CN108118373B - The electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating - Google Patents
The electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating Download PDFInfo
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- CN108118373B CN108118373B CN201711408702.3A CN201711408702A CN108118373B CN 108118373 B CN108118373 B CN 108118373B CN 201711408702 A CN201711408702 A CN 201711408702A CN 108118373 B CN108118373 B CN 108118373B
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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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- 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
- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
- C25F1/02—Pickling; Descaling
- C25F1/04—Pickling; Descaling in solution
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a kind of electro-deposition restorative procedures of crystallizer copper dash-board injury nickel cobalt coating, it is using slotless electro-deposition techniques in-situ immobilization；The slotless electro-deposition techniques in-situ immobilization is that the nickel plate as anode is dipped to basic sediment liquid in the crystallizer copper dash-board injury nickel cobalt coating surface reciprocating movement as cathode, to deposit nickel cobalt repair layer in crystallizer copper dash-board injury nickel cobalt coating surface.Using slotless electro-deposition techniques, the in-situ immobilization on copper plate of crystallizer damages nickel cobalt coating to the present invention, it can effectively solve the problem that corner coating of the existing technology is thin, repairs the problems such as number is limited, obtained nickel cobalt repair layer thickness is uniform, corner and face are substantially all at 500~1000 μm, and the defects of can also effectively solving existing pin hole, point and dross during conventional electrodeposition using the friction repeatedly between anode and cathode, obtained nickel cobalt repair layer compact structure, surface are smooth.
Description
Technical field
The invention belongs to electro-deposition techniques fields, and in particular to a kind of electro-deposition of crystallizer copper dash-board injury nickel cobalt coating is repaired
Compound method.
Background technique
Currently, commonly interior coating includes nickel coating, ferronickel coating and nickel cobalt coating to copper plate of crystallizer, plated with pure nickel
Layer is compared with ferronickel coating, and nickel cobalt coating is other than possessing similar physical and chemical performance, and also two big advantages: (1) hardness is more
Higher hardness is still able to maintain under height, especially high temperature；(2) chemical stability is more preferable, especially thermal stability and high-temperature wearable
Damage performance is greatly improved.
In entire continuous casting production process, copper plate of crystallizer not only bears washing away for high-temperature molten steel, and by steel billet, guarantor
The friction for protecting slag, makes coating serious wear in copper plate of crystallizer, internal coating is needed to be repaired at this time, and common repair methods
It has the disadvantage that
(1) it needs first to remove damage nickel cobalt coating and part of matrix by the way of machining, then be electroplated again again
Nickel cobalt coating.It is more and more thinner to will lead to matrix in this way, largely effects on reparation number, can not just be repaired again after usually repairing 4~5 times
It is multiple.
(2) lower relative to its facial current density due to crystallizer corner, facial coating and corner after conventional reparation
Thickness of coating differs greatly and (usually differs 4~5 times) namely corner coating is relatively thin, and in actually using, crystallizer corner coating
Often more easy to wear, therefore, repairing effect is also undesirable.
Summary of the invention
The purpose of the present invention is to solve the above problem, provides that a kind of reparation number is unrestricted, repair layer thickness is uniform
Crystallizer copper dash-board injury nickel cobalt coating electro-deposition restorative procedure.
Realizing the technical solution of the object of the invention is: a kind of electro-deposition reparation side of crystallizer copper dash-board injury nickel cobalt coating
Method, it is using slotless electro-deposition techniques in-situ immobilization；The slotless electro-deposition techniques in-situ immobilization is will be as the nickel of anode
Plate dips basic sediment liquid in the crystallizer copper dash-board injury nickel cobalt coating surface reciprocating movement as cathode, thus in crystallizer copper
Dash-board injury nickel cobalt coating surface deposits nickel cobalt repair layer.
The basic sediment formula of liquid is as follows: 220~280g/L of nickel sulfate, 10~50g/L of cobaltous sulfate, citric acid ammonia 40g/
L, acetic acid ammonia 40g/L, pH=7.5~8.0.Deposition process parameters are as follows: deposition voltage is 8~14V, and anode movement speed is 10
~14m/min, sedimentation time are 0.5~2h.
The present invention further includes successively carrying out before depositing nickel cobalt repair layer to crystallizer copper dash-board injury nickel cobalt coating surface
The pretreatments such as polishing, the net oil removing of electricity, activation, deposition bottoming nickel layer.
