CN105921706A - On-line repair method for continuous casting crystallizer copper plate - Google Patents
On-line repair method for continuous casting crystallizer copper plate Download PDFInfo
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- CN105921706A CN105921706A CN201610333391.8A CN201610333391A CN105921706A CN 105921706 A CN105921706 A CN 105921706A CN 201610333391 A CN201610333391 A CN 201610333391A CN 105921706 A CN105921706 A CN 105921706A
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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
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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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
- C25D5/10—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
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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
- C25D7/00—Electroplating characterised by the article coated
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- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention belongs to the technical field of surface processing and electroplating, in particular to a repair method for a continuous casting crystallizer copper plate. The repair method for the continuous casting crystallizer copper plate comprises the steps of performing correction before plating, plating layer removal, copper plating, processing, electroplating of a plating layer, correction after plating and secondary processing on the copper plate. An electroplating solution adopted for the copper plating is composed of copper sulfate, sulphuric acid, chlorine ions, 2-mercaptobenzimidazole, ethylenethiourea and sodium 3,3'-dithiodipropane sulfonate. Process conditions for the copper plating are as follows: the temperature is 10-40 DEG C, the cathode-current density is 1-10 A/dm<2>, an anode is a phosphorous copper anode or a phosphorous copper ball, and the stirring condition is stirring by a circulating pump or air stirring. By means of the repair method, the service life of the copper plate is prolonged; meanwhile, the cost is reduced; the operation efficiency and income are improved; and the sustainable utilization of the crystallizer copper plate is realized.
Description
Technical field
The present invention relates to plating surface treatment technical field, be specifically related to the side of reparation online of a kind of continuous casting crystallizer copper plate
Method, it is adaptable to repair the copper plate of crystallizer reaching to repair the limit that the casting continuously such as iron and steel, non-ferrous metal uses.
Background technology
Conticaster is the key equipment of steel-making, and crystallizer is the core component of conticaster, and its quality directly influences
The quality of strand and the operating rate of conticaster.It is cold that the molten steel of boiling and melted covering slag liquid directly contact copper plate of crystallizer surface
But become strand, and along with the sliding friction between inwall and strand, severe operating environment requirements copper plate of crystallizer surface has
Preferably heat conductivity, higher mechanical strength, the wearability having had well and corrosion resisting property.
In steelmaking process, molten steel constantly by crystallizer, connects after being condensed into hard green shell below crystallizer
Continuous pull-out, it is achieved produce continuously.Along with developing rapidly of steel and iron industry, the performance of crystallizer material surface is proposed increasingly
High requirement, the development of crystallizer has high mechanical properties, good heat conductivity, wearability and decay resistance by continuing towards
Direction develop.What domestic and international application was most at present is in copper plate of crystallizer electroplating surface Cr, Ni, Ni ~ Co, Co ~ Ni, thermal spraying
Etc. coating, improve wearability and the corrosion resistance of copper coin.
Along with continuous casting to high efficiency develop, become the service life of continuous cast mold restriction continuous casting produce one important because of
Element.Continuous cast mold is repaired, extends its service life, even water rate to improving, it is ensured that slab quality, and improve enterprise
Technological Economy efficiency tool be of great significance.The method repairing continuous cast mold conventional has: plasma spraying NiCr-
Cr3C2Coating (Chen Jian, Liu Xue waft, Liang Huan. the research of crystallizer chromium zirconium copper surface plasma spraying nickel chromium triangle-chromium carbide coating,
Material Leader, 2010,11(24): 525-528), laser fusion covered nickel base coating (punishment flies, Hou Danhui, Zhang Yifei, Gong Minghui. a kind of
Alloy coat of crystallizer surface laser cladding and preparation method thereof, application number: 200810012662) and plating (Hou Fengyan, Tan
Xinghai County, Huang Li, Fang Ming, Li Chaoxiong. thin band continuous casting crystallization roller or strand continuous cast mold surface repairing method. application number:
200810201318.0) etc.；In above-mentioned restorative procedure, plasma spraying layer porosity is high, and in machinery between continuous cast mold
Property combine, be on active service after a period of time and easily peel off.Although it is strong to define combination between laser fusion covered nickel base coating and continuous cast mold
Spending high metallurgical binding, but laser reflectivity height is caused laser melting coating efficiency low by continuous cast mold, coating is easy to crack.And electroplate
Technology produces work as the hotter process for treating surface of current research, the continuous casting that Comparatively speaking can better adapt to continuous cast mold
Condition, it is thus achieved that preferably repairing effect, extends the service life of copper plate of crystallizer, reduces cost of manufacture etc..But current plating
Recovery technique repairing effect is limited, does not also reach the level of new crystallizer, needs to be further improved and enhanced.
