CN105562636B - A kind of preparation method for the copper plate of crystallizer for being plated with permivar layer - Google Patents
A kind of preparation method for the copper plate of crystallizer for being plated with permivar layer Download PDFInfo
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- CN105562636B CN105562636B CN201511015713.6A CN201511015713A CN105562636B CN 105562636 B CN105562636 B CN 105562636B CN 201511015713 A CN201511015713 A CN 201511015713A CN 105562636 B CN105562636 B CN 105562636B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
- B22D11/057—Manufacturing or calibrating the moulds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
- B22D11/059—Mould materials or platings
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a kind of preparation method for the copper plate of crystallizer for being plated with permivar layer, the composition of the copper plate of crystallizer is by mass percentage：Ni：1 2%；Be：0.05 0.2%；Al：0.5 0.7%, Zr：3.0 5.0%；Mn：1.2 1.4%；Mg：1 3%；Cr：0.8 1.2%；Zn：14.0 16.0%；Remaining is Cu, and the preparation method includes preparing crystallizer using the copper alloy with mentioned component, and in the electroplating surface coating layer of crystallizer, the composition for electroplating the plating solution used for：The 240g/l of nickel sulfate 220, the 19g/l of nickel chloride 17, the 5.5g/l of cobaltous sulfate 4.5, the 8.5g/l of ferric sulfate 7.5, the 27g/l of boric acid 23, the 7g/l of potassium sulfate 5, the 40g/l of sodium chloride 30, the 0.4g/l of lauryl sodium sulfate 0.2, the 22ml/L of additive 20, wherein it is added to and adds in 1l water the solution prepared using 10 12g sodium gluconates, 33 37g ascorbic acid and 22 26g dextrin, electroplating technical conditionses is：PH value 2.3 3.5, the 4.2A/dm of current density 3.82, 44 46 DEG C of temperature, untill being electroplated to thickness of coating as 1.3 1.5mm.
Description
Technical field
The present invention relates to electroplating technology, more particularly to a kind of system for the copper plate of crystallizer for being plated with permivar layer
Preparation Method.
Background technology
Copper plate of crystallizer is conticaster important component, and molten steel flows through conticaster crystallizer by being cooled into steel billet.Even
Cast in throwing production process, steel billet contacts with each other with copper coin surface produces friction, and copper coin surface produces abrasion, generally use function
Property electroplating technology in the good and wear-resisting material of one layer of heat conductivility of its coating surface, mitigate copper coin surface abrasion to reach, carry
High copper coin repairs number, extends the purpose of copper coin service life.It is fast-developing with Development of Continuous Casting Technique, copper plate electroplating technology：Plating
Layer material from elemental metals to alloy material develop, from chromium to nickel to ferronickel, nickel cobalt (alloy) develop, plating form from composite bed to
Individual layer develops, and this functional plating is different from Common platings, and coating is thicker, usual thickness 0.2mm-2mm, inevitable band
Carry out coating internal stress and accumulate to obtain larger problem, for copper coin in continuous casting, coating working face is in high-temperature molten steel and cooling water
In environment, colding and heat succeed each other frequently, induction coating cracks, and obscission occurs sometimes in coating, influences copper coin throwing steel transportation amount,
Influence conticaster production efficiency.And electroplating work procedure is more, production cycle length.
Notification number is CN1239752C application for a patent for invention《The method of electroformed nickel-cobalt alloy》Disclose a kind of galvanizer
Skill, its electroplate liquid are by NiSO4·7H2O、NiCl2·6H2O、FeSO4·7H2O、CoSO4·7H2O、NaCl、H3BO3、
C12H25SO4Na, additive are formulated by a certain percentage, and the patent application efficiently solves coating and basal body binding force difference
Problem, improve the service life of copper plate of crystallizer.
The content of the invention
It is an object of the invention to propose a kind of preparation method for the copper plate of crystallizer for being plated with permivar layer, the party
Method is adjusted to the component of copper plate of crystallizer so that intensity is higher, and heat conductivility is more preferable, and passes through the tune to solution composition
It is whole so that the adhesion of coating and matrix is good, stress is small, extends the service life of crystallizer.
