CN105780074A - Steel piece cyanide-free copper plating method adopting applied magnetic field - Google Patents
Steel piece cyanide-free copper plating method adopting applied magnetic field Download PDFInfo
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- CN105780074A CN105780074A CN201610279721.XA CN201610279721A CN105780074A CN 105780074 A CN105780074 A CN 105780074A CN 201610279721 A CN201610279721 A CN 201610279721A CN 105780074 A CN105780074 A CN 105780074A
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- C25D5/006—
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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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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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
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- Chemical Kinetics & Catalysis (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a steel piece cyanide-free copper plating method which comprises the following steps: step 1, carrying out treatment including polishing, oil removing, cleaning, activating and the like on a plated steel piece; step 2, putting the plated steel piece and a pure copper plate into an electroplating liquid by taking the pretreated plated steel piece as a cathode and the pure copper plate as an anode, applying voltage at two sides of the cathode and the anode, applying a pulse magnetic field to an electroplating bath, and carrying out electroplating by ensuring that the direction of the magnetic field is vertical to the movement direction of copper ions in the electroplating liquid; and step 3, carrying out treatment including cleaning, passivation, drying and the like on the electroplated steel piece. By adopting the method disclosed by the invention to plate copper for a steel statue, the deposition rate of a clad layer is high, the surface is bright and smooth, and the technology is easy to control.
Description
Technical field
The present invention relates to a kind of cyanide-free copper electroplating method, particularly relate to the cyanideless electro-plating copper method of a kind of steel and iron parts statue.
Background technology
Casting in bronze statue is very popular because of its simple and unsophisticated outward appearance attractive in appearance, and copper alloy has good corrosion resistance, not oxidizable under dry environment.But due to copper resource-constrained, price is higher, generally adopting other aboundresources, cheap metal or alloy, as ferrum, rustless steel etc. make statue, then statue in bronze is copied in copper facing thereon.At active metal or alloy, adding man-hour as the surface such as ferrum, zinc carries out plating, wide variety of is cyanide copper plating technique.Cyanide copper plating technique easily operates, and obtained coating is careful, adhesion good, but cyanide is severe poisonous chemicals, adopts cyanide copper plating technique that the health of operator has very big harm, and cost for wastewater treatment is high, it is easy to cause environmental pollution.To this, namely the development and application of cyanide-free copper electroplating technique becomes a trend in electroplating technology field.In cyanide-free copper electroplating technique, electroplate liquid is made up of Multiple components, including main salt, chelating agent, conducting salt and other additive, such as buffer agent, brightener etc..Compared with traditional cyanide copper plating technique, cyanide-free copper electroplating technique typically requires electroplates in a heated condition, the too high stability that can affect plating solution of temperature, so that technique is wayward, produces and maintenance cost increases；Coating deposition rate is slow, and production efficiency is low, and the coating of gained is careful not, tight；Especially, when needs increase thickness of coating, owing to electroplating time length can cause coating coarse grains, hole increases, thus affecting coating performance.
Summary of the invention
Goal of the invention: for prior art Problems existing, the invention discloses a kind of steel and iron parts cyanide-free copper electroplating method adopting externally-applied magnetic field.
Technical scheme: the invention discloses a kind of steel and iron parts cyanide-free copper electroplating method, comprise the steps: step one: plated steel and iron parts is polished, oil removing, cleaning, the pretreatment such as activation；Step 2: with pretreated plated steel and iron parts for negative electrode, with fine copper plate for anode, plated steel and iron parts and fine copper plate are put in electroplate liquid, voltage is applied at negative electrode and anode both sides, simultaneously at the additional pulsed magnetic field of electroplating bath, magnetic direction is electroplated with in electroplate liquid, the copper ion direction of motion is vertical；Step 3: the steel and iron parts after plating is carried out, is passivated, the post processing such as dries.
Preferably, plated steel and iron parts is positioned over electroplating bath central authorities, and two fine copper plates are placed respectively as anode in electroplating bath both sides.
