CN101967662A - Trivalent chromium electroplate liquid capable of forming black clad layer - Google Patents
Trivalent chromium electroplate liquid capable of forming black clad layer Download PDFInfo
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- CN101967662A CN101967662A CN 201010521853 CN201010521853A CN101967662A CN 101967662 A CN101967662 A CN 101967662A CN 201010521853 CN201010521853 CN 201010521853 CN 201010521853 A CN201010521853 A CN 201010521853A CN 101967662 A CN101967662 A CN 101967662A
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Abstract
The invention discloses trivalent chromium electroplate liquid capable of forming a black clad layer. Each liter of the trivalent chromium electroplate liquid comprises the following raw materials: a cylinder opening agent, 20 to 150g of stabilizing agent, 10 to 20g of cobalt chloride or manganese chloride, 0.6 to 1.5g of ferric chloride, and 1 to 10g of wetting agent, wherein each liter of cylinder opening agent consists of 5 to 30g of blackening agent, 90 to 140g of chromic salt, 180 to 300g of L conducting salt, 25 to 90g of pH buffering agent. The trivalent chromium electroplate liquid capable of forming the black clad layer has simple components and is easy to maintain; and the formed black clad layer has deep black color and high adhesion.
Description
Technical field
The present invention relates to a kind of electro-plating method that forms the trivalent chromium plating liquid of black coating and use this plating bath.
Background technology
Sexavalent chrome is the property swallowed poisonous substance/imbedibility utmost point poisonous substance, and skin contact may cause sensitivity; More may cause the heredity genetic flaw, sucking may be carcinogenic, environment there is lasting danger, sexavalent chrome is rejected just gradually as electroplate liquid, and chromic toxicity only is chromic 1%, sewage disposal is easy, and the sticking power of the coating that trivalent chromium bath forms is fine, and therefore trivalent chromium plating technology has obtained development fast in recent years.Black chromium electrolytic coating has good especially physical and chemical performance, and magnificent serious decorative appearance is not only arranged, and corrosion-resistant, high temperature resistant, even rises to about 500 ℃ when temperature, black chromium plating also can remain unchanged look, embrittlement not, its good thermal stability.Therefore black chromium plating black etc. than other coating such as black nickel plating, Zincing passivation, anodizing and is had more characteristic, be widely used in as the protected decoration coating that reduces reflection coefficient or as the functional coating that particular requirement is arranged, have in fields such as light industry, instrument, aerospace and use very widely and development prospect.
The trivalent chromium plating liquid composition of existing formation black coating is very complicated, difficult in maintenance mostly, and sticking power is relatively poor, and coating black is often more shallow, does not satisfy the demand of industry.
Summary of the invention
The purpose of this invention is to provide a kind of trivalent chromium plating liquid that forms black coating.
The technical solution used in the present invention is:
A kind of trivalent chromium plating liquid that forms black coating, it contains following raw material: open the cobalt chloride of stablizer, 10-20g/L of cylinder agent, 20-150g/L or Manganous chloride tetrahydrate, the iron(ic) chloride of 0.6-1.5g/L, the wetting agent of 1-10g/L, wherein, opening the cylinder agent is made up of blackening agent for surface, 90-140g/L chromic salt, 180-300g/L conducting salt, the 25-90g/L pH buffer reagent of 5-30g/L.
Blackening agent for surface is at least a in halfcystine, the Gelucystine.
Chromic salt is a chromium chloride.
Conducting salt is at least a in Repone K, sodium-chlor, magnesium chloride, ammonium chloride, Sodium tetrafluoroborate, potassium fluoborate, the Ammonium sulfamate.
The pH buffer reagent is at least a in boric acid, the aluminum chloride.
Stablizer is at least a in sodium formiate, potassium formiate, ammonium formiate, sodium acetate, potassium acetate, ammonium acetate, sodium oxalate, potassium oxalate, ammonium oxalate, sodium malonate, propanedioic acid potassium, propanedioic acid ammonium, sodium tartrate, ammonium tartrate, Trisodium Citrate, Tripotassium Citrate, ammonium citrate, sodium glycolate, oxyacetic acid potassium, alcohol acid phosphate, glycine, L-Ala, the aspartic acid.
Wetting agent is at least a in OP emulsifying agent, sodium sulfo-succinate, OT aerosol, the sodium lauryl tri(oxyethyl) sulfate.
The invention has the beneficial effects as follows: the trivalent chromium plating liquid composition that forms black coating is simple, safeguards that the coating black of formation is darker easily, adheres to better.
