CN103820828A - Nanometer Ni-Co-B coating technology for copper plate/copper tube of continuous casting crystallizer - Google Patents
Nanometer Ni-Co-B coating technology for copper plate/copper tube of continuous casting crystallizer Download PDFInfo
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- CN103820828A CN103820828A CN201410041180.8A CN201410041180A CN103820828A CN 103820828 A CN103820828 A CN 103820828A CN 201410041180 A CN201410041180 A CN 201410041180A CN 103820828 A CN103820828 A CN 103820828A
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Abstract
The invention discloses a nanometer Ni-Co-B coating technology for a copper plate/copper tube of a continuous casting crystallizer. The nanometer Ni-Co-B coating technology comprises the following steps: grinding, removing oil, washing with water, clamping, removing ionized water, activating, electroplating and washing with water. The coating has higherhardness and strong anti-corrosion capability, the electroplating deposition rate is high, and the coating is lustrous, bright, colorful, smooth and mirror-like, and is free of cracks. Besides, the depth capability and the coverage capability of the solution are stronger. Compared with chromium plating, the depth capability is 17.5 times of the traditional chromium plating, and the coverage capability is 3.2 times of the traditional chromium plating. The pollution to environments is smaller, and the treatment technology of waste water, waste liquid and waste gas is simple.
Description
Technical field
The invention belongs to electroplating technology, spy relates to a kind of nanometer Ni-Co-B plating process of continuous casting crystallizer copper plate/copper pipe.
Background technology
Be applied to its technique of the comparatively common electrolytic coating of continuous caster crystallizer copperplate/copper pipe continuous casting is in the past: Ni-Co alloy layer, Cr coating, Ni-Fe coating, Ni-Co alloy layer+Cr coating etc.Each copper coin/pipe producer is basic identical for the technological process of production of crystallizer copper pipe coating, and the key distinction is on electroplating technology formula slightly different.Except Ni-Fe coating range of application is more limited, other three kinds of coating all obtain extensive space.In using, continuous caster is most widely used with Cr coating, take the steel transportation amount of Ni-Co alloy layer+Cr coating as optimum.But also there is certain deficiency in above two kinds of electroplating technologies:
Cr coating low production cost, simple to operate, process stabilizing, so should be the most extensive, Ni-Co alloy layer+Cr coating is due to the difference of coating structure, the wear resisting property of copper pipe entirety is promoted, and steel transportation amount is also for the highest, but the maximum shortcoming of above two kinds of coating is exactly all to have used Cr
6+electroplating technology, Cr
6+be the strict emphasis blowdown thing of controlling of China, its emission request management intensity is constantly strengthened, due to the pressure from environment aspect, hexavalent chromium plating process application is day by day narrow.
Summary of the invention
In view of above-mentioned present situation, the invention provides a kind of nanometer Ni-Co-B plating process of continuous casting crystallizer copper plate/copper pipe.Making the main component of its nanometer Ni-Co-B electroplating technology is Ni
2+and Co
2+, these two kinds of ions are compared with Cr
6+the impact that compares environment is smaller, is not the pollutent of the strict discharge of controlling of country, and environmental protection pressure is little.The wear resistance of coating is strong, and the steel transportation amount of crystallizer copper pipe is high.