Summary of the invention
In view of this, it is an object of the invention to provide the restorative procedure of a kind of continuous casting crystallizer copper plate, utilize this method can
So that the copper plate of crystallizer reaching to repair the limit repairs utilization again, and plate on the mother metal surface of copper plate of crystallizer
Copper, the problem of thickness low LCL after solution mold copper plate wear, the copper plate of crystallizer after being repaired by said method can be complete
Meet the needs that continuous casting produces, be possible not only to be greatly improved the service life of copper coin, and can cost efficiency, it is possible to achieve can
Sustainable utilization.
For achieving the above object, the technical solution adopted in the present invention is:
The restorative procedure of a kind of continuous casting crystallizer copper plate, comprises the following steps:
Step S1: the copper plate of crystallizer being intended to scrap is corrected, it is ensured that copper plate of crystallizer flatness before processing is not more than
0.2mm/m；
Step S2: be removed processing to the coating on copper plate of crystallizer surface to be scrapped；
Step S3: the copper plate of crystallizer surface to be scrapped is implemented plating copper facing operation,
Consisting of of the electroplate liquid used:
Copper sulfate: 150 ~ 280g/L, sulphuric acid: 50 ~ 100g/L, chloride ion: 10 ~ 120mL/L, 2-mercaptobenzimidazole: 0.0003 ~
0.015g/L, ethylene thiourea: 0.0002 ~ 0.01g/L, sodium polydithio-dipropyl sulfonate: 0.005 ~ 0.3g/L,
The process conditions of copper facing operation are:
Temperature: 10 ~ 40 DEG C, cathode-current density: 1 ~ 10A/dm2, anode: phosphor-copper angle or phosphorous copper balls, stirring condition: circulating pump stirs
Mix or air stirring,
Step S4: the copper coin after plating copper facing being carried out polish, removes surface oxide layer and rejected region, ultrasonic examination is closed
Lattice, surface roughness < 3.2 μm of copper coin after machining；
Step S5: the copper coin after machining is carried out galvanization coating operation；
Step S6: the coating copper coin after plating is corrected, it is ensured that the flatness of copper coin is not more than 0.08mm/m；
Step S7: require copper coin is carried out whole processing according to design, complete the reparation to copper coin.
Further, in step S3, consisting of of described electroplate liquid:
Copper sulfate: 200 ~ 250g/L, sulphuric acid: 70 ~ 80g/L, chloride ion: 50 ~ 80mL/L, 2-mercaptobenzimidazole: 0.005 ~
0.012g/L, ethylene thiourea: 0.001 ~ 0.008g/L, sodium polydithio-dipropyl sulfonate: 0.12 ~ 0.20g/L.
Further, in step S3, the described phosphorous 0.05 ~ 0.07wt% in phosphor-copper angle.
Further, in step S3, the phosphorous 0.03 ~ 0.05wt% of described phosphorous copper balls.
Further, in step S3, the copper facing thickness on copper plate of crystallizer surface is 0.5 ~ 15mm.
Further, in step S5, the electroplate liquid that described galvanization coating operation is used forms and process control condition is:
Nickel sulfamic acid: 450 ~ 600g/L；Sulfamic acid cobalt: 7 ~ 12g/L；Boric acid: 30 ~ 40g/L；Nickel dichloride.: 10 ~ 12g/L；Second
Base sodium hexy1 sulfate: 0.002 ~ 0.08mL/L；Benzyl-thiazolinyl pyridinium inner salt: 40 ~ 50mL/L；
Electric current density: 2 ~ 8A/dm2；PH:3.0-4.5；Stirring condition: circulating pump stirring or compressed air stirring；
After thickness of coating reaches technological requirement, i.e. stop electroplating activity.
Compared with prior art, it has the beneficial effect that the present invention:
The present invention is directed to current copper plate of crystallizer, to repair probability high, and need to roll off the production line reparations, and reparation scrap for several times after the money that causes
Source waste problem, it is proposed that a kind of can carry out repair process to reaching the reparation copper plate of crystallizer i.e. to be scrapped of the limit online,
To extending the service life of copper coin, reduce cost simultaneously, improve working performance and income, it is achieved copper plate of crystallizer sustainable
Use.
