CN1796609A - Technique for plating alnico in copper plate type of crystallizer of conticaster - Google Patents
Technique for plating alnico in copper plate type of crystallizer of conticaster Download PDFInfo
- Publication number
- CN1796609A CN1796609A CN 200410061436 CN200410061436A CN1796609A CN 1796609 A CN1796609 A CN 1796609A CN 200410061436 CN200410061436 CN 200410061436 CN 200410061436 A CN200410061436 A CN 200410061436A CN 1796609 A CN1796609 A CN 1796609A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- nickel
- electroplating
- ion
- slot type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000007747 plating Methods 0.000 title claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 11
- 229910052802 copper Inorganic materials 0.000 title claims description 11
- 239000010949 copper Substances 0.000 title claims description 11
- 229910000828 alnico Inorganic materials 0.000 title 1
- 238000009713 electroplating Methods 0.000 claims abstract description 23
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 8
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 6
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 3
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 229910017709 Ni Co Inorganic materials 0.000 claims description 6
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 6
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- LFLCNBLTOXIVOQ-UHFFFAOYSA-N hydron;octan-3-yl sulfate Chemical class CCCCCC(CC)OS(O)(=O)=O LFLCNBLTOXIVOQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 9
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- RZBAOHIEEDMCNK-UHFFFAOYSA-J S(N)([O-])(=O)=O.[Co+2].[Ni+2].S(N)([O-])(=O)=O.S(N)([O-])(=O)=O.S(N)([O-])(=O)=O Chemical compound S(N)([O-])(=O)=O.[Co+2].[Ni+2].S(N)([O-])(=O)=O.S(N)([O-])(=O)=O.S(N)([O-])(=O)=O RZBAOHIEEDMCNK-UHFFFAOYSA-J 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical compound [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
This invention provides a continuous caster copperplate slot electroplating of nickel-cobalt alloys, with the main characteristic of a slot electroplating facility. In this technique, amino-sulfonate system is adopted as electroplating fluid and nickel is adopted as anode. Nickel ion is supplemented in an anode dissolution manner, and cobalt ion is supplemented in a cobalt amino-sulfonate continuous addition manner. The current density is 0.5~25A/sq dm, the temperature is 45~60 deg.C and the pH value is 4.0~5.5. Compared to current technologies, this invention has the advantages of large universality of the facility, wide application, high efficiency, low internal stress of coatings and high toughness. It furthest reduces the generation of thermal cracks and allows a current density of as high as 25A/sq dm. Besides, the cobalt content can be variated at different sites and thickness of the copperplate in a range of 5~80% according to the requirements.
Description
Technical field
The invention belongs to field of metal surface treatment technology, be specifically related to a kind of slot type that is used for continuous caster crystallizer copperplate and electroplate sulfamate nickel cobalt (alloy) technology.
Background technology
In the prior art, the form of continuous caster crystallizer copperplate electroplating surface roughly has three kinds, and has following deficiency:
1, the copper plate electroplating layer adopts the Rhometal layer, and this technology is electroplated system ferrous oxidation is easily taken place, and technology stability is poor, and the coating internal stress is big, easily produces thermal crack;
2, adopt the sulfate system nickel-cobalt alloy plating, the sulfate system current density upper limit is little, and production efficiency is low, and the coating internal stress is bigger.
3, the copper plate of crystallizer electroplating device adopts built-up type, and application surface is little, and is inapplicable for partial crystallization device copper coin.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art and provide that a kind of coating internal stress is low, toughness is high, can reduce the generation of thermal crack to greatest extent, the continuous caster crystallizer copperplate slot type Ni-Co alloy electroplating process of electroplating device highly versatile.
Technical program of the present invention lies in:
1, the copper plate electroplating layer is the nickel cobalt (alloy) layer, adopts sulfamate system plating solution Ni-Co alloy electroplating process, and wherein anode is a metallic nickel, and nickel ion adopts the mode of anode dissolution to replenish, and the mode that cobalt ion adopts the thionamic acid cobalt salt to add is continuously replenished;
2, the composition of electroplate liquid and processing condition are:
Nickel sulfamic acid (in nickel ion) 20~100g/L
Nickelous chloride 0.5~1g/L
Thionamic acid cobalt (in cobalt ion) 0.1~30g/L
Boric acid 25~45g/L
Wetting agent 0.05~0.20g/L
Current density 0.5~25A/dm
2
45~60 ℃ of temperature
pH 4.0~5.5
3, electroplating device is the slot type electroplating device.
The said wetting agent of the present invention is sodium lauryl sulphate salt or sodium 2-ethylhexyl sulfate salt, polyxyethylated alkylphenol sodium sulfate salt etc.
Compared with prior art, the present invention has the electroplating device highly versatile, application surface is wider, the coating internal stress is low, toughness is high, can reduce the generation of thermal crack to greatest extent, and the permission current density can be up to 25A/dm
2, high efficiency, its cobalt contents can be as required advantage such as changes at different sites, the different thickness of copper coin in 5%~80% scope.
