CN103726081A - Cyanide-free alkaline copper plating method for improving impermeable carbon copper film - Google Patents

Cyanide-free alkaline copper plating method for improving impermeable carbon copper film Download PDF

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CN103726081A
CN103726081A CN201410029439.7A CN201410029439A CN103726081A CN 103726081 A CN103726081 A CN 103726081A CN 201410029439 A CN201410029439 A CN 201410029439A CN 103726081 A CN103726081 A CN 103726081A
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concentration
solution
plating
pulse
cyanide
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CN201410029439.7A
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Chinese (zh)
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袭建军
赵君
王志刚
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哈尔滨辰能工大环保科技股份有限公司
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Priority to CN201410029439.7A priority Critical patent/CN103726081A/en
Publication of CN103726081A publication Critical patent/CN103726081A/en

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Abstract

The invention relates to a cyanide-free alkaline copper plating method for improving an impermeable carbon copper film, relates to a copper plating method for improving the performance of an impermeable carbon copper film, and aims at solving the problems that negative electrode deoiling alone causes hydrogen brittleness and impurity precipitation and positive electrode deoiling alone results in easy dissolution of parts. The method comprises steps of firstly, removing oil stain and dirt on the surface of a workpiece through an electrochemical method; secondly, activating the surface of the workpiece; thirdly, washing and drying; fourthly, carrying out pulse electroplating in a coating bath with an external overlaying magnetic field; fifthly, washing and passivating. Due to the introduction of the pulse electro-deposition and the overlaying magnetic field, the bonding strength of a plating layer and a substrate is improved, the temperature of plating solution is lowered, the heating cost for electroplating is saved, the problem that citrate is easy to mould because the traditional copper plating method by using citrate is carried out at high temperature is solved, and the method can substitutes for the technology of cyaniding copper plating in impermeable carbon copper plating. According to the method, the bonding strength of the plating layer and the substrate is improved, the temperature of the plating solution is lowered, and the heating cost for electroplating is saved.

Description

A kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film
Technical field
The present invention relates to a kind of processing method, especially design improves the Electrocoppering method of anti-carburizing copper plating film performance.
Background technology
To iron and steel local surfaces, anti-carburizing copper facing is in gear, the widely used methods of hydraulic part such as aircraft industry, automotive industry, agricultural machine.Anti-carburizing copper facing mainly plays a part matrix surface and heat to ooze media isolated, so copper plate must have good compactness, thermotolerance, chemical stability and good bonding force having on certain thickness basis.Because electric current distribution in workpiece shape and electroplating process is uneven, copper layer thickness increase also can cause workpiece size precision and how much essence platings to reduce, and becomes one of copper-plated difficult problem of anti-carburizing.
Traditional anti-carburizing copper facing adopts cyanide copper plating process, but because its discharging of waste liquid has severe toxicity, contaminate environment, so for many years, electroplate investigator's exploration and find out the cyanide-free copper electroplating formula with prussiate characteristic, as acid copper-plating, pyrophosphate copper plating, trolamine copper facing, quadrol copper facing, the copper facing of citric acid-tartrate, organic polyphosphonic acid (HEDP) copper facing, nitrilotriacetic acid(NTA) copper facing, the acid copper facing of glucose, fluoroborate copper facing and the copper facing of thionamic acid system etc.But because bonding strength and compactness do not reach requirement, also do not have to be applied to the cyanide-free copper electroplating technique on anti-cement copper layer at present.
Summary of the invention
The object of the invention is to overcome the defect of prior art, a kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film is provided, the method simple operation and cost, can make to combine closely between coating and anti-carburized gears matrix, and copper facing is respond well.Solving independent negative electrode oil removing produces hydrogen embrittlement, separates out impurity and the easy dissolved problem of anode oil removing part separately.
A kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film of the present invention, comprises the steps:
One, electrochemical process is removed workpiece surface greasy dirt and dirt: by pending workpiece, be placed in temperature and be the electrochemical degreasing solution of 60 ℃~75 ℃, adopt the pulse power to carry out electrolytic degreasing;
Wherein, electrolytic degreasing condition is as follows: cathode current density is 6~8A/dm 2, the recurrence interval is 0.02s~0.002s, anodic current density is 6~8A/dm 2, the recurrence interval is 0.02s~0.002s, anode and cathode pulse number is than (3~10): 1;
Described electrochemical degreasing solution ratio is as follows: in every 1L solution, contain the trisodium phosphate solution that sodium hydroxide solution that concentration is 15~25g/L, sodium carbonate solution that concentration is 20~30g/L and concentration are 10~20g/L;
Two, workpiece is carried out to surface active: by the workpiece after step 1 electrochemical treatment, being placed in quality percentage composition is 5%~10% citric acid solution, at ambient temperature, carries out surface activation process 1~2min;
Three, the workpiece surface after step 2 activation treatment is washed, after the workpiece after washing is dried up, stand-by;
Four, in the coating bath in additional stack magnetic field, carry out pulse plating processing: the workpiece after step 3 is dried up, be placed in plating bath, in the coating bath in additional stack magnetic field, carry out pulse plating;
Wherein, plating condition is as follows: the temperature of plating bath is 20~35 ℃; Magnetic induction density is 100G~1000G, and pulsed electrical parameter is: forward current density is 0.5~2A/dm 2, forward dutycycle is 50%~90%, negative current density is 0.1~1A/dm 2, negative sense dutycycle is 5~30%, and pulse-repetition is 200~2000Hz, and pulse number is 1~10, plating time 10~120min;
Described plating bath proportioning is as follows: in every 1L electrolytic solution, containing concentration is the main enveloping agent solution of 130~270g/L, concentration is the Seignette salt of 20~35g/L, concentration is the main salts solution of 40~55g/L, concentration is the pH adjusting agent solution of 10~20g/L, concentration is the brightening agent solution of 0.001~0.1g/L, concentration is the 2-mercaptobenzimidazole solution of 0.001~0.1g/L, concentration is the polyglycol solution of 0.01~0.1g/L and the isothiazolinone solution that concentration is 0.01~0.5g/L,
Five, the workpiece surface after step 4 plating is washed, and dried up.
The present invention comprises following beneficial effect:
The present invention has increased the introducing in pulse electrodeposition and stack magnetic field the bonding strength of coating and matrix, reduced the temperature of plating solution, saved the heating cost in electroplating process, improved traditional citrate copper-plating under comparatively high temps, to carry out and caused the easy grow mold of Citrate trianion, can replace the technique of cyanide electroplating in anti-carburizing copper facing.
The present invention has solved independent negative electrode oil removing by pulse electrolysis oil removing and has produced hydrogen embrittlement, separates out impurity and the easy dissolved problem of anode oil removing part separately.
Because sulfuric acid, hydrochloric acid etc. carries out pickling, in ensuing electroplating process, introduce unavoidably foreign ion, so select citric acid to carry out metallic surface activation, remove foreign ion.
Accompanying drawing explanation
Fig. 1 is the plating schematic diagram in additional stack of the present invention magnetic field; Wherein, the 1st, pulse power source control display screen, the 2nd, pulse power cathode output end, the 3rd, pulse power cathode output end, the 4th, workpiece to be plated, the 5th, electrolysis copper coin, the 6th, plating tank, the 7th, stack magnetic field, the 8th, shell, the 9th, electrolytic solution;
Fig. 2 is the cyanide-free copper electroplating rete of embodiment 1 preparation and the figure of copper film tissue topography prepared by direct current electrode position;
Fig. 3 is the figure of copper film tissue topography prepared by control group (direct current electrode position).
