CN105177656B - A kind of elemental nickel transition zone of crystallizer copper pipe electrodeposited chromium - Google Patents
A kind of elemental nickel transition zone of crystallizer copper pipe electrodeposited chromium Download PDFInfo
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- CN105177656B CN105177656B CN201510676425.9A CN201510676425A CN105177656B CN 105177656 B CN105177656 B CN 105177656B CN 201510676425 A CN201510676425 A CN 201510676425A CN 105177656 B CN105177656 B CN 105177656B
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- copper pipe
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Abstract
The invention discloses a kind of elemental nickel transition zone of crystallizer copper pipe electrodeposited chromium, the elemental nickel transition zone is between crystallizer copper pipe and electrodeposited chromium layers, about 34 μm of thickness of coating, the nickel chromium triangle metallurgical bonding layer three-decker that ambrose alloy metallurgical bonding layer, pure-nickel-layer and the nickel that the transition zone includes being formed between nickel and copper pipe are formed with chromium；The transition zone by being plated on crystallizer copper pipe, it is described electroplate the solution composition that uses for：The 600g/L of nickel sulfamic acid 500, the 35g/L of nickel sulfate 25, the 65g/L of lauryl sodium sulfate 55；Electroplating technology is：PH4 6, about 45 55 DEG C of bath temperature, the 6.5A/dm of cathode-current density 4.52, the 20min of immersion plating time about 10.
Description
Technical field
The present invention relates to electroplating technology, more particularly to a kind of elemental nickel transition zone of crystallizer copper pipe electrodeposited chromium.
Background technology
Crystallizer is the important component of smeltery's conticaster, and crystallizer copper pipe is the important portion on crystallizer
Part.Because high-temperature molten steel is directly through crystallizer copper pipe, to make continuous casting work process stabilization, equipment and operating personnel's peace are ensured again
Entirely, it is desirable to which crystallizer copper pipe has good high temperature resistant, wear-resistant and decay resistance.By being produced in the chromium plating of copper pipe inwall
Go out the crystallizer copper pipe with hard chromium, because of the high temperature resistant for being greatly improved crystallizer copper pipe, wear-resistant and decay resistance,
And simple production process, efficiency high, cost are low, and obtain more universal application.But inwall is coated with the crystallizer copper of hard chrome
Pipe, easily generation coating comes off in continuous casting production process, so as to shorten the service life of crystallizer copper pipe.Its reason is copper-based
Physical Properties Difference is larger between body and hard chromium, and particularly their thermal coefficient of expansion and difference in hardness are larger, it is difficult to suitable
The temperature environment of continuous casting production process is answered to change.
CN1804144A discloses a kind of combination crystalline substance device copper pipe with transition chrome plating and hard chromium, and it includes base
Body copper pipe and the hard chromium for being placed in copper pipe inner surface, it is characterised in that be provided between copper pipe inwall and surface hard chromium
Chrome plating is crossed, the thermal coefficient of expansion of the transition chrome plating is 1.68 × 10-5/ DEG C to 0.84 × 10-5/ DEG C between, hardness exists
HV450 is between HV950.Although the problem of patent application has paid attention to plating exfoliation, it also uses appropriate settling mode,
The method for using chromium plating transition zone, but its transition zone is still chromium, and its still no fundamentally two kinds of solution chromium and copper are not
Spallation problems caused by same materials variances, therefore its using effect is not still very good.
CN1465753A also discloses that a kind of electroplating method for internal surface of crystallizer, and it uses nickel cobalt (alloy) as transition zone,
Although also solving the problems, such as the difference in material properties of chromium and copper, because it uses alloy layer, solution composition is complicated, plating
Technological requirement is high, and the alloying component of alloy layer not temperature, is not easy accurate correspondence control, therefore there is also coating to differ
Cause, it is unstable the defects of.
Also have in the prior art using nickel and report of other metal component alloys as transition zone, but with above-mentioned patent class
Seemingly, the complicated alloy electroplating bath of configuration is required to, electroplating technology control requires high, and coating is unstable, inconsistent.In the prior art
There is not yet only with report of the nickel as transition zone.