Embodiment
Copper coin specification 850 * 400 * 70
Thickness of coating: electroplate 3mm, processing back 1.5mm.
Cobalt contents 15% in the coating.
Step:
1, removes machine oil on the copper coin with scrubbing powder, clean with gasoline or acetone again.
2, in the alkali groove through electrochemical deoiling, electrolytic degreasing.The alkali lye composition is:
Sodium hydroxide 35g/L
Yellow soda ash 30g/L
Tertiary sodium phosphate 30g/L
90 ℃ of working temperatures
5 minutes electrochemical deoiling time
30 minutes electrolytic degreasing time
Electrolytic current density 3A/dm
2
3, tape, assemble the protection negative electrode.
4, carry out electrolytic pickling activation 5~10 minutes, acid solution is 98%H
2SO
4200ml/l, current density is 5A/dm
2, workpiece is made anode, and stainless steel plate is made negative electrode.
5, the plating tank with 1500 * 1000 * 1000 specifications places on the working face, in groove, inject the sulfamate system plating solution 1200L that is fit to requirement, the interior titanium basket that is placed with the metallic nickel button is put into plating tank anode one end, connect heating, circulation filtering pipeline and power circuit.Being heated to solution temperature is 40~45 ℃, circulating filtration 5~30 minutes.
6, the copper coin after the pre-treatment is placed the plating tank cathode terminal, connect power supply, continue heated solution to temperature required, begin to electroplate, the composition of electroplate liquid and processing condition are:
Electroplate liquid connects following prescription and prepares with distilled water or deionized water:
Nickel sulfamic acid (in nickel ion) 60g/L
Nickelous chloride 1g/L
Thionamic acid cobalt (in cobalt ion) 3.0g/L
Boric acid 35g/L
Sodium lauryl sulphate 0.05g/L
Processing condition are during plating:
55~58 ℃ of temperature
pH 4.0
Current density 5A/dm
2
The solution stirring mode stirs with the liquor pump filtration cycle
In the galvanized process, cobalt ion replenishes according to the mode that analytical results adopts the thionamic acid cobalt liquor to add continuously; When reaching 2.5~3mm, the copper coin thickness of coating finishes to electroplate.
In electroplating process, the concentration of the cobalt ion in the cobalt preferential deposition ie in solution constantly reduces, in order to guarantee the consistence of cobalt contents in the coating, the thionamic acid cobalt liquor will join in the electroplate liquid continuously in galvanized process, and last till in the whole electroplating process, to before plating, analyze simultaneously, with the amount of determining in electroplate liquid, to add the cobalt metal ionic concentration in the electroplating solution, guarantee that in galvanized process, the content of thionamic acid cobalt liquor is not less than 2.5g/L in the electroplate liquid.
Claims (3)
1, a kind of continuous caster crystallizer copperplate slot type Ni-Co alloy electroplating process comprises and copper coin is carried out oil removing before electroplating that the electrolytic pickling pre-treatment is characterized in that: this process using slot type electroplating device; Adopt sulfamate system plating solution nickel-cobalt alloy plating, in electroplating technology, anode is a metallic nickel, and nickel ion adopts the anode dissolution mode to replenish, and the mode that cobalt ion adopts the thionamic acid cobalt salt to add is continuously replenished, and its current density is 0.5~25A/d m
2, temperature is 45~60 ℃, pH is 4.0~5.5.