Preferred as another kind, the voltage being applied to the plated steel and iron parts of negative electrode and anode fine copper plate both sides is a unipolar pulse power supply.
Preferred as another kind, the voltage being applied to the plated steel and iron parts of negative electrode and anode fine copper plate both sides is the bipolar pulse power.
Beneficial effect: the present invention by applying a pulsed magnetic field in cyanideless electro-plating process, make cyanideless electro-plating coating crystal grain more uniform, faster, surface brightness, flatness are superior to conventional cyanide-free copper electroplating technique to coating deposition rate, also superior to the cyanide-free copper electroplating technique that externally-applied magnetic field is uniform steady magnetic field；Electroplating process carries out at normal temperatures, bath stability, and technique is easily-controllable；Added pulsed magnetic field is low frequency low-intensity magnetic field, it is easy to accomplish.
Accompanying drawing explanation
Fig. 1 is electroplanting device schematic diagram of the present invention.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, it is further elucidated with the present invention.
In figure, the plated iron and steel statue of 1-, 2-copper plate, 3-copper coil, 4-electroplating power supply, 5-externally-applied magnetic field power supply, 6-electroplate liquid, 7-electroplating bath.
The invention discloses the cyanide-free copper electroplating method of a kind of steel and iron parts, the electroplate liquid used consists of: basic copper carbonate 60～70g/L, citric acid 260～280g/L, sodium potassium tartrate tetrahydrate 30～40g/L, sodium bicarbonate 10～15g/L, 2-mercaptobenzoimidazole 0.002～0.004g/L, selenium dioxide 0.008～0.02g/L.
Embodiment one:
The cyanide-free copper electroplating method of steel and iron parts disclosed in the present embodiment, sequentially includes the following steps:
Step one: 1. successively treat steel plating ferrum statue polish with 320 orders, 600 order sand paper, make matrix surface smooth, smooth, and remove the obvious burr of matrix surface and oxide layer；2. the statue to be plated after pair polishing is immersed in the electrochemical deoiling liquid of 70～90 DEG C 20 minutes and carries out oil removing, consisting of of this electrochemical deoiling liquid: sodium hydroxide 10～15g/L, sodium carbonate 20～30g/L, sodium silicate 50～70g/L, sodium phosphate 10～15g/L；3. it is under 70 DEG C～80 DEG C and electric current density 2A/dm2～4A/dm2 in temperature, use electrolytic degreasing liquid that plated steel and iron parts statue is first carried out catholyte oil removing 1 minute, carry out anode electrolysis oil removing 30 seconds again, consisting of of this electrolytic degreasing liquid: sodium hydroxide 45g/L～55g/L, sodium carbonate 25g/L～35g/L, tertiary sodium phosphate 15g/L～25g/L, sodium silicate 3g/L～7g/L；4. it is hot water wash 15s at 50 DEG C～60 DEG C in temperature, then under room temperature, washes 10s～15s；5. use the hydrochloric acid solution process 10s～15s of hydrochloric acid and the volume ratio 1:1 of water, then carry out washing 10s～15s；6. use volume fraction to be the sulfuric acid treatment 10s～15s of 10% and wash 10s～15s, last deionization washing 10s～15s, obtain pretreated plated iron and steel statue.
Step 2: pretreated plated iron and steel statue is positioned over electroplating bath central as negative electrode, two blocks of fine copper plates are positioned over electroplating bath both sides as anode, plated iron and steel statue and fine copper plate are put in electroplate liquid, DC voltage is applied at negative electrode and anode both sides, being 20～30 DEG C in temperature, cathode-current density is 0.12～0.5A/dm2, the additional uniform and stable magnetic field of electroplating bath, the magnetic induction in this magnetic field is 80～120 Gausses, and negative electrode is carried out electro-coppering 5～15 minutes when being vertical direction by magnetic direction.
With the naked eye observe the statue surface after copper facing with magnifier, have part surface not covered by coating.