The present invention is directed to copper plate of crystallizer to be scrapped, carried out long-term tracking test and exploration, even shut out to reduce
Scrapping of exhausted copper plate of crystallizer, it is proposed that being suitable for the restorative procedure of such copper plate of crystallizer, it includes plating copper coin front school
Just, coating, copper facing, processing, galvanization coating, plating post-equalization and the step of secondary operations are removed.Copper coin is made by correction before plating
In subsequent treatment, keep suitable flatness, be conducive to copper plate of crystallizer overlay coating is processed, improve the plating of copper coin
Layer quality；Remove coating and refer to remove the existing coating of crystallizer, in order to avoid affecting the most copper-plated actual effect and flatness；Plating
Copper, is that copper plate of crystallizer surface carries out a copper plating treatment, repairs existing abrasion, make up mother metal copper surface defect and/
Or increase the thickness of mother metal copper；Processing, is processed, to remove surface oxide layer and rejected region, really after copper facing
Protect the surface after copper facing to meet the requirements, in order to follow-up coating electroplating activity；Galvanization coating, in order to increase copper coin after reparation
Corrosion resistance and wearability, extend its service life, and existing galvanization coating can be used to carry out operation, such as copper electroplating layer, nickel
Cobalt alloy layer, dilval layer etc., need to mate according to different process；Plating post-equalization, after being to ensure that galvanization coating operation
The flatness of copper plate of crystallizer, improve the serviceability of copper plate of crystallizer；Secondary operations, is to carry out above-mentioned copper plate of crystallizer
Final processing, to meet the needs that continuous casting produces.Before and after above steps through, sequentially operation, it is ensured that repair in repair process
Compound body amount and the requirement of precision, make existing copper coin timber and new coating be closely linked simultaneously, become an entirety, make
Copper plate of crystallizer after must repairing can fully meet the needs that crystallizer continuous casting produces, and the use of copper coin is not only greatly improved
Life-span, and significantly reduce operating cost, increase benefit, save existing resource, it is achieved the sustainable use of copper plate of crystallizer.
For copper coating step proposed by the invention, the copper plate of crystallizer to be scrapped has been usually subjected to long-term use
Repeatedly repairing, for the relatively new product of its surface quality, defect is more complicated, and changing factor is more, and quality controllability is relatively low, and
Prior art for the copper-plating technique of such copper plate of crystallizer, to this, not the invention provides for crystallizer to be scrapped
The copper-plating technique of copper coin, mainly includes electroplate liquid composition and electroplating technology.Tested by the several years, practice have shown that for existing on market
For the crystallizer to be scrapped having, this copper-plating technique is the most applicable, also achieves satisfied practice effect.
The present invention proposes the online restorative procedure for copper plate of crystallizer to be scrapped, by this method, copper plate of crystallizer
Service life be greatly improved, be expected to realize sustainable use, do not scrap, and without reparation of rolling off the production line, improve operation
Efficiency, frequency of maintenance and expense all significantly reduce.The copper plate of crystallizer repaired by this restorative procedure, after heat treatment, plating
Layer is strong with basal body binding force, the excellent performance such as hardness, decay resistance and porosity.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment
It is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under not making creative work premise, broadly falls into the model of present invention protection
Enclose.
Chemical substance used in the present invention, the molecular formula of 2-mercaptobenzimidazole is C7H6N2S, No. CAS is 583-39-1.
The chemical formula of ethylene thiourea is C3H6SN2, No. CAS is 96-45-7.The molecular formula of sodium polydithio-dipropyl sulfonate is
C6H12O6S4Na2, No. CAS is 27206-35-5.
Copper plate of crystallizer to be scrapped described in the present invention refers to cannot be further continued for using after n time (n >=1) repairs
Copper plate of crystallizer, the reparation reason of indication and mode can be varied, do not limit the invention.
