when processing permeates in advance
The temperature of agent solution is 30 DEG C~40 DEG C, time of penetration 10min.
And the comparative example 4 for permeating the cyanideless electro-plating processing of process in advance without ultrasonic wave, other operating procedures of comparative example 4 are set
It is identical as the process flow of above-mentioned processing；And comparative example 5, the treatment process and the embodiment of the present invention 1~7 of comparative example 5 are basic
It is identical, the difference is that replacing plating cyanide-free alkaline copper plating with cyanide electroplating.
After Examples 1 to 7 and comparative example 1~5 carry out subsequent plating, thermal shock test is carried out during the drying process, is observed
Binding force situation determines that pre- bleeding agent technique influences the binding force of cyanide-free alkaline copper plating coating and kirsite matrix, gained knot
Fruit see the table below 2.
Table 2
Note: requiring according to Zinc alloy electroplating, and 120 DEG C of thermal shock tests blistering is considered as unqualified, and 150 DEG C of thermal shock tests are not blistering
It is good to be considered as binding force.
Zinc alloy workpiece used in the embodiment of the present invention is that die casting is poor, the 3# zinc alloy workpiece of surface porosity, non-cyanide alkali
Copper facing uses the cyanide-free alkaline copper plating product of certain company of organic phospho acid salt system.
From the result of upper table 2 it is found that the product that the cyanogenless electroplating technology of the embodiment of the present invention 1~7 obtains, passes through 120 DEG C
Thermal shock test testing product is qualified, and embodiment 1 is respectively adopted to zinc alloy workpiece before Alkali CyanideFree Copper Electroplating Technology is electroplated
Pre- bleeding agent in~7 carries out infiltration processing, improves the binding force of copper coating Yu kirsite matrix, and Examples 1 to 5 obtains
Product, the binding force of copper coating and kirsite matrix is good, can achieve the effect that cyanide electroplating, can substitute cyaniding plating
Process for copper carries out industrialization promotion.
And 1~4 products obtained therefrom of comparative example is unqualified, specially the ultrasonic wave of comparative example 1~3 in advance infiltration processing in pre- infiltration
The dosage of each complexing agent is different from embodiment in saturating agent, and products obtained therefrom is unqualified, and comparative example 4 is not before being electroplated cyanide-free alkaline copper plating
Increase the electroplating technology that permeates in advance of ultrasonic wave, after 120 DEG C of baking 60min, workpiece surface vesicle, products obtained therefrom is also unqualified.
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 pre- bleeding agent composition, which is characterized in that including the first complexing agent, the second complexing agent and third complexing agent；
Wherein, first complexing agent is succinate, and second complexing agent is in tartrate and gluconate
At least one, second complexing agent are selected from least one of ethylenediamine and glycerol；
The w/v of first complexing agent, second complexing agent and the third complexing agent is (15~30) g:(10
~35) g:(1~4.5) mL.
2. pre- bleeding agent composition according to claim 1, which is characterized in that second complexing agent be tartrate and
The weight ratio of the mixture of gluconate, the tartrate and the gluconate is (5~20): (5~25).
3. a kind of pre- bleeding agent, which is characterized in that the pre- bleeding agent include the first complexing agent of 15g/L~30g/L, 10g/L~
The second complexing agent of 35g/L and 1mL/L~4.5mL/L third complexing agent；
First complexing agent be succinate, second complexing agent in tartrate and gluconate at least one
Kind, the third complexing agent is selected from least one of ethylenediamine and glycerol.
4. pre- bleeding agent according to claim 3, which is characterized in that in the pre- bleeding agent, the tartrate
Concentration is 10g/L~20g/L, and the concentration of the gluconate is 0~25g/L；
Alternatively, the concentration of the tartrate is 0~20g/L, the concentration of the gluconate is 10g/L~25g/L；
Alternatively, in the pre- bleeding agent, the concentration of the tartrate is 5g/L~20g/L, the gluconate it is dense
Degree is 5g/L~25g/L.
5. pre- bleeding agent according to claim 3, which is characterized in that in the pre- bleeding agent, the ethylenediamine it is dense
Degree is 0~2.5mL/L, and the concentration of the glycerol is 0~2mL/L, and the content of the ethylenediamine and the glycerol at least one
It is a to be not zero.
6. according to the described in any item pre- bleeding agents of claim 3~5, which is characterized in that the pH value of the pre- bleeding agent be 8~
14。
7. a kind of copper facing preprocess method, which comprises the following steps:
Workpiece to be plated is subjected to immersion treatment using the described in any item pre- bleeding agents of claim 3~6.
8. copper facing preprocess method according to claim 7, which is characterized in that the temperature of the immersion treatment be 30 DEG C~
40 DEG C, the time is 5min~20min.
9. copper facing preprocess method according to claim 8, which is characterized in that the immersion treatment under ultrasound condition into
Row, the sound intensity of the ultrasound are 200w/m2~300w/m2。
10. a kind of cyanide-free copper electroplating method, which comprises the following steps:
Workpiece to be plated is subjected to immersion treatment using the described in any item pre- bleeding agents of claim 3~5；
Copper facing is carried out using non-cyanide plating copper liquid to the workpiece to be plated Jing Guo the immersion treatment.
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