CN104878421A - Manufacturing method of nickel/zinc cobalt alloy double-layer electroplated steel plate - Google Patents
Manufacturing method of nickel/zinc cobalt alloy double-layer electroplated steel plate Download PDFInfo
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- CN104878421A CN104878421A CN201510329310.2A CN201510329310A CN104878421A CN 104878421 A CN104878421 A CN 104878421A CN 201510329310 A CN201510329310 A CN 201510329310A CN 104878421 A CN104878421 A CN 104878421A
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Abstract
The invention discloses a manufacturing method of a nickel/zinc cobalt alloy double-layer electroplated steel plate. The manufacturing method comprises the steps of firstly conducting scale removal and cleaning on a cold-rolled sheet steel plate with the thickness ranging from 0.4-2.5 mm, using 20-30% by mass of diluted hydrochloric acid to perform activation, performing nickel electroplating, conducting heat treatment on the steel plate plated with nickel under the conditions of the temperature ranging from 500 DEG C to 700 DEG C and annealing time of 0.3-2 hours, electroplating zinc cobalt alloy on the surface of the steel plate subjected to heat treatment after nickel plating, using water to wash the steel plate subjected to zinc cobalt alloy electroplating, then using chromate to perform electrochemical cathode passivating treatment, performing thorough water flushing after passivating treatment is completed, using hot air to blow and dry the steel plate so as to obtain a finished product, namely the nickel/zinc cobalt alloy double-layer electroplated steel plate. The electroplated steel plate manufactured by means of the manufacturing method overcomes the defect of 'white rust' of a zinc plated layer, so that the service life of the steel plate is remarkably prolonged, and the quality of the product is improved.
Description
Technical field
The present invention relates to electroplating technology field, refer to a kind of manufacture method at Cold Rolled Sheet Steel electroplating nickel on surface/zinc-cobalt alloy double-layer electroplating steel plate particularly, this nickel/zinc-cobalt alloy double-layer electroplating steel plate is mainly used in the steel-sheet surface treatments such as car panel, home appliance panel and various office appliances.
Background technology
In order to improve the corrosion resistance nature of steel plate, will carry out surface treatment to steel plate, the most frequently used surface treatment method has application various organic or inorganic coating, pot galvanize or its alloy layer and electroplates various metal or alloy coating.
Nickel is the material with silvery white metal, and the hardness value of nickel is higher, and corrosion resistance nature is better, so can improve surface hardness and the corrosion resistance nature of steel plate in surface of steel plate nickel plating.But generally single nickel coating hole is more, and nickel coating is comparatively hard, and processing characteristics is poor, so will understand better at zinc-plated its corrosion resistance nature such as grade of surface electrical and processing characteristics again after general nickel plating.
Zinc coating has the metalluster of Bluish white and corrosion resistance nature is better, thus people usually through hot dip or electric plating method by zinc coated or galvanic deposit to the surface of ferrous materials to improve the corrosion resistance nature of steel.Compared with pot galvanize, electrogalvanizing steel plate due to the sticking power of zinc layers and steel matrix good, zinc layers evenly and is often used to the outside plate etc. of various superior automobile panel and various high-grade household electrical appliance in the surface arrangement of steel plate.But, electroplate the corrosion resistance nature of the Coated Steel of single metallic zinc or poor, particularly in humidity or under there is corrosive medium existent condition, zinc is easy to the corrosion product generating white loose, be commonly called as " white rust ", in order to improve the corrosion resistance nature of single zinc coating, people take the method for electroplating various alloy and substitute single zinc coating, as zn-fe alloy coating, zn-ni alloy deposits etc., these alloy layers are compared with single zinc coating, significantly can improve the corrosion resistance nature of Coated Steel, extend the work-ing life of steel.