The invention provides the restorative procedure of a kind of continuous casting crystallizer copper plate, comprise the following steps:
Step S1, correction: the copper plate of crystallizer being intended to scrap is corrected, it is ensured that copper plate of crystallizer flatness before processing is not
More than 0.2mm/m；Calibrating (base measuring) pressure meter is used to carry out the correction of copper coin；
Step S2, removal coating: be removed processing to the coating on copper plate of crystallizer surface to be scrapped；
Step S3, copper facing: the copper plate of crystallizer surface to be scrapped is implemented plating copper facing operation,
Consisting of of the electroplate liquid used:
Copper sulfate: 150 ~ 280g/L, sulphuric acid: 50 ~ 100g/L, chloride ion: 10 ~ 120mL/L, 2-mercaptobenzimidazole: 0.0003 ~
0.015g/L, ethylene thiourea: 0.0002 ~ 0.01g/L, sodium polydithio-dipropyl sulfonate: 0.005 ~ 0.3g/L,
The process conditions of copper facing operation are:
Temperature: 10 ~ 40 DEG C, cathode-current density: 1 ~ 10A/dm2, anode: phosphor-copper angle or phosphorous copper balls, stirring condition: circulating pump stirs
Mix or air stirring,
Step S4, processing: the copper coin after plating copper facing is carried out polish, removes surface oxide layer and rejected region, ultrasound wave
Detect a flaw qualified, surface roughness < 3.2 μm of copper coin after machining；
Step S5, galvanization coating: the copper coin after machining is carried out galvanization coating operation；
Step S6, plating post-equalization: the coating copper coin after plating is corrected, it is ensured that the flatness of copper coin is not more than 0.08mm/
m；
Step S7, secondary operations: require copper coin is carried out whole processing according to design, complete the reparation to copper coin.
In the present invention, in step S3, the composition of described electroplate liquid is preferably:
Copper sulfate: 200 ~ 250g/L, sulphuric acid: 70 ~ 80g/L, chloride ion: 50 ~ 80mL/L, 2-mercaptobenzimidazole: 0.005 ~
0.012g/L, ethylene thiourea: 0.001 ~ 0.008g/L, sodium polydithio-dipropyl sulfonate: 0.12 ~ 0.20g/L.In the present invention, chlorine
Ion is provided by hydrochloric acid, and the addition of chloride ion addition correspondence hydrochloric acid, unit mL/L represents.
In the present invention, in step S3, the described phosphorous 0.05 ~ 0.07wt% in phosphor-copper angle.
In the present invention, in step S3, the phosphorous 0.03 ~ 0.05wt% of described phosphorous copper balls.
In the present invention, in step S3, the copper facing thickness on copper plate of crystallizer surface is 0.5 ~ 15mm, the most optional
Selecting copper facing thickness is 0.5mm, 1.0mm, 5mm, 10mm, 12mm, 15mm etc.；Compared with prior art, the copper facing thickness of the present invention
Significantly improve, the thickest can reach 15 millimeters,
When the present invention provides that in step S5, galvanization coating is copper coating, the electroplate liquid composition used and process control condition are such as
Under: nickel sulfamic acid: 450 ~ 600g/L；Sulfamic acid cobalt: 7 ~ 12g/L；Boric acid: 30 ~ 40g/L；Nickel dichloride.: 10 ~ 12g/L；Second
Base sodium hexy1 sulfate: 0.002 ~ 0.08mL/L；Benzyl-thiazolinyl pyridinium inner salt: 40 ~ 50mL/L；Electric current density: 2 ~ 8A/dm2；PH:
3.0-4.5；Stirring condition: circulating pump stirring or compressed air stirring；After thickness of coating reaches technological requirement, i.e. stop plating
Operation.Concrete control parameter is as shown in table 3.
Seven group embodiments are set forth below, and the present invention is described in further detail.
In seven groups of embodiments, in copper facing operation, the composition of electroplate liquid is as shown in table 1 below.
The composition (one) of electroplate liquid in table 1 copper facing operation
| Embodiment sequence number | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Copper sulfate/g/L | 150 | 180 | 200 | 210 | 230 | 250 | 280 |
| Sulphuric acid/g/L | 50 | 62 | 70 | 75 | 80 | 93 | 100 |
| Chloride ion mL/L | 10 | 35 | 50 | 65 | 80 | 105 | 120 |
| 2-mercaptobenzimidazole/g/L | 0.0003 | 0.0008 | 0.0012 | 0.005 | 0.01 | 0.012 | 0.015 |
| Ethylene thiourea/g/L | 0.0002 | 0.001 | 0.0015 | 0.003 | 0.005 | 0.008 | 0.01 |
| Sodium polydithio-dipropyl sulfonate/g/L | 0.005 | 0.012 | 0.075 | 0.12 | 0.18 | 0.24 | 0.3 |
In seven groups of embodiments, in copper facing operation, the process control condition of electroplate liquid is as shown in table 2 below.