Embodiment
Embodiment one: a kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film of present embodiment, comprises the steps:
One, electrochemical process is removed workpiece surface greasy dirt and dirt: by pending workpiece, be placed in temperature and be the electrochemical degreasing solution of 60 ℃~75 ℃, adopt the pulse power to carry out electrolytic degreasing;
Wherein, electrolytic degreasing condition is as follows: cathode current density is 6~8A/dm 2, the recurrence interval is 0.02s~0.002s, anodic current density is 6~8A/dm 2, the recurrence interval is 0.02s~0.002s, anode and cathode pulse number is than (3~10): 1;
Described electrochemical degreasing solution ratio is as follows: in every 1L solution, contain the trisodium phosphate solution that sodium hydroxide solution that concentration is 15~25g/L, sodium carbonate solution that concentration is 20~30g/L and concentration are 10~20g/L;
Two, workpiece is carried out to surface active: by the workpiece after step 1 electrochemical treatment, being placed in quality percentage composition is 5%~10% citric acid solution, at ambient temperature, carries out surface activation process 1~2min;
Three, the workpiece surface after step 2 activation treatment is washed, after the workpiece after washing is dried up, stand-by;
Four, in the coating bath in additional stack magnetic field, carry out pulse plating processing: the workpiece after step 3 is dried up, be placed in plating bath, in the coating bath in additional stack magnetic field, carry out pulse plating;
Wherein, plating condition is as follows: the temperature of plating bath is 20~35 ℃; Magnetic induction density is 100G~1000G, and pulsed electrical parameter is: forward current density is 0.5~2A/dm 2, forward dutycycle is 50%~90%, negative current density is 0.1~1A/dm 2, negative sense dutycycle is 5~30%, and pulse-repetition is 200~2000Hz, and pulse number is 1~10, plating time 10~120min;
Described plating bath proportioning is as follows: in every 1L electrolytic solution, containing concentration is the main enveloping agent solution of 130~270g/L, concentration is the Seignette salt of 20~35g/L, concentration is the main salts solution of 40~55g/L, concentration is the pH adjusting agent solution of 10~20g/L, concentration is the brightening agent solution of 0.001~0.1g/L, concentration is the 2-mercaptobenzimidazole solution of 0.001~0.1g/L, concentration is the polyglycol solution of 0.01~0.1g/L and the isothiazolinone solution that concentration is 0.01~0.5g/L,
Five, the workpiece surface after step 4 plating is washed, and dried up.
Present embodiment has increased the introducing in pulse electrodeposition and stack magnetic field the bonding strength of coating and matrix, reduced the temperature of plating solution, saved the heating cost in electroplating process, improved traditional citrate copper-plating under comparatively high temps, to carry out and caused the easy grow mold of Citrate trianion, can replace the technique of cyanide electroplating in anti-carburizing copper facing.
Present embodiment has solved independent negative electrode oil removing by pulse electrolysis oil removing and has produced hydrogen embrittlement, separates out impurity and the easy dissolved problem of anode oil removing part separately.
Because sulfuric acid, hydrochloric acid etc. carries out pickling, in ensuing electroplating process, introduce unavoidably foreign ion, so select citric acid to carry out metallic surface activation, remove foreign ion.
Embodiment two: present embodiment is different from embodiment one: the electrolytic degreasing condition described in step 1 is as follows: cathode current density is 7A/dm 2, the recurrence interval is 0.02s~0.01s, anodic current density is 7A/dm 2, the recurrence interval is 0.02s~0.01s, anode and cathode pulse number is than (5~7): 1.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: the electrochemical degreasing solution ratio described in step 1 is as follows: contain the trisodium phosphate solution that sodium hydroxide solution that concentration is 20~25g/L, sodium carbonate solution that concentration is 25~30g/L and concentration are 15~20g/L in every 1L solution.Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: the citric acid solution quality percentage composition described in step 2 is 7%~10%.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: the plating condition described in step 4 is as follows: the temperature of plating bath is 20~35 ℃; Magnetic induction density is 300G~1000G, and pulsed electrical parameter is forward current density 1~2A/dm 2, forward dutycycle is 70%~90%, negative current density is 0.5~1A/dm 2, negative sense dutycycle is 15~30%, and pulse-repetition is 1000~2000Hz, and pulse number is 1~6, plating time 50~120min.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: the plating condition described in step 4 is as follows: the temperature of plating bath is 20~35 ℃; Magnetic induction density is 500G~1000G, and pulsed electrical parameter is forward current density 1.5~2A/dm 2, forward dutycycle is 80%~90%, negative current density is 0.8~1A/dm 2, negative sense dutycycle is 20~30%, and pulse-repetition is 1500~2000Hz, and pulse number is 1~4, plating time 100~120min.