The content of the invention
It is an object of the invention to propose a kind of elemental nickel transition zone of crystallizer copper pipe electrodeposited chromium.Using the elemental nickel mistake
Layer is crossed, can realize that the adhesion of coating and matrix is good, so as to fundamentally solve chromium with being peeled off caused by copper product difference
Problem.
To use following technical scheme up to this purpose, the present invention：
A kind of elemental nickel transition zone of crystallizer copper pipe electrodeposited chromium, the elemental nickel transition zone are located at crystallizer copper pipe and electricity
Between chromium coating, about 3-4 μm of thickness of coating, the transition zone includes ambrose alloy metallurgical bonding layer, the pure nickel formed between nickel and copper pipe
The nickel chromium triangle metallurgical bonding layer three-decker that layer and nickel are formed with chromium；The transition zone by being plated on crystallizer copper pipe,
It is described electroplate the solution composition that uses for：Nickel sulfamic acid 500-600g/L, nickel sulfate 25-35g/L, lauryl sodium sulfate
55-65g/L；Electroplating technology is：PH4-6, about 45-55 DEG C of bath temperature, cathode-current density 4.5-6.5A/dm2, the immersion plating time
About 10-20min.
The present invention, as transition zone, because elemental nickel does not form alloy with other elements, more holds only with elemental nickel
Nickel and copper pipe and follow-up chromium coating after plating is easily caused to form the metallurgical transition zone that alloy is combined respectively, i.e., in copper pipe and nickel
Between there is cupro-nickel binder course, and there is the binder course of nickel nichrome between nickel and follow-up chromium coating, substantially in most
The copper of layer has copper, corronil, nickel, nichrome, chromium coating five-layer structure to outermost chromium, so as to realize thermal expansion system
Several perfect transitions.
It is 3-4 μm that the present invention, which controls transition region thickness, will cause transition effect unobvious less than 3 microns, and particularly can not
Realize and form perfect transition layer structure with copper and subsequent plating layer, and higher than 4 μm, first, causing efficiency low, cost is high, more attaches most importance to
What is wanted is that by blocked up due to transition zone thermal coefficient of expansion can not be made to realize that copper to the continuous transition of subsequent plating layer, is unfavorable on the contrary
Antistrip performance.
Above-mentioned plating elemental nickel transition zone can be as the transition zone of other follow-up electrodeposited coatings in addition to electrodeposited chromium, such as follow-up cobalt
Alloy, tungsten alloy etc..
A kind of follow-up chromium coating of citing but not limited to this can use following component and technique：The solution composition of chromium coating
For：Chromic anhydride 140-150g/l, sulfuric acid 1.0-1.2g/l, chromium sulfate 5-7g/l, formic acid 3-5g/l, sodium sulphate 6-8g/l；Electrodeposited chromium
Layer technique be：PH3.5-4, it is 35-45 DEG C in temperature, current density 44-48A/dm2, electroplating time 30-40min.
The beneficial effects of the invention are as follows：
1. and compare through actual use, the transition zone system with not using transition zone or use chromium transition zone or use nickel alloy
Standby crystallizer copper pipe compares, and service life can extend more than 50%.
2. the nickel simple substance transition zone of the present invention, creative employs organic nickel salt nickel sulfamic acid and inorganic nickel sulfuric acid
The combination of nickel, and the proportioning of the two is determined, the ratio of organic nickel salt will be significantly higher than inorganic nickel, and experiment shows, amino sulphur
Sour nickel is higher than 600g/L, or nickel sulfate is higher than 35g/L, and the adhesion for causing transition zone and subsequent plating layer is bad, and amino
Nickel sulphonic acid is less than 500g/L, or nickel sulfate is less than 25g/L, and the combination effect for causing transition zone and matrix is bad, transition zone
It is not fine and close.