The process control condition of electroplate liquid in table 2 copper facing operation
| Embodiment sequence number | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Temperature/DEG C | 10~12 | 13~15 | 18~20 | 23~25 | 28~30 | 32~35 | 38~40 |
| Cathode-current density/ A/dm2 | 1 | 2.5 | 4 | 5.5 | 7 | 8.5 | 10 |
| Anode | Phosphor-copper angle (0.05wt%P) | Phosphor-copper angle (0.06wt%P) | Phosphor-copper angle (0.07wt%P) | Phosphorous copper balls (0.03wt%P) | Phosphorous copper balls (0.03wt%P) | Phosphorous copper balls (0.04wt%P) | Phosphorous copper balls (0.05wt% P) |
| Stirring condition | Circulating pump stirs | Air stirring | Air stirring | Air stirring | Air stirring | Air stirring | Air stirring |
Composition and the control condition of the galvanization coating technique that above-mentioned seven groups of experiments are used are as follows.
Electroplate liquid composition and process control condition in table 3 galvanization coating operation
| Embodiment sequence number | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Nickel sulfamic acid/g/L | 450 | 480 | 500 | 510 | 520 | 550 | 600 |
| Sulfamic acid cobalt/g/L | 7 | 7.5 | 8.0 | 8.5 | 8.5 | 10 | 12 |
| Boric acid/g/L | 30 | 30.5 | 31 | 31.5 | 32 | 35 | 40 |
| Nickel dichloride ./g/L | 10 | 10 | 10 | 10 | 10 | 12 | 12 |
| Ethylhexyl sulfate/mL/L | 0.002 | 0.005 | 0.008 | 0.01 | 0.01 | 0.05 | 0.08 |
| Benzyl-thiazolinyl pyridinium inner salt/mL/L | 40 | 42 | 45 | 45 | 45 | 48 | 50 |
| Electric current density/A/dm2 | 2 | 3 | 4 | 4 | 4 | 6 | 8 |
| PH | 3.0 | 3.0 | 3.1 | 3.2 | 3.2 | 4 | 4.5 |
| Stirring condition | Circulating pump stirs | Circulating pump stirs | Circulating pump stirs | Compressed air stirs | Compressed air stirs | Compressed air stirs | Compressed air stirs |
Based on above-mentioned experiment, the present invention also explores addO-on therapy sulfosalicylic acid in the electroplate liquid of copper facing operation forms, and adds
Dosage is 0.0006 ~ 0.0018g/L, has done 4 groups of experiments for adding sulfosalicylic acid, has formed as shown in table 4 below.
The composition (two) of electroplate liquid in table 4 copper facing operation
| Embodiment sequence number | 7 | 8 | 9 | 10 |
| Copper sulfate/g/L | 200 | 210 | 230 | 250 |
| Sulphuric acid/g/L | 70 | 75 | 80 | 80 |
| Chloride ion mL/L | 50 | 65 | 80 | 80 |
| 2-mercaptobenzimidazole/g/L | 0.005 | 0.007 | 0.010 | 0.012 |
| Ethylene thiourea/g/L | 0.001 | 0.003 | 0.005 | 0.008 |
| Sodium polydithio-dipropyl sulfonate/g/L | 0.12 | 0.15 | 0.18 | 0.20 |
| Sulfosalicylic acid/g/L | 0.0006 | 0.0010 | 0.0015 | 0.0018 |
| Process control condition | Refering to embodiment 4 | Refering to embodiment 4 | Refering to embodiment 5 | Refering to embodiment 5 |
The invention is intended to preferably illustrate, the significance of progress of the present invention is described, enumerate following representative contrast
Example 1 ~ 3.
Comparative example 1
This comparative example carries out coating process for new continuous casting crystallizer copper plate, i.e. without it is carried out step S1 of the present invention ~ step
The process of rapid S3, specifically includes following steps:
1) Pre-treatment before plating: continuous casting crystallizer copper plate surface is carried out conventional Pre-treatment before plating, including machine tooling, organic solvent
Cleaning, alkali degreasing, electrolytic degreasing, machinery sandblasting wharf's pavement quality and sonic cleaning；
2) galvanization coating: the copper coin after machining is carried out galvanization coating operation is identical with step S5 of the embodiment of the present invention 5；
3) plating post-equalization: the coating copper coin after plating is corrected, it is ensured that the flatness of copper coin is not more than 0.08mm/m；
4) require copper coin to be processed and cleans according to design.