Application number be 200910063258.5 Chinese invention patent disclose a kind of manufacture method of nickel zinc double-layer electroplating steel plate, the method first plates one deck nickel on the surface of steel plate, again the steel plate of nickel plating is heat-treated, one deck Rhometal layer is formed at surface of steel plate, and then on Rhometal layer electro-galvanizing, so both make the corrosion resisting property of steel plate be greatly enhanced, solve again the bonding force problem of coating and matrix.But although the nickel electroplated in this way/zinc double-layer electroplating steel plate improves the bonding force of coating and matrix and the corrosion resistance nature of coating, but the corrosion resistance nature of the zinc coating on top layer or poor, particularly in humidity or under having corrosive medium existent condition, zinc is easy to generate " white rust ".In order to improve the corrosion resistance nature of the single zinc coating in top layer,
Summary of the invention
Technical problem to be solved by this invention is just to provide the manufacture method of a kind of nickel/zinc-cobalt alloy double-layer electroplating steel plate.
For solving the problems of the technologies described above, the manufacture method of a kind of nickel/zinc-cobalt alloy double-layer electroplating steel plate provided by the invention, comprises the following steps:
1) be that 0.4 ~ 2.5mm cold rolling is rolled the first de-scaling rust cleaning of steel sheet, cleans, is the dilute hydrochloric acid activation of 20 ~ 30%, electroplated nickel plating by thickness with massfraction,
2) steel plate having plated nickel being placed in temperature is heat-treat under 500 ~ 700 DEG C of conditions, annealing time 0.3 ~ 2h; To form Rhometal layer at surface of steel plate, during annealing, the shielding gas such as hydrogenation or nitrogen in stove, is being oxidized to prevent steel plate;
3) zinc cobalt alloy plating film is electroplated
Plating nickel and through heat treated surface of steel plate electro-galvanizing cobalt-base alloy, the electroplate liquid formulation of plating zinc cobalt alloy plating film consists of: zinc chloride (ZnCl
2): 70 ~ 85g/L, cobalt chloride (CoCl
26H
2o): 4 ~ 16g/L, sodium-chlor (NaCl): 185 ~ 215g/L, boric acid (H
3bO
3): 18 ~ 22g/L;
4) Passivation Treatment:
Washed by the steel plate having plated zinc cobalt alloy plating film, then carry out electrochemical cathode Passivation Treatment with chromic salt, the complete rear water of passivation is rinsed well, obtains finished product with hot blast drying, is nickel/zinc-cobalt alloy double-layer electroplating steel plate.
Further, the formula of described nickel plating solution consists of: the single nickel salt (NiSO of 240 ~ 260g/L
47H
2o), the sodium-chlor (NaCl6H of 4 ~ 6g/L
2o), the boric acid (H of 30 ~ 35g/L
3bO
3), 45 ~ 55g/L magnesium sulfate (MgSO
47H
2o), the Sodium Fluoride (NaF) of 4 ~ 6g/L.
Again further, described step 1) in, in electroplating technology: pH value: 4 ~ 4.5, temperature is 45 ~ 50 DEG C, cathode current density: 1 ~ 1.5A/dm
2, thickness of coating: 0.5 ~ 3.0g/m
2.
Again further, described step 3) in, the electroplate liquid formulation of plating zinc cobalt alloy plating film consists of: the zinc chloride (ZnCl of 70 ~ 85g/L
2), the cobalt chloride (CoCl of 4 ~ 16g/L
26H
2o), the sodium-chlor (NaCl) of 185 ~ 215g/L and the boric acid (H of 18 ~ 22g/L
3bO
3).
Again further, described step 3) in, electroplating technology: pH value: 5.0 ~ 5.5, temperature is 20 ~ 35 DEG C, and cathode current density is 1 ~ 4A/dm
2, anode material: zine plate; Thickness of coating: 5g ~ 10/m
2, cobalt contents 0.3 ~ 0.9% in coating.
Again further, described step 4) in, chromating liquid consists of: the potassium bichromate (K of 190 ~ 210g/L
2cr
2o
7) and the vitriol oil (H of 8 ~ 10mL/L
2sO
4).
Again further, described step 4) in, passivating solution working temperature: room temperature, electrochemical cathode passivation electricity: during electrochemical cathode passivation, passivation electricity is not less than 2C/dm
2, passivation time: 10 ~ 20 seconds.