3. transition zone solution composition of the present invention is simple, only it is made up of three kinds of components, adding other components will cause cost to increase
Add, performance does not significantly improve but, and component is more complicated, and uncontrollable factor is more, more causes transition zone performance unstable.And this
Three kinds of components, lacking any one will cause coating performance drastically to deteriorate, do not reach as transition zone requirement and with its effect,
Coating even can not be formed.Therefore, present invention process plating solution is prepared simple, and control is easy, easy to operate.With electroplating nickel alloy mistake
The technique for crossing layer is compared, and cost reduces about 40%.
Embodiment
Embodiment one
A kind of elemental nickel transition zone of crystallizer copper pipe electrodeposited chromium, the elemental nickel transition zone are located at crystallizer copper pipe and electricity
Between chromium coating, about 3 μm of thickness of coating, the transition zone includes ambrose alloy metallurgical bonding layer, the pure-nickel-layer formed between nickel and copper pipe
And the nickel chromium triangle metallurgical bonding layer three-decker that nickel is formed with chromium；The transition zone is by being plated on crystallizer copper pipe, institute
State the solution composition that uses of plating for：Nickel sulfamic acid 500g/L, nickel sulfate 35g/L, lauryl sodium sulfate 55g/L；Plating
Technique is：PH4,55 DEG C of bath temperature, cathode-current density 4.5A/dm2, immersion plating time 20min.
The component that uses of subsequent plating layer and technique coordinated with the transition zone for：The solution composition of chromium coating is：Chromic anhydride
140g/l, sulfuric acid 1.2g/l, chromium sulfate 5g/l, formic acid 5g/l, sodium sulphate 6g/l；The technique of electrodeposited chromium layers is：PH3.5, in temperature
Spend for 45 DEG C, current density 44A/dm2, electroplating time 40min.
Embodiment two
A kind of elemental nickel transition zone of crystallizer copper pipe electrodeposited chromium, the elemental nickel transition zone are located at crystallizer copper pipe and electricity
Between chromium coating, about 4 μm of thickness of coating, the transition zone includes ambrose alloy metallurgical bonding layer, the pure-nickel-layer formed between nickel and copper pipe
And the nickel chromium triangle metallurgical bonding layer three-decker that nickel is formed with chromium；The transition zone is by being plated on crystallizer copper pipe, institute
State the solution composition that uses of plating for：Nickel sulfamic acid 600g/L, nickel sulfate 25g/L, lauryl sodium sulfate 65g/L；Plating
Technique is：PH6,45 DEG C of bath temperature, cathode-current density 6.5A/dm2, immersion plating time 10min.
The component that uses of subsequent plating layer and technique coordinated with the transition zone for：The solution composition of chromium coating is：Chromic anhydride
150g/l, sulfuric acid 1.0g/l, chromium sulfate 7g/l, formic acid 3g/l, sodium sulphate 8g/l；The technique of electrodeposited chromium layers is：PH4, in temperature
For 35 DEG C, current density 48A/dm2, electroplating time 30min.
Embodiment three
A kind of elemental nickel transition zone of crystallizer copper pipe electrodeposited chromium, the elemental nickel transition zone are located at crystallizer copper pipe and electricity
Between chromium coating, about 3.5 μm of thickness of coating, the transition zone includes ambrose alloy metallurgical bonding layer, the pure nickel formed between nickel and copper pipe
The nickel chromium triangle metallurgical bonding layer three-decker that layer and nickel are formed with chromium；The transition zone by being plated on crystallizer copper pipe,
It is described electroplate the solution composition that uses for：Nickel sulfamic acid 550g/L, nickel sulfate 30g/L, lauryl sodium sulfate 60g/L；Electricity
Depositing process is：PH5,50 DEG C of bath temperature, cathode-current density 5A/dm2, immersion plating time 15min.
The component that uses of subsequent plating layer and technique coordinated with the transition zone for：The solution composition of chromium coating is：Chromic anhydride
145g/l, sulfuric acid 1.1g/l, chromium sulfate 6g/l, formic acid 4g/l, sodium sulphate 7g/l；The technique of electrodeposited chromium layers is：PH4, in temperature
For 40 DEG C, current density 46A/dm2, electroplating time 35min.