Comparative example 2
The restorative procedure of this comparative example continuous casting crystallizer copper plate, substantially the same manner as Example 9, except that: in copper facing operation
Consisting of of electroplate liquid:
Copper sulfate: 230g/L, sulphuric acid: 80g/L, chloride ion: 70mL/L, ethylene thiourea: 0.005g/L, polydithio-dipropyl sulfonic acid
Sodium: 0.10g/L, sulfosalicylic acid: 0.0020g/L.
Comparative example 3
The restorative procedure of this comparative example continuous casting crystallizer copper plate, substantially the same manner as Example 9, except that: in copper facing operation
Consisting of of electroplate liquid:
Copper sulfate: 230g/L, sulphuric acid: 80g/L, chloride ion: 70mL/L, ethylene thiourea: 0.005g/L, polydithio-dipropyl sulfonic acid
Sodium: 0.10g/L, sulfosalicylic acid: 0.0005g/L.
To embodiment 3 ~ 6,8 ~ 9 and hardness, porosity, decay resistance and the knot of comparative example 1 ~ 3 gained copper plate of crystallizer
Close intensity etc. be measured or evaluate, as shown in table 5 below.
Table 5 testing result
| Embodiment sequence number/detection project | 3 | 4 | 5 | 6 | 8 | 9 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Hardness/HV | 731 | 805 | 859 | 848 | 862 | 892 | 912 | 465 | 432 |
| Porosity/% | 0.03 | 0.02 | 0.01 | 0.02 | 0.01 | 0.01 | 0.02 | 0.08 | 0.12 |
| Rate of corrosion/mg/m in 10%HCL2•h | 2.52 | 2.38 | 2.25 | 2.32 | 2.21 | 2.05 | 2.25 | 3.65 | 4.00 |
| 10%H2SO4Middle rate of corrosion/mg/m2•h | 2.73 | 2.62 | 2.43 | 2.59 | 2.50 | 2.31 | 2.45 | 5.01 | 5.34 |
| Bond strength/N/mm2 | 421 | 432 | 448 | 432 | 452 | 468 | 470 | 234 | 262 |
| Steel-passing amount (low middle pulling rate)/ten thousand tons | 12 | 13 | 15 | 14 | 15 | 17 | 18 | 9 | 8 |
By above-mentioned detection tables of data it can be seen that after 1. new copper plate of crystallizer is carried out conventional galvanization coating, its hardness, hole
Rate, decay resistance and bond strength etc. are more or less the same, especially for using the crystallizer to be scrapped after the inventive method reparation
It is that the properties of embodiment 9 maintains an equal level with comparative example 1 substantially, has unexpected technique effect.2. in comparative example 2
Without adding 2-mercaptobenzimidazole, the content keeping copper sulfate, sulphuric acid, chloride ion and ethylene thiourea is constant, adjusts poly-two sulfur two
Propane sulfonic acid sodium and the content of sulfosalicylic acid, the sodium polydithio-dipropyl sulfonate content after combination is 0.10g/L, sulfosalisylic
Acid is 0.0020g/L, controls technique constant, and the properties of the copper plate of crystallizer after using comparative example 2 restorative procedure to repair is equal
Substantially being inferior to restorative procedure of the present invention, illustrate that the coordination collocation property of copper-plating technique of the present invention is more excellent, effect is more prominent.3. comparative example
The content of sulfosalicylic acid is lowered by 3, is set to 0.0005g/L, and the copper plate of crystallizer after using the method to repair is except knot
Outside conjunction intensity slightly improves, remaining performance is the most substantially inferior to comparative example 2.Have between the component of this explanation copper-plating technique of the present invention
Mutually synergism, when arranging in pairs or groups reasonable, effect doubles, contrary then can not get the result wanted, and even differs greatly.4. than
The relatively embodiment of the present invention 3 ~ 6 acquired results, it can be clearly seen that, the properties of embodiment 5 is intended to be substantially better than embodiment 3,
This explanation is in the rational range of choice, and component and technique are also required to reasonably coordinate competence exertion to go out more preferable effect.
5. embodiment 9 is repaired the properties of gained copper plate of crystallizer and is substantially better than embodiment 5.From the point of view of acid copper-plating mechanistic point,
The copper plating solution being probably interpolation sulfosalicylic acid makes copper bivalent ions step-by-step reduction speed more coordinate, and balance is more
Good, and then affect its copper facing effect so that the copper plate of crystallizer properties repaired is the most excellent, basically reaches comparative example 1
Effect.