To use following technical scheme up to this purpose, the present invention：
A kind of preparation method for the copper plate of crystallizer for being plated with permivar layer, the composition of the copper plate of crystallizer press matter
Measuring percentage is：Ni：1-2%；Be：0.05-0.2%；Al：0.5-0.7%, Zr：3.0-5.0%；Mn：1.2-1.4%；Mg：
1-3%；Cr：0.8-1.2%；Zn：14.0-16.0%；Remaining is Cu, and the preparation method includes using with mentioned component
Copper alloy prepares crystallizer, and in the electroplating surface coating layer of crystallizer, the composition for electroplating the plating solution used for：Nickel sulfate
220-240g/l, nickel chloride 17-19g/l, cobaltous sulfate 4.5-5.5g/l, ferric sulfate 7.5-8.5g/l, boric acid 23-27g/l, sulfuric acid
Potassium 5-7g/l, sodium chloride 30-40g/l, lauryl sodium sulfate 0.2-0.4g/l, additive 20-22ml/L, adopted wherein being added to
With 10-12g sodium gluconates, 33-37g ascorbic acid and 22-26g dextrin add in 1L water the solution prepared, electroplating technology bar
Part is：PH value 2.3-3.5, current density 3.8-4.2A/dm2, 44-46 DEG C of temperature, it is about 1.3- to be electroplated to thickness of coating
Untill 1.5mm.
The present invention has the advantages that：
1) present invention is adjusted to the composition of roll surface copper alloy, based on the brass for adding zinc, adds Ni,
The elements such as Be, Al, Zr, Mn, Mg, Cr play the advantage of alloying element interaction, and the copper for obtaining high intensity and high-termal conductivity closes
Golden material, HBS are more than 245；Softening temperature is more than 580 DEG C.
2) adjustment of base material copper alloy composition is directed to, plating solution composition when being electroplated to continuous cast mold roll surface is changed
Enter, change pure nickel plating as the joint plating of nickel cobalt iron, to improve the decay resistance of coating；Using the main salt of sulfate bath and addition
Agent system, sulfate bath system are small compared to the disposable input cost of the systems such as sulfamate；Additive sodium gluconate,
Ascorbic acid and dextrin can make the increase of coating compression, by adding additive, reduce coating internal stress, while additive has
The effect of coating leveling ability is improved, is also had and is improved coating brightness, improves ductility of electrodeposited film effect；By adjusting iron in plating solution
Salt, cobalt salt and nickel salt content, nickel, cobalt, iron content in coating are controlled, in the production of continuous casting throwing, nickel cobalt iron plating hot tearing quantity
Reduce, coating come off probability reduction.Cause coating while corrosion resistance is obtained with good thermal fatigue resistance simultaneously
Can, and relatively low thermal stress, while wearability improves.So that solution composition and copper alloy are coordinated into split-phase.
3) coating after testing, obtained using the plating solution of the present invention has following performance：Coating hardness is 260-280HV；
The internal stress of coating is only 38-43N/mm2.The matrix for being coated with coating of the present invention is subjected to thermal fatigue test, in 600 DEG C of temperature
It is lower insulation 5 minutes, then in the quenching-in water in room temperature, then be incubated 5 minutes at a temperature of 600 DEG C, repeat it is such insulation and
Quenching test 500 times, as a result finds, coating combined with matrix it is intact, the defects of coating surface flawless, peeling, bubbling.Using
The crystallizer continuous casting of coating of the present invention is coated with, coating is intact after the heat of direct casting 43.Commented according to GB6461-2002 salt fogs
To sentence standard to be tested, coating of the invention is significantly larger than the resisting salt fog corrosion time as defined in standard, therefore, coating of the invention
Excellent anti-corrosion performance.