Principle of the present invention
The pure zinc coating that top layer is electroplated by the present invention changes plating zinc cobalt alloy plating film into, and the passivation of chromic salt electrochemical cathode is carried out to the zinc cobalt alloy plating film of plating, the nickel made in this way/zinc-cobalt alloy double-layer electroplating steel plate just can solve the problem that zinc coating produces " white rust ", thus significantly can improve the work-ing life of steel plate, the corrosion resistance nature of this nickel/zinc-cobalt alloy double-layer electroplating steel plate is 3 ~ 4 times of nickel/zinc double-layer electroplating steel plate.
Beneficial effect of the present invention is:
The manufacture method of nickel of the present invention/zinc-cobalt alloy double-layer electroplating steel plate, one deck nickel is first plated exactly specifically on the surface of steel plate, in order to improve the sticking power of nickel layer and steel matrix, the steel plate being coated with nickel to be heat-treated, to form one deck layer of iron-nickel alloy at surface of steel plate, in layer of iron-nickel alloy, plating contains the zinc cobalt alloy plating film of cobalt 0.3 ~ 1.0% again, then nickel/zinc-cobalt alloy the double-layer electroplating steel plate of method to plating of chromic salt electrochemical cathode passivation is adopted to carry out the passivation of chromic salt electrochemical cathode, nickel/zinc-cobalt alloy the double-layer electroplating steel plate of such making is compared with nickel/zinc double-layer electroplating steel plate, its corrosion resistance nature can be largely increased, the corrosion resistance nature of the nickel that identical thickness of coating and identical passivation technology make/zinc-cobalt alloy double-layer electroplating steel plate is 3 ~ 4 times of nickel/zinc double-layer electroplating steel plate.The nickel made in this way/zinc-cobalt alloy double-layer electroplating steel plate can solve " white rust " problem of zinc coating, thus significantly can improve the work-ing life of steel plate and improve the quality of finished product.
Embodiment
In order to explain the present invention better, illustrate main contents of the present invention further below in conjunction with specific embodiment, but content of the present invention is not only confined to following examples.
Embodiment 1
The manufacture method of nickel/zinc-cobalt alloy double-layer electroplating steel plate is as follows:
(1) by sample size be 100 × 50 × 1.5mm the first de-scaling rust cleaning of Cold Rolled Sheet Steel, clean, dilute hydrochloric acid with 20% activates, nickel plating, the formula of nickel plating solution consists of: single nickel salt (NiSO
47H
2o): 260g/L, sodium-chlor (NaCl6H
2o): 4g/L, boric acid (H
3bO
3): 30g/L, magnesium sulfate (MgSO
47H
2o): 55g/L, Sodium Fluoride (NaF): 4g/L; Electroplating technology: pH value: 4.5, temperature: 50 DEG C, cathode current density: 1A/dm
2, thickness of coating: 0.5g/m
2.
(2) heat-treated at 500 DEG C of temperature by the steel plate having plated nickel, annealing time 1 hour, to form Rhometal layer at surface of steel plate, during annealing, the shielding gas such as hydrogenation or nitrogen in stove, is being oxidized to prevent steel plate.
(3) zinc cobalt alloy plating film is electroplated
Plating nickel and through heat treated surface of steel plate electro-galvanizing cobalt-base alloy, the electroplate liquid formulation of plating zinc cobalt alloy plating film consists of: zinc chloride (ZnCl
2): 85g/L, cobalt chloride (CoCl
26H
2o): 16g/L, sodium-chlor (NaCl): 215g/L, boric acid (H
3bO
3): 22g/L;
Electroplating technology:
PH value: 5.5, temperature: 20 DEG C, cathode current density: 1A/dm
2, anode material: zine plate.Thickness of coating: 5g/m
2, cobalt contents 0.3 ~ 0.9% in coating.
(4), Passivation Treatment:
Washed by the steel plate having plated zinc cobalt alloy plating film, then carry out electrochemical cathode Passivation Treatment with chromic salt, chromating liquid consists of: potassium bichromate (K
2cr
2o
7): 190g/L, the vitriol oil (H
2sO
4): 10mL/L, passivating solution working temperature: room temperature, electrochemical cathode passivation electricity: during electrochemical cathode passivation, passivation electricity is not less than 2C/dm
2.Passivation time: 10 seconds, the complete rear water of passivation is rinsed well, gets product with hot blast drying.