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. elemental nickel transition zone of crystallizer copper pipe electrodeposited chromium, it is characterised in that：The elemental nickel transition zone is positioned at crystallization Between device copper pipe and electrodeposited chromium layers, 3.5 μm of thickness of coating, the transition zone includes the ambrose alloy metallurgical binding formed between nickel and copper pipe The nickel chromium triangle metallurgical bonding layer three-decker that layer, pure-nickel-layer and nickel are formed with chromium；The transition zone is by being plated on crystallizer On copper pipe, it is described electroplate the solution composition that uses for：Nickel sulfamic acid 550g/L, nickel sulfate 30g/L, lauryl sodium sulfate 60g/L；Electroplating technology is：PH=5,50 DEG C of bath temperature, cathode-current density 5A/dm2, immersion plating time 15min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0282759A1 (en) * | 1987-03-18 | 1988-09-21 | DANIELI & C. OFFICINE MECCANICHE S.p.A. | Method for the rehabilitation of a crystallizer of a continuous casting ingot mould |
| CN1465753A (en) * | 2002-06-25 | 2004-01-07 | 首钢总公司 | Electroplating method for internal surface of crystallizer |
| CN104451789A (en) * | 2014-12-30 | 2015-03-25 | 广西师范大学 | Plating solution for electroplating nickel on aluminum-based carbon nanotube |
| CN104499032A (en) * | 2014-12-30 | 2015-04-08 | 广西师范大学 | Plating solution for electroplating Ni/graphene compound heat conduction film on surface of substrate |
| CN105154958A (en) * | 2015-09-22 | 2015-12-16 | 郑州磨料磨具磨削研究所有限公司 | Method for preparing electroplated diamond grinding wheel with orderly arranged abrasive materials |
-
2015
- 2015-10-19 CN CN201510676425.9A patent/CN105177656B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0282759A1 (en) * | 1987-03-18 | 1988-09-21 | DANIELI & C. OFFICINE MECCANICHE S.p.A. | Method for the rehabilitation of a crystallizer of a continuous casting ingot mould |
| CN1465753A (en) * | 2002-06-25 | 2004-01-07 | 首钢总公司 | Electroplating method for internal surface of crystallizer |
| CN104451789A (en) * | 2014-12-30 | 2015-03-25 | 广西师范大学 | Plating solution for electroplating nickel on aluminum-based carbon nanotube |
| CN104499032A (en) * | 2014-12-30 | 2015-04-08 | 广西师范大学 | Plating solution for electroplating Ni/graphene compound heat conduction film on surface of substrate |
| CN105154958A (en) * | 2015-09-22 | 2015-12-16 | 郑州磨料磨具磨削研究所有限公司 | Method for preparing electroplated diamond grinding wheel with orderly arranged abrasive materials |
Non-Patent Citations (1)
| Title |
|---|
| "宝钢铬锆铜结晶器铜板的研究开发";王隆寿;《宝钢技术》;20000430(第2000-2期);第55-59页 * |
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Inventor after: Wu Weijia Inventor before: Jiang Shaoqun |
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Effective date of registration: 20180208 Address after: No. 506-1, Xin Qiong village, Tai Po Town, Yongchun County, Quanzhou, Fujian Province Applicant after: Yongchun County, the village of elegant home Address before: 315113 Zhejiang city of Ningbo province Yinzhou District east Wu Dong Wuzhong Road No. 225 Applicant before: Jiang Shaoqun |
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Effective date of registration: 20190917 Address after: 538000 Optimus Sky, 5000 Qisha Avenue, Bus Town, Port District, Fangchenggang City, Guangxi Zhuang Autonomous Region. No. 10, 1-2 floors, 3 buildings in Haiao City Patentee after: Guangxi Shengchang Logistics Co., Ltd. Address before: 362600 No. 506-1 Xinqiong Village, Dapu Town, Yongchun County, Quanzhou City, Fujian Province Patentee before: Yongchun County, the village of elegant home |