Embodiment two:
The present embodiment and embodiment one are different in that: electroplating time is 45 minutes.Other are identical with embodiment one.
With the naked eye observe the statue surface after copper facing with magnifier, surface is all covered by coating, and coating has a small amount of impurity.
Embodiment three:
The present embodiment and embodiment one are different in that: the magnetic field being applied to outside electroplating bath is a pulsed magnetic field, the magnetic induction of described pulsed magnetic field is 80～120 Gausses, the direction of described pulsed magnetic field is vertical with the copper ion direction of motion in electroplate liquid, with direct impulse 20～30 seconds, negative-going pulse 5～15 seconds is a cycle, circulation carry out to total electroplating time be 5～15 minutes.Other are identical with embodiment one.
With the naked eye observe the statue surface after copper facing with magnifier, coating light is uniformly, it does not have impurity, bubble.
Embodiment four:
The present embodiment and embodiment two are different in that: the voltage being applied to the plated iron and steel sculpture of negative electrode and anode fine copper plate both sides is a unipolar pulse power supply, electric current density 0.1～0.5A/dm2, pulse frequency 700～1200Hz, circulation to total electroplating time is 5～15 minutes.Other are identical with embodiment three.
With the naked eye observe the statue surface after copper facing with magnifier, coating light is uniformly, it does not have impurity, bubble.
Embodiment five:
The present embodiment and embodiment two are different in that: the voltage being applied to the plated iron and steel sculpture of negative electrode and anode fine copper plate both sides is the bipolar pulse power, with forward current density 0.8～3.0A/dm2, negative current density 0.4～1.5A/dm2, pulse frequency 700～1200Hz, circulation to total electroplating time is 5～15 minutes.Other are identical with embodiment three.
With the naked eye observe the statue surface after copper facing with magnifier, coating light is uniformly, it does not have impurity, bubble.
Claims (5)
1. a steel and iron parts cyanide-free copper electroplating method, comprises the steps:
Step one: plated steel and iron parts is polished, oil removing, cleaning, the pretreatment such as activation；
Step 2: with pretreated plated steel and iron parts for negative electrode, with fine copper plate for anode, puts in the electroplate liquid of electroplating bath by plated statue and fine copper plate, applies voltage in negative electrode and anode both sides, is 20～30 DEG C in temperature, carries out plating 5～15 minutes under condition；
Step 3: the steel and iron parts after plating is carried out, is passivated, the post processing such as dries；
Described step one preprocessing process is: 1. successively treat steel plating ferrum statue polish with 320 orders, 600 order sand paper, make matrix surface smooth, smooth, and remove the obvious burr of matrix surface and oxide layer；2. the statue to be plated after pair polishing is immersed in the electrochemical deoiling liquid of 70～90 DEG C 20 minutes and carries out oil removing, consisting of of this electrochemical deoiling liquid: sodium hydroxide 10～15g/L, sodium carbonate 20～30g/L, sodium silicate 50～70g/L, sodium phosphate 10～15g/L；3. it is under 70 DEG C～80 DEG C and electric current density 2A/dm2～4A/dm2 in temperature, use electrolytic degreasing liquid that plated steel and iron parts statue is first carried out catholyte oil removing 1 minute, carry out anode electrolysis oil removing 30 seconds again, consisting of of this electrolytic degreasing liquid: sodium hydroxide 45g/L～55g/L, sodium carbonate 25g/L～35g/L, tertiary sodium phosphate 15g/L～25g/L, sodium silicate 3g/L～7g/L；4. it is hot water wash 15s at 50 DEG C～60 DEG C in temperature, then under room temperature, washes 10s～15s；5. use the hydrochloric acid solution process 10s～15s of hydrochloric acid and the volume ratio 1:1 of water, then carry out washing 10s～15s；6. use volume fraction to be the sulfuric acid treatment 10s～15s of 10% and wash 10s～15s, last deionization washing 10s～15s, obtain pretreated plated iron and steel statue；
Consisting of of electroplate liquid in described step 2: basic copper carbonate 60～70g/L, citric acid 260～280g/L, sodium potassium tartrate tetrahydrate 30～40g/L, sodium bicarbonate 10～15g/L, 2-mercaptobenzoimidazole 0.002～0.004g/L, selenium dioxide 0.008～0.02g/L；
It is characterized in that: in step 2, at the additional pulsed magnetic field of electroplating bath, electroplating process carries out in magnetic field, the magnetic induction in described magnetic field is 80～120 Gausses, the direction in described magnetic field is vertical with the copper ion direction of motion in electroplate liquid, with direct impulse 20～30 seconds, negative-going pulse 5～15 seconds was a cycle, circulation carry out to total electroplating time be 5～15 minutes.