Processing step of the present invention is as follows:
1, configuration tank liquor:
(1) get single nickel salt: 180-230g/L, nickelous chloride: 40-45 g/L, rose vitriol: 45-55 g/L, boric acid: No. 4, No. 3, No. 2, No. 1,45-50 g/L, FLT-6 MU: 50-100ml/L, FLT-6 MU: 30-80ml/L, FLT-6 MU: 19-25ml/L, FLT-6 MU: 20-30ml/L;
(2) add the deionized water of cumulative volume 1/3, be heated to 60-70 ℃;
(3) boric acid that takes formula ratio first dissolves;
(4) getting respectively rose vitriol, single nickel salt and nickelous chloride is dissolved in groove;
(5) fully stir with 1-3ml/l hydrogen peroxide, then add potassium permanganate, static 4-8 hour, adds 1-2g/l gac and stirs static filtration, and energising maintains current density at 0.1-0.15 ampere/square decimeter 8-12 hour;
(6) No. MU2, No. 1, FLT-6 that adds FLT-6 MU, is stirred to solution Clear & Transparent;
(7) continue to stir, in stirring, add No. 3, the water-reducible FLT-6 MU of deionization, No. MU4, FLT-6 with 5 times, then add deionized water to prescribed volume, adjust plating solution potential of hydrogen between 3.8-5.5, obtain plating solution for subsequent use;
2, polishing: polishing mode is to use 280# and 400# silicon carbide paper successively polish copper coin/copper pipe R angle and four sides, makes it spill matrix surface, removes surface film oxide and greasy dirt;
3, oil removing: use acid degreasing fluid, oil removing at ambient temperature, till presenting moisture film to the flushing of matrix surface water;
4, washing: rinse out the impurity of copper coin/copper pipe surface, avoid polluting tank liquor;
5, be installed: the copper coin/copper pipe after cleaning is installed to and is electroplated on workstation, the titanium anode that nickel button is housed is put into copper coin/copper pipe, recycling clamp is fixed anode, and the distance between anode and copper coin/copper pipe is controlled between 20mm;
6, deionized water: other harmful ions that rinse out copper coin/copper pipe surface;
7, activation: with salt acid soak copper coin/copper pipe 1-2 minute, remove the zone of oxidation of copper coin/copper pipe surface, activation matrix surface, increases the bonding force between copper coin/copper pipe and coating;
8, electroplate: utilize submersible pump plating solution to be imported from coating bath to copper coin/copper pipe, after copper coin/copper pipe is filled plating solution, connect wire, firing current is electroplated;
Electric current given: by the area of electroplating copper coin/copper pipe, then according to the current density of 2-10A/ square decimeter, calculate given electric current;
9 washings: electroplate after finishing copper coin/copper pipe is unloaded, rinse out the residual plating solution of copper coin/copper pipe surface with tap water, obtain nanometer:
ni-Co-Bcopper coin/the copper pipe of coating.
The effect that nanometer Ni-Co-B plating process of the present invention has is:
1, there is higher hardness and resistance to corrosion.Coating hardness is about 720HV, can reach 900HV through heat treatment hardness.
2, electroplating deposition speed is fast.The fastest sedimentation rate can reach 40mm/h, and sedimentation velocity is 2 times of chromium plating.
3, coating bright in color, bright-coloured, level and smooth, is mirror-like, there is no crackle.
4, coating internal stress is smaller, has good bonding force with matrix surface.
5, degree of depth ability and the covering power of solution are more intense, and it is 17.5 times that degree of depth ability is compared in its chromium plating, and covering power is 3.2 times.
6, current efficiency, higher than 96%, is 4 times of chromium plating efficiency.
7, environmental pollution is smaller, and waste water, waste liquid, waste gas treatment process are simple.
Embodiment
Below in conjunction with processing method, the invention will be further described.
Embodiments of the invention, take 150x150 model crystallizer copper pipe as example: the steel transportation amount of plating Cr layer copper pipe is 3500-4000 ton, the steel transportation amount of Ni-Co alloy layer+Cr coating copper pipe is 4000-4500 ton, and the steel transportation amount of nanometer Ni-Co-B coating copper pipe is 6000-7000 ton.