The nickel plated out like this/zinc-cobalt alloy double-layer electroplating steel plate is compared with the nickel/zinc double-layer electroplating steel plate of identical thickness of coating, and surface of steel plate can not produce " white rust ", and its corrosion resistance nature is 3 ~ 4 times of the nickel/zinc double-layer electroplating steel plate of identical thickness of coating.
Embodiment 2
(1) be that 100 × 50 × 0.4mm cold rolling is rolled the first de-scaling rust cleaning of steel sheet, cleaned, dilute hydrochloric acid with 25% activates, nickel plating by thickness, the formula of nickel plating solution consists of: single nickel salt (NiSO
47H
2o): 240g/L, sodium-chlor (NaCl6H
2o): 6g/L, boric acid (H
3bO
3): 35g/L, magnesium sulfate (MgSO
47H
2o): 45g/L, Sodium Fluoride (NaF): 6g/L;
Electroplating technology: pH value: 4, temperature: 45 DEG C, cathode current density: 1.5A/dm
2.Thickness of coating: 3.0g/m
2.
(2) heat-treated at 700 DEG C of temperature by the steel plate having plated nickel, annealing time 0.3 hour, to form Rhometal layer at surface of steel plate, during annealing, the shielding gas such as hydrogenation or nitrogen in stove, is being oxidized to prevent steel plate.
(3) zinc cobalt alloy plating film is electroplated
Plating nickel and through heat treated surface of steel plate electro-galvanizing cobalt-base alloy, the electroplate liquid formulation of plating zinc cobalt alloy plating film consists of: zinc chloride (ZnCl
2): 70g/L, cobalt chloride (CoCl
26H
2o): 4g/L, sodium-chlor (NaCl): 185g/L, boric acid (H
3bO
3): 18g/L;
Electroplating technology:
PH value: 5.0, temperature: 35 DEG C, cathode current density: 4A/dm
2, anode material: zine plate.Thickness of coating: 10g/m
2, cobalt contents 0.3 ~ 0.9% in coating.
(4) Passivation Treatment:
Washed by the steel plate having plated zinc cobalt alloy plating film, then carry out electrochemical cathode Passivation Treatment with chromic salt, chromating liquid consists of: potassium bichromate (K
2cr
2o
7): 210g/L, the vitriol oil (H
2sO
4): 8mL/L, passivating solution working temperature: room temperature, electrochemical cathode passivation electricity: during electrochemical cathode passivation, passivation electricity is not less than 2C/dm
2.Passivation time: 15 seconds, the complete rear water of passivation is rinsed well, gets product with hot blast drying.
The nickel plated out like this/zinc-cobalt alloy double-layer electroplating steel plate is compared with the nickel/zinc double-layer electroplating steel plate of identical thickness of coating, and surface of steel plate can not produce " white rust ", and its corrosion resistance nature is 3 ~ 4 times of the nickel/zinc double-layer electroplating steel plate of identical thickness of coating.
Embodiment 3
(1) be that 100 × 50 × 2.5mm cold rolling is rolled the first de-scaling rust cleaning of steel sheet, cleaned, dilute hydrochloric acid with 30% activates, nickel plating by thickness, the formula of nickel plating solution consists of: single nickel salt (NiSO
47H
2o): 250g/L, sodium-chlor (NaCl6H
2o): 5g/L, boric acid (H
3bO
3): 31g/L, magnesium sulfate (MgSO
47H
2o): 50g/L, Sodium Fluoride (NaF): 5g/L;
Electroplating technology: pH value: 4, temperature: 46 DEG C, cathode current density: 1.2A/dm
2.Thickness of coating: 1.5g/m
2.
(2) heat-treated at 550 DEG C of temperature by the steel plate having plated nickel, annealing time 2 hours, to form Rhometal layer at surface of steel plate, during annealing, the shielding gas such as hydrogenation or nitrogen in stove, is being oxidized to prevent steel plate.