Production practices
4 high casting speed continuous casting machines of certain steel mill, ladle 150t, size of plate blank 1650 × 240mm, design pulling rate 1.5 ~ 2.0m/min,
Using the continuous casting crystallizer copper plate of comparative example 1, the wear extent of copper coin is 0.20mm, and once drawing steel amount is 901 stoves；Use embodiment
The continuous casting crystallizer copper plate of 5, the wear extent of copper coin is 0.25mm, and once drawing steel amount is 840 stoves；Continuous casting crystallizer copper plate is replaced
After continuous casting crystallizer copper plate for the embodiment of the present invention 9, the wear extent of copper plate of crystallizer reduces to 0.18mm, and one time steel transportation amount improves
To for 895 stoves.
Production practices show, use restorative procedure of the present invention repair after copper plate of crystallizer service life can close to or
Reach the service life of new copper plate of crystallizer, and wear extent is little.
By above-mentioned experiment and practice have shown that, by this restorative procedure, the service life of copper plate of crystallizer to be scrapped is prolonged
Long, and sustainable use can be realized according to this reparation, do not scrap, and without reparation of rolling off the production line, improve operation effect
Rate, reduces the maintenance cost of crystallizer, as a example by dragon becomes: produces 15000000 tons of steel per year and about needs 100 set copper plate of crystallizer, and a noose
The price of brilliant device copper coin just can save 700 ~ 12,000,000 yuan in 7 ~ 120,000, one years.If the sustainable profit of a set of copper plate of crystallizer
With, then the saving of cost is considerable.
Claims (6)
1. the restorative procedure of a continuous casting crystallizer copper plate, it is characterised in that comprise the following steps:
Step S1: the copper plate of crystallizer being intended to scrap is corrected, it is ensured that copper plate of crystallizer flatness before processing is not more than
0.2mm/m；
Step S2: be removed processing to the coating on copper plate of crystallizer surface to be scrapped；
Step S3: the copper plate of crystallizer surface to be scrapped is implemented plating copper facing operation,
Consisting of of the electroplate liquid used:
Copper sulfate: 150 ~ 280g/L, sulphuric acid: 50 ~ 100g/L, chloride ion: 10 ~ 120mL/L, 2-mercaptobenzimidazole: 0.0003 ~
0.015g/L, ethylene thiourea: 0.0002 ~ 0.01g/L, sodium polydithio-dipropyl sulfonate: 0.005 ~ 0.3g/L,
The process conditions of copper facing operation are:
Temperature: 10 ~ 40 DEG C, cathode-current density: 1 ~ 10A/dm2, anode: phosphor-copper angle or phosphorous copper balls, stirring condition: circulating pump stirs
Mix or air stirring,
Step S4: the copper coin after plating copper facing being carried out polish, removes surface oxide layer and rejected region, ultrasonic examination is closed
Lattice, surface roughness < 3.2 μm of copper coin after machining；
Step S5: the copper coin after machining is carried out galvanization coating operation；
Step S6: the coating copper coin after plating is corrected, it is ensured that the flatness of copper coin is not more than 0.08mm/m；
Step S7: require copper coin is carried out whole processing according to design, complete the reparation to copper coin.
2. the restorative procedure of continuous casting crystallizer copper plate as claimed in claim 1, it is characterised in that: in step S3, described electroplate liquid
Consist of:
Copper sulfate: 200 ~ 250g/L, sulphuric acid: 70 ~ 80g/L, chloride ion: 50 ~ 80mL/L, 2-mercaptobenzimidazole: 0.005 ~
0.012g/L, ethylene thiourea: 0.001 ~ 0.008g/L, sodium polydithio-dipropyl sulfonate: 0.12 ~ 0.20g/L.
3. the restorative procedure of continuous casting crystallizer copper plate as claimed in claim 1, it is characterised in that: in step S3, described phosphor-copper angle
Phosphorous 0.05 ~ 0.07wt%.
4. the restorative procedure of continuous casting crystallizer copper plate as claimed in claim 1, it is characterised in that: in step S3, described phosphorous copper balls
Phosphorous 0.03 ~ 0.05wt%.
5. the restorative procedure of continuous casting crystallizer copper plate as claimed in claim 1, it is characterised in that: in step S3, copper plate of crystallizer
The copper facing thickness on surface is 0.5 ~ 15mm.