Embodiment
Embodiment one
A kind of preparation method for the copper plate of crystallizer for being plated with permivar layer, the composition of the copper plate of crystallizer press matter
Measuring percentage is：Ni：1%；Be：0.2%；Al：0.5%, Zr：5.0%；Mn：1.2%；Mg：3%；Cr：0.8%；Zn：
16.0%；Remaining is Cu；, the preparation method includes preparing crystallizer using the copper alloy with mentioned component, and is crystallizing
The electroplating surface coating layer of device, it is described electroplate the composition of plating solution that uses for：Nickel sulfate 220g/l, nickel chloride 19g/l, cobaltous sulfate
4.5g/l, ferric sulfate 8.5g/l, boric acid 27g/l, potassium sulfate 5g/l, sodium chloride 40g/l, lauryl sodium sulfate 0.2g/l, add
Add agent 22ml/L, add in 1L water what is prepared using 10g sodium gluconates, 37g ascorbic acid and 22g dextrin wherein being added to
Solution, the process conditions are：P H value 2.3-3.5, current density 3.8A/dm2, 44-46 DEG C of temperature, it is electroplated to thickness of coating
Untill 1.3mm.
Embodiment two
A kind of preparation method for the copper plate of crystallizer for being plated with permivar layer, the composition of the copper plate of crystallizer press matter
Measuring percentage is：Ni：2%；Be：0.05%；Al：0.7%, Zr：3.0%；Mn：1.4%；Mg：1%；Cr：1.2%；Zn：
14.0%；Remaining is Cu；The preparation method includes preparing crystallizer using the copper alloy with mentioned component, and in crystallizer
Electroplating surface coating layer, it is described electroplate the composition of plating solution that uses for：Nickel sulfate 240g/l, nickel chloride 17g/l, cobaltous sulfate
5.5g/l, ferric sulfate 7.5g/l, boric acid 23g/l, potassium sulfate 7g/l, sodium chloride 30g/l, lauryl sodium sulfate 0.4g/l, add
Add agent 20ml/L, add in 1L water what is prepared using 12g sodium gluconates, 33g ascorbic acid and 26g dextrin wherein being added to
Solution, the process conditions are：P H value 2.3-3.5, current density 4.2A/dm2, 44-46 DEG C of temperature, it is electroplated to thickness of coating
Untill 1.5mm.
Embodiment three
A kind of preparation method for the copper plate of crystallizer for being plated with permivar layer, the composition of the copper plate of crystallizer press matter
Measuring percentage is：Ni：1.5%；Be：0.12%；Al：0.6%, Zr：4.0%；Mn：1.3%；Mg：2.0%；Cr：1.0%；
Zn：15.0%；Remaining is Cu；The preparation method includes preparing crystallizer using the copper alloy with mentioned component, and is tying
The electroplating surface coating layer of brilliant device, it is described electroplate the composition of plating solution that uses for：Nickel sulfate 230g/l, nickel chloride 18g/l, sulfuric acid
Cobalt 5.0g/l, ferric sulfate 8.0g/l, boric acid 24g/l, potassium sulfate 6g/l, sodium chloride 35g/l, lauryl sodium sulfate 0.3g/l,
Additive 21ml/L, add in 1L water and prepare using 11g sodium gluconates, 34g ascorbic acid and 24g dextrin wherein being added to
Solution, the process conditions are：P H value 2.3-3.5, current density 4A/dm2, 44-46 DEG C of temperature, it is electroplated to thickness of coating
Untill 1.4mm.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (1)
- A kind of 1. preparation method for the copper plate of crystallizer for being plated with permivar layer, it is characterised in that the copper plate of crystallizer Composition be by mass percentage：Ni：1-2%；Be：0.05-0.2%；Al：0.5-0.7%, Zr：3.0-5.0%；Mn：1.2- 1.4%；Mg：1-3%；Cr：0.8-1.2%；Zn：14.0-16.0%；Remaining is Cu, and the HBS hardness of the copper coin is more than 245； Softening temperature is more than 580 DEG C；The preparation method includes preparing crystallizer using the copper alloy with mentioned component, and is crystallizing The electroplating surface coating layer of device, it is described electroplate the composition of plating solution that uses for：Nickel sulfate 220-240g/l, nickel chloride 17-19g/ L, cobaltous sulfate 4.5-5.5g/l, ferric sulfate 7.5-8.5g/l, boric acid 23-27g/l, potassium sulfate 5-7g/l, sodium chloride 30-40g/l, Lauryl sodium sulfate 0.2-0.4g/l, wherein additive 20-22ml/L, additive are using 10-12g sodium gluconates, 33- 37g ascorbic acid and 22-26g dextrin add in 1L water the solution prepared, and electroplating technical conditionses are：PH value 2.3-3.5, electric current Density 3.8-4.2A/dm2, 44-46 DEG C of temperature, untill being electroplated to thickness of coating as 1.3-1.5mm；Coating hardness is 260- 280HV ；The internal stress of coating is only 38-43N/mm2。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201511015713.6A CN105562636B (en) | 2015-12-31 | 2015-12-31 | A kind of preparation method for the copper plate of crystallizer for being plated with permivar layer |
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| CN201511015713.6A CN105562636B (en) | 2015-12-31 | 2015-12-31 | A kind of preparation method for the copper plate of crystallizer for being plated with permivar layer |
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| CN105562636A CN105562636A (en) | 2016-05-11 |
| CN105562636B true CN105562636B (en) | 2018-03-23 |
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| CN106637936B (en) * | 2016-12-26 | 2019-04-30 | 浙江大学 | A kind of graphene-iron composite fibre and preparation method thereof |
| CN108642547A (en) * | 2018-05-28 | 2018-10-12 | 西南石油大学 | A kind of method that electro-deposition prepares graphene-Ni-Fe-Co alloy layers |
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| CN101116900A (en) * | 2007-09-04 | 2008-02-06 | 广州市锐优表面科技有限公司 | Method for preparing strengthened coatings on the continuance casting crystallizer surface |
| CN101524746A (en) * | 2009-04-03 | 2009-09-09 | 鞍山金维表面工程技术有限公司 | Technological method for repairing continuous caster crystallizer copperplate by coating WC alloy |
| CN101724873A (en) * | 2008-10-31 | 2010-06-09 | 鞍钢重型机械有限责任公司 | Functional electroplating process of copperplates of crystallizers |
| CN102039384A (en) * | 2009-10-23 | 2011-05-04 | 宝山钢铁股份有限公司 | Composite coating layer on surface of high-resistant crystallizer or crystallizing roller and manufacturing method thereof |
| CN103069025A (en) * | 2010-08-27 | 2013-04-24 | 古河电气工业株式会社 | Copper alloy sheet and manufacturing method for same |
| CN103614751A (en) * | 2013-11-22 | 2014-03-05 | 西峡龙成特种材料有限公司 | Copper-plate nickel-manganese-alloy electroplated layer of continuous-casting crystallizer and preparation process thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63149345A (en) * | 1986-12-15 | 1988-06-22 | Nippon Mining Co Ltd | High strength copper alloy having high electrical conductivity and improved heat resistance |
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- 2015-12-31 CN CN201511015713.6A patent/CN105562636B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101116900A (en) * | 2007-09-04 | 2008-02-06 | 广州市锐优表面科技有限公司 | Method for preparing strengthened coatings on the continuance casting crystallizer surface |
| CN101724873A (en) * | 2008-10-31 | 2010-06-09 | 鞍钢重型机械有限责任公司 | Functional electroplating process of copperplates of crystallizers |
| CN101524746A (en) * | 2009-04-03 | 2009-09-09 | 鞍山金维表面工程技术有限公司 | Technological method for repairing continuous caster crystallizer copperplate by coating WC alloy |
| CN102039384A (en) * | 2009-10-23 | 2011-05-04 | 宝山钢铁股份有限公司 | Composite coating layer on surface of high-resistant crystallizer or crystallizing roller and manufacturing method thereof |
| CN103069025A (en) * | 2010-08-27 | 2013-04-24 | 古河电气工业株式会社 | Copper alloy sheet and manufacturing method for same |
| CN103614751A (en) * | 2013-11-22 | 2014-03-05 | 西峡龙成特种材料有限公司 | Copper-plate nickel-manganese-alloy electroplated layer of continuous-casting crystallizer and preparation process thereof |
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