2. steel and iron parts cyanide-free copper electroplating method according to claim 1, it is characterised in that: plated steel and iron parts is positioned over electroplating bath central authorities, and two fine copper plates are placed respectively as anode in electroplating bath both sides.
3. steel and iron parts cyanide-free copper electroplating method according to claim 1, it is characterised in that: described in be applied to the voltage of the plated steel and iron parts of negative electrode and anode fine copper plate both sides be a DC voltage, cathode-current density is 0.12～0.5A/dm2.
4. steel and iron parts cyanide-free copper electroplating method according to claim 1, it is characterized in that: described in be applied to the voltage of the plated steel and iron parts of negative electrode and anode fine copper plate both sides be a unipolar pulse power supply, electric current density 0.1～0.5A/dm2, pulse frequency 700～1200Hz, circulation to total electroplating time is 5～15 minutes.
5. steel and iron parts cyanide-free copper electroplating method according to claim 1, it is characterized in that: described in be applied to the voltage of the plated steel and iron parts of negative electrode and anode fine copper plate both sides be the bipolar pulse power, with forward current density 0.8～3.0A/dm2, negative current density 0.4～1.5A/dm2, pulse frequency 700～1200Hz, circulation to total electroplating time is 5～15 minutes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610279721.XA CN105780074A (en) | 2016-04-29 | 2016-04-29 | Steel piece cyanide-free copper plating method adopting applied magnetic field |
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| CN201610279721.XA CN105780074A (en) | 2016-04-29 | 2016-04-29 | Steel piece cyanide-free copper plating method adopting applied magnetic field |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107190288A (en) * | 2017-06-19 | 2017-09-22 | 沈阳飞机工业（集团）有限公司 | A kind of preparation method of HEDP copper facing imporosity thin layer |
| CN111593376A (en) * | 2020-06-15 | 2020-08-28 | 深圳市缤纷珠宝开发有限公司 | Method for electrodepositing bright copper |
| CN114214682A (en) * | 2021-12-22 | 2022-03-22 | 东莞市金瑞五金股份有限公司 | Electroplating process for copper plating of workpiece and electroplating equipment thereof |
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| CN103726081A (en) * | 2014-01-22 | 2014-04-16 | 哈尔滨辰能工大环保科技股份有限公司 | Cyanide-free alkaline copper plating method for improving impermeable carbon copper film |
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| CN103726081A (en) * | 2014-01-22 | 2014-04-16 | 哈尔滨辰能工大环保科技股份有限公司 | Cyanide-free alkaline copper plating method for improving impermeable carbon copper film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107190288A (en) * | 2017-06-19 | 2017-09-22 | 沈阳飞机工业（集团）有限公司 | A kind of preparation method of HEDP copper facing imporosity thin layer |
| CN111593376A (en) * | 2020-06-15 | 2020-08-28 | 深圳市缤纷珠宝开发有限公司 | Method for electrodepositing bright copper |
| CN114214682A (en) * | 2021-12-22 | 2022-03-22 | 东莞市金瑞五金股份有限公司 | Electroplating process for copper plating of workpiece and electroplating equipment thereof |
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