6. the restorative procedure of continuous casting crystallizer copper plate as claimed in claim 1, it is characterised in that: in step S5, described plating plating
The electroplate liquid that layer operation is used forms and process control condition is:
Nickel sulfamic acid: 450 ~ 600g/L；Sulfamic acid cobalt: 7 ~ 12g/L；Boric acid: 30 ~ 40g/L；Nickel dichloride.: 10 ~ 12g/L；Second
Base sodium hexy1 sulfate: 0.002 ~ 0.08mL/L；Benzyl-thiazolinyl pyridinium inner salt: 40 ~ 50mL/L；
Electric current density: 2 ~ 8A/dm2；PH:3.0-4.5；Stirring condition: circulating pump stirring or compressed air stirring；
After thickness of coating reaches technological requirement, i.e. stop electroplating activity.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637312A (en) * | 2017-03-07 | 2017-05-10 | 龙游运申制版有限公司 | Copper plating solution for plate roller and preparation method of copper plating solution |
| CN108856660A (en) * | 2018-06-29 | 2018-11-23 | 振石集团东方特钢有限公司 | A kind of application method of crystallizer copper plate of plate blank continuous casting machine |
| CN109355684A (en) * | 2018-11-28 | 2019-02-19 | 德阳深捷科技有限公司 | A kind of increasing material manufacturing structure and increasing material manufacturing method and apparatus applied to continuous cast mold |
| CN109550910A (en) * | 2017-09-25 | 2019-04-02 | 上海宝钢工业技术服务有限公司 | The restorative procedure of chamber crystallizer narrow-surface copper |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063249A (en) * | 1991-06-27 | 1992-08-05 | 孙沛岩 | A kind of regeneration new process of crystallizer |
| RU2202440C2 (en) * | 2000-11-21 | 2003-04-20 | Открытое акционерное общество "Северсталь" | Method for repairing narrow walls of mold of machine for continuous steel casting |
| CN101724874A (en) * | 2008-10-17 | 2010-06-09 | 上海宝钢设备检修有限公司 | Surface repairing method for thin-strip continuous casting crystallizing roller or casting blank continuous casting crystallizer |
| KR20110065964A (en) * | 2009-12-10 | 2011-06-16 | 주식회사 포스코 | Method for repairing of cooling roll |
| CN103320820A (en) * | 2013-06-18 | 2013-09-25 | 河南江河机械有限责任公司 | Acid bright copper-plating electroplating process |
| CN103895280A (en) * | 2013-11-21 | 2014-07-02 | 青岛云路新能源科技有限公司 | Repairing composite layer of amorphous/nanocrystalline cooling roller and preparation method of repairing composite layer |
-
2016
- 2016-05-19 CN CN201610333391.8A patent/CN105921706B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063249A (en) * | 1991-06-27 | 1992-08-05 | 孙沛岩 | A kind of regeneration new process of crystallizer |
| RU2202440C2 (en) * | 2000-11-21 | 2003-04-20 | Открытое акционерное общество "Северсталь" | Method for repairing narrow walls of mold of machine for continuous steel casting |
| CN101724874A (en) * | 2008-10-17 | 2010-06-09 | 上海宝钢设备检修有限公司 | Surface repairing method for thin-strip continuous casting crystallizing roller or casting blank continuous casting crystallizer |
| KR20110065964A (en) * | 2009-12-10 | 2011-06-16 | 주식회사 포스코 | Method for repairing of cooling roll |
| CN103320820A (en) * | 2013-06-18 | 2013-09-25 | 河南江河机械有限责任公司 | Acid bright copper-plating electroplating process |
| CN103895280A (en) * | 2013-11-21 | 2014-07-02 | 青岛云路新能源科技有限公司 | Repairing composite layer of amorphous/nanocrystalline cooling roller and preparation method of repairing composite layer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637312A (en) * | 2017-03-07 | 2017-05-10 | 龙游运申制版有限公司 | Copper plating solution for plate roller and preparation method of copper plating solution |
| CN109550910A (en) * | 2017-09-25 | 2019-04-02 | 上海宝钢工业技术服务有限公司 | The restorative procedure of chamber crystallizer narrow-surface copper |
| CN109550910B (en) * | 2017-09-25 | 2021-12-28 | 上海宝钢工业技术服务有限公司 | Repair method for narrow-face copper plate of chamfering crystallizer |
| CN108856660A (en) * | 2018-06-29 | 2018-11-23 | 振石集团东方特钢有限公司 | A kind of application method of crystallizer copper plate of plate blank continuous casting machine |
| CN109355684A (en) * | 2018-11-28 | 2019-02-19 | 德阳深捷科技有限公司 | A kind of increasing material manufacturing structure and increasing material manufacturing method and apparatus applied to continuous cast mold |
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