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: the plating condition described in step 4 is as follows: the temperature of plating bath is 25~30 ℃; Magnetic induction density is 800G~1000G, and pulsed electrical parameter is forward current density 1.8~2A/dm 2, forward dutycycle is 80%~90%, negative current density is 0.8~1A/dm 2, negative sense dutycycle is 25~30%, and pulse-repetition is 1800~2000Hz, and pulse number is 1~2, plating time 110~120min.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: the plating bath proportioning described in step 4 is as follows: containing concentration in every 1L electrolytic solution is the main enveloping agent solution of 180~270g/L, concentration is the Seignette salt of 25~35g/L, concentration is the main salts solution of 45~55g/L, concentration is the pH adjusting agent solution of 15~20g/L, concentration is the brightening agent solution of 0.01~0.1g/L, concentration is the 2-mercaptobenzimidazole solution of 0.01~0.1g/L, concentration is the polyglycol solution of 0.05~0.1g/L and the isothiazolinone solution that concentration is 0.1~0.5g/L.Other is identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: the plating bath proportioning described in step 4 is as follows: containing concentration in every 1L electrolytic solution is the main enveloping agent solution of 200~270g/L, concentration is the Seignette salt of 30~35g/L, concentration is the main salts solution of 50~55g/L, concentration is the pH adjusting agent solution of 18~20g/L, concentration is the brightening agent solution of 0.05~0.1g/L, concentration is the 2-mercaptobenzimidazole solution of 0.05~0.1g/L, concentration is the polyglycol solution of 0.08~0.1g/L and the isothiazolinone solution that concentration is 0.3~0.5g/L.Other is identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment one to nine: the plating bath proportioning described in step 4 is as follows: containing concentration in every 1L electrolytic solution is the main enveloping agent solution of 250~270g/L, concentration is the Seignette salt of 32~35g/L, concentration is the main salts solution of 52~55g/L, concentration is the pH adjusting agent solution of 20g/L, concentration is the brightening agent solution of 0.08~0.1g/L, concentration is the 2-mercaptobenzimidazole solution of 0.08~0.1g/L, concentration is the polyglycol solution of 0.1g/L and the isothiazolinone solution that concentration is 0.4~0.5g/L.Other is identical with one of embodiment one to nine.
Embodiment 11: present embodiment is different from one of embodiment one to ten: the main complexing agent described in step 4 is that citric acid, main salt are that ventilation breather, pH adjusting agent are that sodium bicarbonate, brightening agent are tin anhydride.Other is identical with one of embodiment one to ten.
Embodiment 12: present embodiment is different from one of embodiment one to 11: described workpiece refers to carbon steel tooth.Other is identical with one of embodiment one to 11.
Below in conjunction with specific examples, the invention will be further described.
Embodiment 1
A kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film of the present embodiment, comprises the steps:
One, electrochemical process is removed carbon steel tooth surface greasy dirt and dirt: by pending carbon steel tooth, be placed in temperature and be the electrochemical degreasing solution of 70 ℃, adopt the pulse power to carry out electrolytic degreasing;
Wherein, electrolytic degreasing condition is as follows: cathode current density is 8A/dm 2, the recurrence interval is 0.02s, anodic current density is 8A/dm 2, the recurrence interval is 0.02s, anode and cathode pulse number compares 8:1;
Described electrochemical degreasing solution ratio is as follows: in every 1L solution, contain the trisodium phosphate solution that sodium hydroxide solution that concentration is 15g/L, sodium carbonate solution that concentration is 30g/L and concentration are 15g/L;
Two, carbon steel tooth is carried out to surface active: by the carbon steel tooth after step 1 electrochemical treatment, being placed in quality percentage composition is 5% citric acid solution, at ambient temperature, carries out surface activation process 2min;
Three, the carbon steel tooth surface after step 2 activation treatment is washed, after the carbon steel tooth after washing is dried up, stand-by;
Four, in the coating bath (structural representation is as shown in Figure 1) in additional stack magnetic field, carry out pulse plating processing: the carbon steel tooth after step 3 is dried up, be placed in plating bath, in the coating bath in additional stack magnetic field, carry out pulse plating;
Wherein, plating condition is as follows: the temperature of plating bath is 20 ℃; Magnetic induction density is 400G, and pulsed electrical parameter is forward current density 1A/dm 2, forward dutycycle is 80%, negative current density is 0.2A/dm 2, negative sense dutycycle is 5%, and pulse-repetition is 500Hz, and pulse number is 1, plating time 30min;
Described plating bath proportioning is as follows: in every 1L electrolytic solution, contain the isothiazolinone solution that citric acid solution that concentration is 260g/L, Seignette salt that concentration is 30g/L, basic carbonate copper solutions that concentration is 45g/L, sodium hydrogen carbonate solution that concentration is 10g/L, tin anhydride solution that concentration is 0.01g/L, 2-mercaptobenzimidazole solution that concentration is 0.005g/L, polyglycol solution that concentration is 0.01g/L and concentration are 0.1g/L;
Five, the carbon steel tooth surface after step 4 plating is washed, and dried up.