The net oil removing of electricity is that the nickel plate as anode is dipped to electric net liquid in the crystallizer copper dash-board injury nickel as cathode
Cobalt coating surface moves back and forth.The electricity net liquid formula is as follows: 25~40g/L of sodium hydroxide, 20~40g/L of sodium carbonate, phosphoric acid
40~160g/L of sodium, 2~5g/L of sodium chloride, pH=11~13.Electric net technological parameter is as follows: the net voltage of electricity is 10V, and anode is mobile
Speed is 8~18m/min, and electric net time is 30s.
The activation is that the nickel plate as anode is dipped to activating solution in the crystallizer copper dash-board injury nickel cobalt plating as cathode
Layer surface moves back and forth.The activation formula of liquid is as follows: concentrated hydrochloric acid 25ml/L, sodium chloride 140g/L, pH=0.2~0.8.Activation
Technological parameter is as follows: activation current density is 10~15A/dm2, activation time is 30~90s.
The deposition bottoming nickel layer is that the nickel plate as anode is dipped to bottoming liquid in the copper plate of crystallizer damage as cathode
Hurt the reciprocating movement of nickel cobalt coating surface, to deposit bottoming nickel layer in crystallizer copper dash-board injury nickel cobalt coating surface.The bottoming
Formula of liquid is as follows: 390~400g/L of nickel sulfate, 15~25g/L of nickel chloride, 19~22ml/L of hydrochloric acid, 68~70ml/L of glacial acetic acid,
PH=0.3~1.0.Deposition process parameters are as follows: depositing temperature is 30~50 DEG C, deposition voltage 12V, and anode movement speed is 6
~8m/min, sedimentation time 1min.
The nickel cobalt repair layer thickness that method of the invention obtains is uniform, up to 500~1000 μm.
The nickel cobalt repair layer hardness that method of the invention obtains is higher, up to 700~850HV.
The good effect that the present invention has:
(1) using slotless electro-deposition techniques, the in-situ immobilization on copper plate of crystallizer damages nickel cobalt coating, Neng Gouyou to the present invention
Effect solves the problems such as corner coating of the existing technology is thin, reparation number is limited, and obtained nickel cobalt repair layer thickness is uniform, angle
Portion and face are substantially all at 500~1000 μm.
(2) method of the invention can also effectively solve conventional electrodeposition mistake using the friction repeatedly between anode and cathode
The defects of pin hole present in journey, point and dross, obtained nickel cobalt repair layer compact structure, surface are smooth.
(3) the nickel cobalt repair layer that method of the invention obtains also have hardness it is high, with basal body binding force is good, wearability is good,
It can satisfy the requirement that continuous casting high temperature draws steel billet.
(4) method equipment of the invention is simple, and easy to operate, good economy performance is easy to implement, especially deposition velocity compared with
Fastly, up to 10~15 μm/min, hence it is evident that it is higher than conventional electrodeposition, it is particularly suitable to be repaired on site with field.
Detailed description of the invention
Fig. 1 is the element power spectrum picture for the nickel cobalt repair layer that the method for embodiment 1 obtains.
Fig. 2 is the scanning electron microscope diagram piece that the nickel cobalt that the method for embodiment 1 obtains repairs layer cross section.
Specific embodiment
(embodiment 1)
It selects five points at random on the present embodiment crystallizer copper dash-board injury nickel cobalt coating to be repaired and carries out microhardness
Detection, is as a result respectively as follows: 440HV, 437HV, 429HV, 436HV, 448HV.
The electro-deposition restorative procedure of the crystallizer copper dash-board injury nickel cobalt coating of the present embodiment has follow steps:
1. polishing.
Successively crystallizer copper dash-board injury nickel cobalt coating surface is polished smooth using the sand paper of 100#, 200#, eliminates corner angle,
Then it is rinsed well and is dried with deionized water, finally pasted damage location surrounding with adhesive tape.
2. electric net oil removing.
Using copper plate of crystallizer connection power cathode as cathode, high-purity nickel terylene is wrapped up and connects positive pole work
For anode, electric net liquid is dipped with nickel plate and is moved back and forth in crystallizer copper dash-board injury nickel cobalt coating surface, to remove copper plate of crystallizer
Damage nickel cobalt coating surface rusty stain and greasy dirt.