1, configuration tank liquor:
(1) first measure the size of coating bath, length, calculate the cubic capacity of coating bath, get single nickel salt: 180g/L, nickelous chloride: 40 g/L, rose vitriol: No. 4, No. 3, No. 2, No. 1,45 g/L, boric acid: 45g/L, FLT-6 MU: 50ml/L, FLT-6 MU: 30ml/L, FLT-6 MU: 19ml/L, FLT-6 MU: 20ml/L, calculates each material and join groove addition;
(2) first add the deionized water of cumulative volume 1/3, reheat 60-70 ℃;
(3) boric acid that takes formula ratio first dissolves;
(4) taking respectively rose vitriol, single nickel salt and nickelous chloride is dissolved in groove;
(5) fully stir with 1-3ml/l hydrogen peroxide, then add potassium permanganate, static 4-8 hour, adds 1-2g/l gac and stirs static filtration, and energising maintains current density at 0.1-0.15 ampere/square decimeter 8-12 hour;
(6) add No. 1, FLT-6 MU, No. MU2, the FLT-6 of regulation, be stirred to solution clear, transparent;
(7) continue to stir, No. MU4, No. 3, FLT-6 that add FLT-6 MU in the stirring deionized water dilution of 5 times (first with), then be added into prescribed volume with deionized water, adjustment plating solution potential of hydrogen is between 3.8-5.5;
2, polishing: polishing mode is to use 280# and 400# silicon carbide paper successively polish copper pipe R angle and four sides, makes it spill matrix surface, removes surface film oxide and greasy dirt;
3, oil removing: use acid degreasing fluid, manual oil removing at ambient temperature, presents moisture film until matrix surface water rinses;
4, washing: rinse out dust and the impurity of copper pipe surface, avoid polluting tank liquor;
5, be installed: the copper pipe after cleaning is installed to and is electroplated on workstation, the titanium anode that nickel button is housed is put into copper pipe, recycling clamp is fixed anode, and the distance between anode and copper pipe is controlled between 20mm;
6, deionized water: utilize submersible pump that deionized water is imported in copper pipe and rinses out the residual hydrochloric acid of copper pipe surface, avoiding entering tank liquor affects bath pH value, after flushing finishes bleeds off deionized water, avoids polluting tank liquor;
7, activation: with salt acid soak matrix 1-2 minute, remove the zone of oxidation of matrix surface, activation matrix surface, increases the bonding force between matrix and coating;
8, electroplate: utilize submersible pump plating solution to be imported from coating bath to copper pipe, after copper pipe is filled plating solution, connect wire, firing current is electroplated;
Electric current given: first calculate the area (square decimeter) of electroplating copper pipe, then according to the current density of 2-10A/ square decimeter, calculate given electric current, given electric current=copper pipe area * current density;
9 washings: electroplate after finishing copper pipe is unloaded, rinse out the residual plating solution of copper pipe surface with tap water, be adsorbed on copper pipe surface after avoiding plating solution dry, affect copper pipe visual appearance.
Electroplating technological parameter:
| Working parameter | Scope |
| Single nickel salt | 180-230g/L |
| Nickelous chloride | 40-45 g/L |
| Rose vitriol | 45-55 g/L |
| Boric acid | 45-50 g/L |
| No. 1, FLT-6 MU | 50-100ml/L |
| No. 2, FLT-6 MU | 30-80ml/L |
| No. 3, FLT-6 MU | 19-25ml/L |
| No. 4, FLT-6 MU | 20-30ml/L |
| Current density A/dm | 2-10A |
| pH | 3.8-5.5(4.8) |
| Temperature | 50-58℃ |
| Anode material | Pure nickel |
| Anode and negative electrode ratio | 1.5-5.0:1.0 |
| Working fluid alr mode | Movable cathode stirs or plating solution circulation stirs |
| Working fluid purification style | 5 microns of filter cores (density) |
| Pump and groove | Polyvinyl chloride polystyrene |
Bath maintenance and control:
1, potential of hydrogen regulates
Control the potential of hydrogen of solution with 50% ammoniacal liquor (analytical pure) or 10% sulfuric acid (analytical pure), while adding these reagent, must very slowly and stablize, avoid the unexpected increase and decrease of local potential of hydrogen.