A control group is set, contrast is under difference plating form, copper facing effect, wherein, control group just changes the plating condition of the present embodiment into direct current electrode position, described direct current electrode position condition is as follows: in every 1L electrolytic solution, contain the citric acid solution that concentration is 260g/L, the Seignette salt that concentration is 30g/L, the basic carbonate copper solutions that concentration is 45g/L, the sodium hydrogen carbonate solution that concentration is 10g/L, the tin anhydride solution that concentration is 0.01g/L, current density is 1A/dm 2, electroplating time 30min.After electroplating, the bonding strength of copper is shown in Table 1, by table 1, can know that the copper electroplating technological process of the anti-carburizing copper plating film performance of the present embodiment has improved the bonding strength of copper coating, meet anti-carburizing copper plating film layer performance requriements, can substitute cyanide electroplating for the anti-carburizing copper-plating technique of gear.
In addition, after the present embodiment is electroplated the copper film electron microscopic observation of copper film and control group the results are shown in Figure 2 and Fig. 3 shown in, the copper film microtexture of being prepared by the copper electroplating technological process of the anti-carburizing copper plating film performance of Fig. 2 and the known the present embodiment of Fig. 3 is more fine and close smooth, and grain-size is more careful.
Bonding strength under the different plating forms of table 1
Embodiment 2
A kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film of the present embodiment, comprises the steps:
One, electrochemical process is removed carbon steel tooth surface greasy dirt and dirt: by pending carbon steel tooth, be placed in temperature and be the electrochemical degreasing solution of 70 ℃, adopt the pulse power to carry out electrolytic degreasing;
Wherein, electrolytic degreasing condition is as follows: cathode current density is 7A/dm 2, the recurrence interval is 0.02s, anodic current density is 7A/dm 2, the recurrence interval is 0.02s, anode and cathode pulse number compares 10:1;
Described electrochemical degreasing solution ratio is as follows: in every 1L solution, contain the trisodium phosphate solution that sodium hydroxide solution that concentration is 20g/L, sodium carbonate solution that concentration is 25g/L and concentration are 10g/L;
Two, carbon steel tooth is carried out to surface active: by the carbon steel tooth after step 1 electrochemical treatment, being placed in quality percentage composition is 8% citric acid solution, at ambient temperature, carries out surface activation process 2min;
Three, the carbon steel tooth surface after step 2 activation treatment is washed, after the carbon steel tooth after washing is dried up, stand-by;
Four, in the coating bath (structural representation is as shown in Figure 1) in additional stack magnetic field, carry out pulse plating processing: the carbon steel tooth after step 3 is dried up, be placed in plating bath, in the coating bath in additional stack magnetic field, carry out pulse plating;
Wherein, plating condition is as follows: the temperature of plating bath is 25 ℃; Magnetic induction density is 600G, and pulsed electrical parameter is forward current density 1.5A/dm 2, forward dutycycle is 60%, negative current density is 0.1A/dm 2, negative sense dutycycle is 10%, and pulse-repetition is 200Hz, and pulse number is 1, plating time 60min;
Described plating bath proportioning is as follows: in every 1L electrolytic solution, contain the isothiazolinone solution that citric acid solution that concentration is 240g/L, Seignette salt that concentration is 20g/L, basic carbonate copper solutions that concentration is 40g/L, sodium hydrogen carbonate solution that concentration is 15g/L, tin anhydride solution that concentration is 0.02g/L, 2-mercaptobenzimidazole solution that concentration is 0.01g/L, polyglycol solution that concentration is 0.05g/L and concentration are 0.02g/L;
Five, the carbon steel tooth surface after step 4 plating is washed, and dried up.