Electric net liquid formula is as follows: sodium hydroxide 30g/L, sodium carbonate 28g/L, sodium phosphate 90g/L, and sodium chloride 3g/L, pH=
12。
Electric net technological parameter is as follows: the net voltage of electricity is 10V, and anode movement speed is 12m/min, and electric net time is 30s.
3. activating.
Using copper plate of crystallizer connection power cathode as cathode, high-purity nickel terylene is wrapped up and connects positive pole work
For anode, activating solution is dipped with nickel plate and is moved back and forth in crystallizer copper dash-board injury nickel cobalt coating surface, to remove copper plate of crystallizer
Damage nickel cobalt coating surface oxide and corrosion product.
It is as follows to activate formula of liquid: concentrated hydrochloric acid 25ml/L, sodium chloride 140g/L, pH=0.5.
Activating process parameter is as follows: activation current density is 12A/dm2, activation time 60s.
4. depositing bottoming nickel layer.
Using copper plate of crystallizer connection power cathode as cathode, high-purity nickel terylene is wrapped up and connects positive pole work
For anode, bottoming liquid is dipped with nickel plate and is moved back and forth in crystallizer copper dash-board injury nickel cobalt coating surface, thus in copper plate of crystallizer
It damages nickel cobalt coating surface and deposits bottoming nickel layer, to improve the bond strength of nickel cobalt repair layer.
Bottoming formula of liquid is as follows: nickel sulfate 400g/L, nickel chloride 20g/L, hydrochloric acid 20ml/L, and glacial acetic acid 70ml/L, pH=
0.6。
Deposition process parameters are as follows: depositing temperature is 40 DEG C, deposition voltage 12V, and anode movement speed is 7m/min, is sunk
The product time is 1min.
5. depositing nickel cobalt repair layer.
Using copper plate of crystallizer connection power cathode as cathode, high-purity nickel terylene is wrapped up and connects positive pole work
For anode, basic sediment liquid is dipped with nickel plate and is moved back and forth in crystallizer copper dash-board injury nickel cobalt coating surface, thus in crystallizer
Copper sheet damages nickel cobalt coating surface and deposits nickel cobalt repair layer.
Basic sediment formula of liquid is as follows: nickel sulfate 260g/L, cobaltous sulfate 50g/L, citric acid ammonia 40g/L, acetic acid ammonia 40g/
L, pH are adjusted to 7.8 through ammonium hydroxide.
Deposition process parameters are as follows: deposition voltage 11V, and anode movement speed is 12m/min, sedimentation time 1h.
The element power spectrum picture for the nickel cobalt repair layer that the method for the present embodiment obtains is shown in Fig. 1.
The scanning electron microscope diagram piece that the nickel cobalt that the method for the present embodiment obtains repairs layer cross section is shown in Fig. 2.
White line [artificial addition is to identify] lower section is loss nickel cobalt coating in Fig. 2, is then nickel cobalt repair layer above white line
As seen from Figure 2: the nickel cobalt repair layer compact structure that the method for the present embodiment obtains, surface is smooth, without needle
The defects of hole, point and dross, especially thickness is uniform, and corner and face are substantially all at 800 μm or so.
It selects five points at random on the nickel cobalt repair layer that the present embodiment obtains and carries out microhardness detection, as a result distinguish
Are as follows: 750HV, 761HV, 752HV, 756HV, 753HV.
Claims (8)
1. a kind of electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating, it is characterised in that: it is heavy using slotless electricity
Product technology in-situ immobilization；The slotless electro-deposition techniques in-situ immobilization is that the nickel plate as anode is dipped basic sediment liquid to make
It is moved back and forth for the crystallizer copper dash-board injury nickel cobalt coating surface of cathode, thus heavy in crystallizer copper dash-board injury nickel cobalt coating surface
Product nickel cobalt repair layer；
The basic sediment formula of liquid is as follows: 220~280g/L of nickel sulfate, 10~50g/L of cobaltous sulfate, ammonium citrate 40g/L, second
Sour ammonium 40g/L, pH=7.5~8.0.
2. the electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating according to claim 1, it is characterised in that: institute
It is as follows to state basic sediment formula of liquid: nickel sulfate 260g/L, cobaltous sulfate 50g/L, ammonium citrate 40g/L, ammonium acetate 40g/L, pH=
7.8。
3. the electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating according to claim 1, it is characterised in that: heavy
Product technological parameter is as follows: deposition voltage is 8~14V, and anode movement speed is 10~14m/min, and sedimentation time is 0.5~2h.