2, adding of additive:
Add an additive according to every 200AH.The concrete additional amount of each additive is as following table:
| Additive title | Additional amount (200AH) |
| No. 1, FLT-6 MU | 600ml |
| No. 2, FLT-6 MU | 600-620ml |
| No. 3, FLT-6 MU | 600ml |
| No. 4, FLT-6 MU | 600ml |
Claims (1)
1. a nanometer Ni-Co-B plating process for continuous casting crystallizer copper plate/copper pipe, its processing step is as follows:
1) configuration tank liquor:
(1) get single nickel salt: 180-230g/L, nickelous chloride: 40-45 g/L, rose vitriol: 45-55 g/L, boric acid: No. 4, No. 3, No. 2, No. 1,45-50 g/L, FLT-6 MU: 50-100ml/L, FLT-6 MU: 30-80ml/L, FLT-6 MU: 19-25ml/L, FLT-6 MU: 20-30ml/L;
(2) add the deionized water of cumulative volume 1/3, be heated to 60-70 ℃;
(3) boric acid that takes formula ratio first dissolves;
(4) getting respectively rose vitriol, single nickel salt and nickelous chloride is dissolved in groove;
(5) fully stir with 1-3ml/l hydrogen peroxide, then add potassium permanganate, static 4-8 hour, adds 1-2g/l gac and stirs static filtration, and energising maintains current density at 0.1-0.15 ampere/square decimeter 8-12 hour;
(6) No. MU2, No. 1, FLT-6 that adds FLT-6 MU, is stirred to solution clear;
(7) continue to stir, in stirring, add No. 3, the water-reducible FLT-6 MU of deionization, No. MU4, FLT-6 with 5 times, then add deionized water to prescribed volume, adjust plating solution potential of hydrogen between 3.8-5.5, obtain plating solution for subsequent use;
2) polishing: polishing mode is to use 280# and 400# silicon carbide paper successively polish copper coin/copper pipe R angle and four sides, makes it spill matrix surface, removes surface film oxide and greasy dirt;
3) oil removing: use acid degreasing fluid, oil removing at ambient temperature, till presenting moisture film to the flushing of matrix surface water;
4) washing: rinse out the impurity of copper coin/copper pipe surface, avoid polluting tank liquor;
5) be installed: the copper coin/copper pipe after cleaning is installed to and is electroplated on workstation, the titanium anode that nickel button is housed is put into copper coin/copper pipe, recycling clamp is fixed anode, and the distance between anode and copper coin/copper pipe is controlled between 20mm;
6) deionized water: other harmful ions that rinse out copper coin/copper pipe surface;
7) activation: with salt acid soak copper coin/copper pipe 1-2 minute, remove the zone of oxidation of copper coin/copper pipe surface, activation matrix surface, increases the bonding force between copper coin/copper pipe and coating;
8) electroplate: utilize submersible pump plating solution to be imported from coating bath to copper coin/copper pipe, after copper coin/copper pipe is filled plating solution, connect wire, firing current is electroplated;
Electric current given: by the area of electroplating copper coin/copper pipe, then according to the current density of 2-10A/ square decimeter, calculate given electric current;
9) washing: electroplate after finishing copper coin/copper pipe is unloaded, rinse out the residual plating solution of copper coin/copper pipe surface with tap water, obtain the copper coin/copper pipe of nanometer Ni-Co-B coating.
Priority Applications (1)
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| CN201410041180.8A CN103820828A (en) | 2014-01-28 | 2014-01-28 | Nanometer Ni-Co-B coating technology for copper plate/copper tube of continuous casting crystallizer |
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| CN201410041180.8A CN103820828A (en) | 2014-01-28 | 2014-01-28 | Nanometer Ni-Co-B coating technology for copper plate/copper tube of continuous casting crystallizer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604397A (en) * | 2017-10-30 | 2018-01-19 | 西峡龙成特种材料有限公司 | The electro-plating method of continuous casting crystallizer copper plate deposit N i Co B alloy layers |
| CN109604126A (en) * | 2018-10-31 | 2019-04-12 | 博罗县东明化工有限公司 | Aluminium alloy sprays pre-treating method |
| CN111074308A (en) * | 2019-12-30 | 2020-04-28 | 福建南平南孚电池有限公司 | Method and device for electroplating nickel-cobalt alloy coating on surface of steel shell |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604397A (en) * | 2017-10-30 | 2018-01-19 | 西峡龙成特种材料有限公司 | The electro-plating method of continuous casting crystallizer copper plate deposit N i Co B alloy layers |
| CN107604397B (en) * | 2017-10-30 | 2019-02-15 | 西峡龙成特种材料有限公司 | The electro-plating method of continuous casting crystallizer copper plate deposit N i-Co-B alloy layer |
| CN109604126A (en) * | 2018-10-31 | 2019-04-12 | 博罗县东明化工有限公司 | Aluminium alloy sprays pre-treating method |
| CN111074308A (en) * | 2019-12-30 | 2020-04-28 | 福建南平南孚电池有限公司 | Method and device for electroplating nickel-cobalt alloy coating on surface of steel shell |
| CN111074308B (en) * | 2019-12-30 | 2021-03-12 | 福建南平南孚电池有限公司 | Method and device for electroplating nickel-cobalt alloy coating on surface of steel shell |
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