2, continuous caster crystallizer copperplate slot type Ni-Co alloy electroplating process according to claim 1 is characterized in that: the consisting of of sulfamate system plating solution:
Nickel sulfamic acid (in nickel ion) 20~100g/L
Nickelous chloride 0.5~1g/L
Thionamic acid cobalt (in cobalt ion) 0.1~30g/L
Boric acid 25~45g/L
Wetting agent 0.05~0.20g/L
3, continuous caster crystallizer copperplate slot type Ni-Co alloy electroplating process according to claim 2 is characterized in that: said wetting agent is sodium lauryl sulphate salt or 2 one ethylhexyl sulfate salt, polyxyethylated alkylphenol sodium sulfate salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410061436 CN1796609A (en) | 2004-12-23 | 2004-12-23 | Technique for plating alnico in copper plate type of crystallizer of conticaster |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410061436 CN1796609A (en) | 2004-12-23 | 2004-12-23 | Technique for plating alnico in copper plate type of crystallizer of conticaster |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1796609A true CN1796609A (en) | 2006-07-05 |
Family
ID=36817922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410061436 Pending CN1796609A (en) | 2004-12-23 | 2004-12-23 | Technique for plating alnico in copper plate type of crystallizer of conticaster |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1796609A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776538A (en) * | 2012-08-01 | 2012-11-14 | 西峡龙成特种材料有限公司 | High-drawing speed continuous casting machine crystallizer copper plate electroplating process |
| CN104985147A (en) * | 2015-05-28 | 2015-10-21 | 西峡龙成特种材料有限公司 | High-casting-speed Ni-Co-Fe alloy clad layer continuous casted crystallizer copper board and preparation technology thereof |
| CN105239116A (en) * | 2015-10-28 | 2016-01-13 | 安徽恒源煤电股份有限公司 | Corrosion resistant composite electroplating liquid |
| CN105256341A (en) * | 2015-10-28 | 2016-01-20 | 安徽恒源煤电股份有限公司 | Electroplate liquid usable for scaffolds made of multiple materials |
| CN105256362A (en) * | 2015-10-10 | 2016-01-20 | 安徽长青电子机械(集团)有限公司 | Composite electroplating bath low in economic cost and high in binding force |
| CN105256340A (en) * | 2015-10-10 | 2016-01-20 | 安徽长青电子机械(集团)有限公司 | Oil-proof and waterproof composite electroplating bath and preparation method thereof |
| CN105256345A (en) * | 2015-10-10 | 2016-01-20 | 安徽长青电子机械(集团)有限公司 | Rustproof composite electroplating bath |
| CN105256361A (en) * | 2015-10-10 | 2016-01-20 | 安徽长青电子机械(集团)有限公司 | Nickel plated nanocomposite electroplating bath |
| CN105256363A (en) * | 2015-10-10 | 2016-01-20 | 安徽长青电子机械(集团)有限公司 | Composite electroplating bath containing nano-sized vanadium carbide |
| CN108315779A (en) * | 2018-04-19 | 2018-07-24 | 南雄市特能宝化学有限公司 | A kind of nickel-plating additive and electro-plating method |
| CN108315775A (en) * | 2018-04-19 | 2018-07-24 | 佛山市特能宝化学原料有限公司 | A kind of nickel plating brightener and electro-plating method |
| CN109628967A (en) * | 2019-01-07 | 2019-04-16 | 安徽马钢表面技术股份有限公司 | A kind of nickel cobalt (alloy) plating solution and its device for copper plate of crystallizer |
-
2004
- 2004-12-23 CN CN 200410061436 patent/CN1796609A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776538A (en) * | 2012-08-01 | 2012-11-14 | 西峡龙成特种材料有限公司 | High-drawing speed continuous casting machine crystallizer copper plate electroplating process |
| CN102776538B (en) * | 2012-08-01 | 2016-06-15 | 西峡龙成特种材料有限公司 | High casting speed continuous casting machine copper plate of crystallizer electroplating technology |
| CN104985147A (en) * | 2015-05-28 | 2015-10-21 | 西峡龙成特种材料有限公司 | High-casting-speed Ni-Co-Fe alloy clad layer continuous casted crystallizer copper board and preparation technology thereof |
| CN105256345A (en) * | 2015-10-10 | 2016-01-20 | 安徽长青电子机械(集团)有限公司 | Rustproof composite electroplating bath |
| CN105256362A (en) * | 2015-10-10 | 2016-01-20 | 安徽长青电子机械(集团)有限公司 | Composite electroplating bath low in economic cost and high in binding force |
| CN105256340A (en) * | 2015-10-10 | 2016-01-20 | 安徽长青电子机械(集团)有限公司 | Oil-proof and waterproof composite electroplating bath and preparation method thereof |
| CN105256361A (en) * | 2015-10-10 | 2016-01-20 | 安徽长青电子机械(集团)有限公司 | Nickel plated nanocomposite electroplating bath |
| CN105256363A (en) * | 2015-10-10 | 2016-01-20 | 安徽长青电子机械(集团)有限公司 | Composite electroplating bath containing nano-sized vanadium carbide |
| CN105256341A (en) * | 2015-10-28 | 2016-01-20 | 安徽恒源煤电股份有限公司 | Electroplate liquid usable for scaffolds made of multiple materials |
| CN105239116A (en) * | 2015-10-28 | 2016-01-13 | 安徽恒源煤电股份有限公司 | Corrosion resistant composite electroplating liquid |
| CN108315779A (en) * | 2018-04-19 | 2018-07-24 | 南雄市特能宝化学有限公司 | A kind of nickel-plating additive and electro-plating method |
| CN108315775A (en) * | 2018-04-19 | 2018-07-24 | 佛山市特能宝化学原料有限公司 | A kind of nickel plating brightener and electro-plating method |
| CN109628967A (en) * | 2019-01-07 | 2019-04-16 | 安徽马钢表面技术股份有限公司 | A kind of nickel cobalt (alloy) plating solution and its device for copper plate of crystallizer |
| CN109628967B (en) * | 2019-01-07 | 2020-06-26 | 安徽马钢表面技术股份有限公司 | Nickel-cobalt alloy plating solution for crystallizer copper plate and device thereof |
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