The present embodiment has increased the introducing in pulse electrodeposition and stack magnetic field the bonding strength of coating and matrix, reduced the temperature of plating solution, saved the heating cost in electroplating process, improved traditional citrate copper-plating under comparatively high temps, to carry out and caused the easy grow mold of Citrate trianion, can replace the technique of cyanide electroplating in anti-carburizing copper facing.
The present embodiment has solved independent negative electrode oil removing by pulse electrolysis oil removing and has produced hydrogen embrittlement, separates out impurity and the easy dissolved problem of anode oil removing part separately.
Because sulfuric acid, hydrochloric acid etc. carries out pickling, in ensuing electroplating process, introduce unavoidably foreign ion, so select citric acid to carry out metallic surface activation, remove foreign ion.

Claims (10)

1. improve a cyanide-free alkaline copper plating preparation method for anti-carburizing copper film, it is characterized in that it comprises the steps:
One, electrochemical process is removed workpiece surface greasy dirt and dirt: by pending workpiece, be placed in temperature and be the electrochemical degreasing solution of 60 ℃~75 ℃, adopt the pulse power to carry out electrolytic degreasing;
Wherein, electrolytic degreasing condition is as follows: cathode current density is 6~8A/dm 2, the recurrence interval is 0.02s~0.002s, anodic current density is 6~8A/dm 2, the recurrence interval is 0.02s~0.002s, anode and cathode pulse number is than (3~10): 1;
Described electrochemical degreasing solution ratio is as follows: in every 1L solution, contain the trisodium phosphate solution that sodium hydroxide solution that concentration is 15~25g/L, sodium carbonate solution that concentration is 20~30g/L and concentration are 10~20g/L;
Two, workpiece is carried out to surface active: by the workpiece after step 1 electrochemical treatment, being placed in quality percentage composition is 5%~10% citric acid solution, at ambient temperature, carries out surface activation process 1~2min;
Three, the workpiece surface after step 2 activation treatment is washed, after the workpiece after washing is dried up, stand-by;
Four, in the coating bath in additional stack magnetic field, carry out pulse plating processing: the workpiece after step 3 is dried up, be placed in plating bath, in the coating bath in additional stack magnetic field, carry out pulse plating;
Wherein, plating condition is as follows: the temperature of plating bath is 20~35 ℃; Magnetic induction density is 100G~1000G, and pulsed electrical parameter is: forward current density is 0.5~2A/dm 2, forward dutycycle is 50%~90%, negative current density is 0.1~1A/dm 2, negative sense dutycycle is 5~30%, and pulse-repetition is 200~2000Hz, and pulse number is 1~10, plating time 10~120min;
Described plating bath proportioning is as follows: in every 1L electrolytic solution, containing concentration is the main enveloping agent solution of 130~270g/L, concentration is the Seignette salt of 20~35g/L, concentration is the main salts solution of 40~55g/L, concentration is the pH adjusting agent solution of 10~20g/L, concentration is the brightening agent solution of 0.001~0.1g/L, concentration is the 2-mercaptobenzimidazole solution of 0.001~0.1g/L, concentration is the polyglycol solution of 0.01~0.1g/L and the isothiazolinone solution that concentration is 0.01~0.5g/L,
Five, the workpiece surface after step 4 plating is washed, and dried up.
2. a kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film according to claim 1, is characterized in that the electrolytic degreasing condition described in step 1 is as follows: cathode current density is 7A/dm 2, the recurrence interval is 0.02s~0.01s, anodic current density is 7A/dm 2, the recurrence interval is 0.02s~0.01s, anode and cathode pulse number is than (5~7): 1.