(3) zinc cobalt alloy plating film is electroplated
Plating nickel and through heat treated surface of steel plate electro-galvanizing cobalt-base alloy, the electroplate liquid formulation of plating zinc cobalt alloy plating film consists of: zinc chloride (ZnCl
2): 75g/L, cobalt chloride (CoCl
26H
2o): 10g/L, sodium-chlor (NaCl): 190g/L, boric acid (H
3bO
3): 20g/L;
Electroplating technology:
PH value: 5.0, temperature: 26 DEG C, cathode current density: 3A/dm
2, anode material: zine plate.Thickness of coating: 8g/m
2, cobalt contents 0.3 ~ 0.9% in coating.
(4) Passivation Treatment:
Washed by the steel plate having plated zinc cobalt alloy plating film, then carry out electrochemical cathode Passivation Treatment with chromic salt, chromating liquid consists of: potassium bichromate (K
2cr
2o
7): 200g/L, the vitriol oil: (H
2sO
4) 9mL/L, passivating solution working temperature: room temperature, electrochemical cathode passivation electricity: during electrochemical cathode passivation, passivation electricity is not less than 2C/dm
2.Passivation time: 12 seconds, the complete rear water of passivation is rinsed well, gets product with hot blast drying.
The nickel plated out like this/zinc-cobalt alloy double-layer electroplating steel plate is compared with the nickel/zinc double-layer electroplating steel plate of identical thickness of coating, and surface of steel plate can not produce " white rust ", and its corrosion resistance nature is 3 ~ 4 times of the nickel/zinc double-layer electroplating steel plate of identical thickness of coating.
Embodiment 4
(1) be that 100 × 50 × 2.0mm cold rolling is rolled the first de-scaling rust cleaning of steel sheet, cleaned, dilute hydrochloric acid with 27% activates, nickel plating by thickness, the formula of nickel plating solution consists of: single nickel salt (NiSO
47H
2o): 254g/L, sodium-chlor (NaCl6H
2o): 5g/L, boric acid (H
3bO
3): 36g/L, magnesium sulfate (MgSO
47H
2o): 52g/L, Sodium Fluoride (NaF): 5g/L;
Electroplating technology: pH value: 4.5, temperature: 50 DEG C, cathode current density: 1.4A/dm
2.Thickness of coating: 2.0g/m
2.
(2) heat-treated at 650 DEG C of temperature by the steel plate having plated nickel, annealing time 0.9 hour, to form Rhometal layer at surface of steel plate, during annealing, the shielding gas such as hydrogenation or nitrogen in stove, is being oxidized to prevent steel plate.
(3) zinc cobalt alloy plating film is electroplated
Plating nickel and through heat treated surface of steel plate electro-galvanizing cobalt-base alloy, the electroplate liquid formulation of plating zinc cobalt alloy plating film consists of: zinc chloride (ZnCl
2): 75g/L, cobalt chloride (CoCl
26H
2o): 15g/L, sodium-chlor (NaCl): 210g/L, boric acid (H
3bO
3): 20g/L,
Electroplating technology:
PH value: 5.0, temperature: 28 DEG C, cathode current density: 3.5A/dm
2, anode material: zine plate.Thickness of coating: 7g/m
2, cobalt contents 0.3 ~ 0.9% in coating.
(4) Passivation Treatment:
Washed by the steel plate having plated zinc cobalt alloy plating film, then carry out electrochemical cathode Passivation Treatment with chromic salt, chromating liquid consists of: potassium bichromate (K
2cr
2o
7): 205g/L, the vitriol oil (H
2sO
4): 9mL/L, passivating solution working temperature: room temperature, electrochemical cathode passivation electricity: during electrochemical cathode passivation, passivation electricity is not less than 2C/dm
2.Passivation time: 14 seconds, the complete rear water of passivation is rinsed well, gets product with hot blast drying.
The nickel plated out like this/zinc-cobalt alloy double-layer electroplating steel plate is compared with the nickel/zinc double-layer electroplating steel plate of identical thickness of coating, and surface of steel plate can not produce " white rust ", and its corrosion resistance nature is 3 ~ 4 times of the nickel/zinc double-layer electroplating steel plate of identical thickness of coating.
Other unspecified part is prior art.Although above-described embodiment is to invention has been detailed description; but it is only the present invention's part embodiment; instead of whole embodiment, people can also obtain other embodiments according to the present embodiment under without creative prerequisite, and these embodiments all belong to scope.