4. the electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating according to claim 3, it is characterised in that: heavy
Product technological parameter is as follows: deposition voltage 11V, and anode movement speed is 12m/min, sedimentation time 1h.
5. according to claim 1 to the electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating described in one of 4, feature
It is: further includes successively being polished crystallizer copper dash-board injury nickel cobalt coating surface, being electric net before depositing nickel cobalt repair layer
Oil removing, activation and deposition bottoming nickel layer.
6. the electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating according to claim 5, it is characterised in that: institute
Stating electric net oil removing is that the nickel plate as anode is dipped to electric net liquid in the crystallizer copper dash-board injury nickel cobalt coating surface as cathode
It moves back and forth；The electricity net liquid formula is as follows: 25~40g/L of sodium hydroxide, 20~40g/L of sodium carbonate, 40~160g/ of sodium phosphate
L, 2~5g/L of sodium chloride, pH=11~13；Electric net technological parameter is as follows: the net voltage of electricity is 10V, anode movement speed is 8~
18m/min, electric net time are 30s.
7. the electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating according to claim 5, it is characterised in that: institute
Stating activation is that the nickel plate as anode is dipped to activating solution is reciprocal in the crystallizer copper dash-board injury nickel cobalt coating surface as cathode
It is mobile；The activation formula of liquid is as follows: concentrated hydrochloric acid 25ml/L, sodium chloride 140g/L, pH=0.2~0.8；Activating process parameter is such as
Under: activation current density is 10~15A/dm2, activation time is 30~90s.
8. the electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating according to claim 5, it is characterised in that: institute
Stating deposition bottoming nickel layer is that the nickel plate as anode is dipped to bottoming liquid in the crystallizer copper dash-board injury nickel cobalt coating as cathode
Surface moves back and forth, to deposit bottoming nickel layer in crystallizer copper dash-board injury nickel cobalt coating surface；The bottoming formula of liquid is as follows:
390~400g/L of nickel sulfate, 15~25g/L of nickel chloride, 19~22ml/L of hydrochloric acid, 68~70ml/L of glacial acetic acid, pH=0.3~
1.0；Deposition process parameters are as follows: depositing temperature is 30~50 DEG C, deposition voltage 12V, and anode movement speed is 6~8m/
Min, sedimentation time 1min.
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| CN201711408702.3A CN108118373B (en) | 2017-12-22 | 2017-12-22 | The electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating |
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| CN201711408702.3A CN108118373B (en) | 2017-12-22 | 2017-12-22 | The electro-deposition restorative procedure of crystallizer copper dash-board injury nickel cobalt coating |
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| CN108118373B true CN108118373B (en) | 2019-12-03 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061810A (en) * | 1991-10-19 | 1992-06-10 | 江汉石油管理局运输公司大修厂 | High-deposition nickel brush-plating solution |
| CN103255451A (en) * | 2013-04-03 | 2013-08-21 | 河南理工大学 | Preparation method of thick high-speed nickel coating by brush plating |
| CN103397360A (en) * | 2010-06-25 | 2013-11-20 | 杨红宇 | Brush plating solution |
| CN103526240A (en) * | 2013-09-23 | 2014-01-22 | 中国人民解放军装甲兵工程学院 | Method for brushing electroplating chrome plating and carbon steel composite matrix |
-
2017
- 2017-12-22 CN CN201711408702.3A patent/CN108118373B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061810A (en) * | 1991-10-19 | 1992-06-10 | 江汉石油管理局运输公司大修厂 | High-deposition nickel brush-plating solution |
| CN103397360A (en) * | 2010-06-25 | 2013-11-20 | 杨红宇 | Brush plating solution |
| CN103255451A (en) * | 2013-04-03 | 2013-08-21 | 河南理工大学 | Preparation method of thick high-speed nickel coating by brush plating |
| CN103526240A (en) * | 2013-09-23 | 2014-01-22 | 中国人民解放军装甲兵工程学院 | Method for brushing electroplating chrome plating and carbon steel composite matrix |
Non-Patent Citations (1)
| Title |
|---|
| "电刷镀纳米晶Ni-Co合金镀层组织结构与性能的研究";郑炜铭等;《福州大学学报（自然科学版）》;20100228;第38卷(第1期);第90-94页 * |
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