3. a kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film according to claim 1, is characterized in that the electrochemical degreasing solution ratio described in step 1 is as follows: in every 1L solution, contain the trisodium phosphate solution that sodium hydroxide solution that concentration is 20~25g/L, sodium carbonate solution that concentration is 25~30g/L and concentration are 15~20g/L.
4. a kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film according to claim 1, is characterized in that the citric acid solution quality percentage composition described in step 2 is 7%~10%.
5. a kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film according to claim 1, is characterized in that the plating condition described in step 4 is as follows: the temperature of plating bath is 20~35 ℃; Magnetic induction density is 300G~1000G, and pulsed electrical parameter is forward current density 1~2A/dm 2, forward dutycycle is 70%~90%, negative current density is 0.5~1A/dm 2, negative sense dutycycle is 15~30%, and pulse-repetition is 1000~2000Hz, and pulse number is 1~6, plating time 50~120min.
6. a kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film according to claim 5, is characterized in that the plating condition described in step 4 is as follows: the temperature of plating bath is 20~35 ℃; Magnetic induction density is 500G~1000G, and pulsed electrical parameter is forward current density 1.5~2A/dm 2, forward dutycycle is 80%~90%, negative current density is 0.8~1A/dm 2, negative sense dutycycle is 20~30%, and pulse-repetition is 1500~2000Hz, and pulse number is 1~4, plating time 100~120min.
7. a kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film according to claim 1, it is characterized in that the plating bath proportioning described in step 4 is as follows: in every 1L electrolytic solution, containing concentration is the main enveloping agent solution of 180~270g/L, concentration is the Seignette salt of 25~35g/L, concentration is the main salts solution of 45~55g/L, concentration is the pH adjusting agent solution of 15~20g/L, concentration is the brightening agent solution of 0.01~0.1g/L, concentration is the 2-mercaptobenzimidazole solution of 0.01~0.1g/L, concentration is the polyglycol solution of 0.05~0.1g/L and the isothiazolinone solution that concentration is 0.1~0.5g/L.
8. a kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film according to claim 7, it is characterized in that the plating bath proportioning described in step 4 is as follows: in every 1L electrolytic solution, containing concentration is the main enveloping agent solution of 200~270g/L, concentration is the Seignette salt of 30~35g/L, concentration is the main salts solution of 50~55g/L, concentration is the pH adjusting agent solution of 18~20g/L, concentration is the brightening agent solution of 0.05~0.1g/L, concentration is the 2-mercaptobenzimidazole solution of 0.05~0.1g/L, concentration is the polyglycol solution of 0.08~0.1g/L and the isothiazolinone solution that concentration is 0.3~0.5g/L.
9. a kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film according to claim 8, it is characterized in that the plating bath proportioning described in step 4 is as follows: in every 1L electrolytic solution, containing concentration is the main enveloping agent solution of 250~270g/L, concentration is the Seignette salt of 32~35g/L, concentration is the main salts solution of 52~55g/L, concentration is the pH adjusting agent solution of 20g/L, concentration is the brightening agent solution of 0.08~0.1g/L, concentration is the 2-mercaptobenzimidazole solution of 0.08~0.1g/L, concentration is the polyglycol solution of 0.1g/L and the isothiazolinone solution that concentration is 0.4~0.5g/L.
10. according to a kind of cyanide-free alkaline copper plating preparation method who improves anti-carburizing copper film described in claim 1,7,8 or 9, it is characterized in that the main complexing agent described in step 4 is that citric acid, main salt are that ventilation breather, pH adjusting agent are that sodium bicarbonate, brightening agent are tin anhydride.