Claims (7)
1. a manufacture method for nickel/zinc-cobalt alloy double-layer electroplating steel plate, is characterized in that: comprise the following steps:
1) be that 0.4 ~ 2.5mm cold rolling is rolled the first de-scaling rust cleaning of steel sheet, cleans, is the dilute hydrochloric acid activation of 20 ~ 30%, electroplated nickel plating by thickness with massfraction;
2) steel plate having plated nickel being placed in temperature is heat-treat under 500 ~ 700 DEG C of conditions, annealing time 0.3 ~ 2h;
3) zinc cobalt alloy plating film is electroplated
Plating nickel and through heat treated surface of steel plate electro-galvanizing cobalt-base alloy;
4) Passivation Treatment:
Washed by the steel plate having plated zinc cobalt alloy plating film, then carry out electrochemical cathode Passivation Treatment with chromic salt, the complete rear water of passivation is rinsed well, obtains finished product with hot blast drying, is nickel/zinc-cobalt alloy double-layer electroplating steel plate.
2. the manufacture method of nickel/zinc-cobalt alloy double-layer electroplating steel plate according to claim 1, it is characterized in that: the formula of described nickel plating solution consists of: the single nickel salt of 240 ~ 260g/L, the sodium-chlor of 4 ~ 6g/L, the boric acid of 30 ~ 35g/L, 45 ~ 5g/L magnesium sulfate, the Sodium Fluoride of 4 ~ 6g/L.
3. the manufacture method of nickel/zinc-cobalt alloy double-layer electroplating steel plate according to claim 1 or 2, is characterized in that: described step 1) in, in electroplating technology: pH value: 4 ~ 4.5, temperature is 45 ~ 50 DEG C, cathode current density: 1 ~ 1.5A/dm
2, thickness of coating: 0.5 ~ 3.0g/m
2.
4. the manufacture method of nickel/zinc-cobalt alloy double-layer electroplating steel plate according to claim 1 or 2, it is characterized in that: described step 3) in, the electroplate liquid formulation of plating zinc cobalt alloy plating film consists of: the zinc chloride of 70 ~ 85g/L, the cobalt chloride of 4 ~ 16g/L, the sodium-chlor of 185 ~ 215g/L and the boric acid of 18 ~ 22g/L.
5. the manufacture method of nickel/zinc-cobalt alloy double-layer electroplating steel plate according to claim 4, is characterized in that: described step 3) in, electroplating technology: pH value: 5.0 ~ 5.5, temperature is 20 ~ 35 DEG C, and cathode current density is 1 ~ 4A/dm
2, anode material: zine plate; Thickness of coating: 5 ~ 10g/m
2, cobalt contents 0.3 ~ 0.9% in coating.
6. the manufacture method of nickel/zinc-cobalt alloy double-layer electroplating steel plate according to claim 1 or 2, is characterized in that: described step 4) in, chromating liquid consists of: the potassium bichromate of 190 ~ 210g/L and the vitriol oil of 8 ~ 10mL/L.
7. the manufacture method of nickel/zinc-cobalt alloy double-layer electroplating steel plate according to claim 1 or 2, it is characterized in that: described step 4) in, passivating solution working temperature: room temperature, electrochemical cathode passivation electricity: during electrochemical cathode passivation, passivation electricity is not less than 2C/dm
2, passivation time: 10 ~ 20 seconds.
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| CN106756577A (en) * | 2016-12-15 | 2017-05-31 | 苏州陈恒织造有限公司 | A kind of processing technology of the piston rod with china protective layer |
| CN110760906A (en) * | 2019-10-29 | 2020-02-07 | 中国地质大学（武汉） | Nano zinc-cobalt alloy coating based on double-pulse electrodeposition and preparation method thereof |
| CN115287656A (en) * | 2022-07-13 | 2022-11-04 | 首钢集团有限公司 | Zinc-aluminum-magnesium composite coating steel plate and preparation method thereof |
| CN115287656B (en) * | 2022-07-13 | 2023-10-13 | 首钢集团有限公司 | Zinc-aluminum-magnesium composite coating steel plate and preparation method thereof |
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