CN201410029439.7A 2014-01-22 2014-01-22 Cyanide-free alkaline copper plating method for improving impermeable carbon copper film CN103726081A (en)

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Cited By (10)

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Publication number Priority date Publication date Assignee Title
CN104532316A (en) * 2014-12-11 2015-04-22 贵州红林机械有限公司 Anti-nitridation process for copper-tin composite plating
CN105154928A (en) * 2015-09-07 2015-12-16 湖州方明环保科技有限公司 Novel cyanide-free alkaline copper plating solution and preparation method thereof
CN105780074A (en) * 2016-04-29 2016-07-20 南京晨光艺术工程有限公司 Steel piece cyanide-free copper plating method adopting applied magnetic field
CN105926011A (en) * 2016-04-29 2016-09-07 南京晨光艺术工程有限公司 Non-cyanide copperizing device for iron and steel parts by using external magnetic field
CN106065486A (en) * 2016-06-10 2016-11-02 太原工业学院 A kind of non-cyanide copper electroplating compound additive and production technology thereof
CN106283142A (en) * 2016-09-22 2017-01-04 张家港清研再制造产业研究院有限公司 A kind of processing method improving Brush Plating anchoring strength of coating
CN106498454A (en) * 2016-10-14 2017-03-15 吴迪 A kind of preparation method of biomass cyanideless electro-plating liquid
CN109338421A (en) * 2018-12-12 2019-02-15 中国航发贵州红林航空动力控制科技有限公司 A kind of cyanide-free copper electroplating technique of high temperature resistant thermo-chemical treatment
CN110129839A (en) * 2019-05-20 2019-08-16 梁生 A kind of preparation method of copper brightener
CN110284162A (en) * 2019-07-22 2019-09-27 广州三孚新材料科技股份有限公司 A kind of photovoltaic conflux welding cyanide-free alkaline copper plating solution and preparation method thereof

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CN102677116A (en) * 2012-06-12 2012-09-19 山东建筑大学 Method for dipulse preplating non-cyanide alkaline copper on ferro matrix
CN103305880A (en) * 2013-04-24 2013-09-18 湖北恒鑫金属表面处理有限公司 Citrate-tartrate dual-complexing non-cyanide alkaline copper-plating electrolyte on steel substrate

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CN1680630A (en) * 2005-01-26 2005-10-12 上海大学 Technology of non-cyanide silver coating
CN102677116A (en) * 2012-06-12 2012-09-19 山东建筑大学 Method for dipulse preplating non-cyanide alkaline copper on ferro matrix
CN103305880A (en) * 2013-04-24 2013-09-18 湖北恒鑫金属表面处理有限公司 Citrate-tartrate dual-complexing non-cyanide alkaline copper-plating electrolyte on steel substrate

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104532316A (en) * 2014-12-11 2015-04-22 贵州红林机械有限公司 Anti-nitridation process for copper-tin composite plating
CN105154928A (en) * 2015-09-07 2015-12-16 湖州方明环保科技有限公司 Novel cyanide-free alkaline copper plating solution and preparation method thereof
CN105780074A (en) * 2016-04-29 2016-07-20 南京晨光艺术工程有限公司 Steel piece cyanide-free copper plating method adopting applied magnetic field
CN105926011A (en) * 2016-04-29 2016-09-07 南京晨光艺术工程有限公司 Non-cyanide copperizing device for iron and steel parts by using external magnetic field
CN106065486A (en) * 2016-06-10 2016-11-02 太原工业学院 A kind of non-cyanide copper electroplating compound additive and production technology thereof
CN106283142A (en) * 2016-09-22 2017-01-04 张家港清研再制造产业研究院有限公司 A kind of processing method improving Brush Plating anchoring strength of coating
CN106498454A (en) * 2016-10-14 2017-03-15 吴迪 A kind of preparation method of biomass cyanideless electro-plating liquid
CN109338421A (en) * 2018-12-12 2019-02-15 中国航发贵州红林航空动力控制科技有限公司 A kind of cyanide-free copper electroplating technique of high temperature resistant thermo-chemical treatment
CN109338421B (en) * 2018-12-12 2020-12-18 中国航发贵州红林航空动力控制科技有限公司 Cyanide-free copper plating process for high-temperature-resistant chemical heat treatment
CN110129839A (en) * 2019-05-20 2019-08-16 梁生 A kind of preparation method of copper brightener
CN110284162A (en) * 2019-07-22 2019-09-27 广州三孚新材料科技股份有限公司 A kind of photovoltaic conflux welding cyanide-free alkaline copper plating solution and preparation method thereof

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