Embodiment
Below in conjunction with embodiment the composition of electroplate liquid is described further.
Embodiment 1
The trivalent chromium plating liquid ingredient that can form black coating is as shown in table 1:
Table 1: the trivalent chromium plating liquid ingredient that can form black coating
| Raw material | Concentration |
| Halfcystine | 10g/L |
| Chromium chloride | 106g/L |
| Ammonium chloride | 90g/L |
| Magnesium chloride | 42g/L |
| Repone K | 80g/L |
| Sodium tetrafluoroborate | 50g/L |
| Boric acid | 45g/L |
| Ammonium formiate | 50g/L |
| Manganous chloride tetrahydrate | 12g/L |
| Iron(ic) chloride | 0.6g/L |
| The OP emulsifying agent | 1g/L |
Embodiment 2
The trivalent chromium plating liquid ingredient that can form black coating is as shown in table 2:
Table 2: the trivalent chromium plating liquid ingredient that can form black coating
| The material title | Concentration |
| Gelucystine | 15g/L |
| Chromium chloride | 130g/L |
| Ammonium chloride | 100g/L |
| Repone K | 80g/L |
| Sodium-chlor | 50g/L |
| Boric acid | 40g/L |
| Potassium formiate | 80g/L |
| Cobalt chloride | 12g/L |
| Iron(ic) chloride | 1.5g/L |
| The OP emulsifying agent | 1.2g/L |
Embodiment 3
It is as shown in table 3 to form black coating electroplate liquid ingredient:
Table 3: black coating electroplate liquid ingredient
| The material title | Concentration |
| Gelucystine | 8g/L |
| Halfcystine | 5g/L |
| Chromium chloride | 110g/L |
| Repone K | 120g/L |
| Sodium-chlor | 100g/L |
| Boric acid | 40g/L |
| Aluminum chloride | 50g/L |
| Ammonium oxalate | 50g/L |
| Cobalt chloride | 20g/L |
| Iron(ic) chloride | 0.7g/L |
| Sodium lauryl tri(oxyethyl) sulfate | 1.5g/L |
Embodiment 4
It is as shown in table 4 to form black coating electroplate liquid ingredient:
Table 4: black coating electroplate liquid ingredient
| The material title | Concentration |
| Halfcystine | 5g/L |
| Chromium chloride | 140g/L |
| Repone K | 20g/L |
| Sodium-chlor | 100g/L |
| Magnesium chloride | 60g/L |
| Boric acid | 25g/L |
| Ammonium oxalate | 100g/L |
| Cobalt chloride | 16g/L |
| Iron(ic) chloride | 1g/L |
| The OP emulsifying agent | 3g/L |
Embodiment 5
It is as shown in table 5 to form black coating electroplate liquid ingredient:
Table 5: black coating electroplate liquid ingredient
| The material title | Concentration |
| Gelucystine | 25g/L |
| Halfcystine | 5g/L |
| Chromium chloride | 90g/L |
| Repone K | 20g/L |
| Sodium-chlor | 170g/L |
| Magnesium chloride | 60g/L |
| Ammonium sulfamate | 50g/L |
| Boric acid | 70g/L |
| Aspartic acid | 20g/L |
| Manganous chloride tetrahydrate | 10g/L |
| Iron(ic) chloride | 1.2g/L |
| The OP emulsifying agent | 5g/L |
| Sodium lauryl tri(oxyethyl) sulfate | 5g/L |
Embodiment 6
It is as shown in table 6 to form black coating electroplate liquid ingredient:
Table 6: black coating electroplate liquid ingredient
| The material title | Concentration |
| Gelucystine | 20g/L |
| Halfcystine | 5g/L |
| Chromium chloride | 125g/L |
| Repone K | 25g/L |
| Sodium-chlor | 75g/L |
| Magnesium chloride | 50g/L |
| Ammonium sulfamate | 55g/L |
| Boric acid | 80g/L |
| L-Ala | 150g/L |
| Manganous chloride tetrahydrate | 20g/L |
| Iron(ic) chloride | 1.1g/L |
| The OT aerosol | 8g/L |
Embodiment 7
It is as shown in table 7 to form black coating electroplate liquid ingredient:
Table 7: black coating electroplate liquid ingredient
| The material title | Concentration |
| Gelucystine | 4g/L |
| Halfcystine | 4g/L |
| Chromium chloride | 120g/L |
| Repone K | 50g/L |
| Sodium-chlor | 50g/L |
| Ammonium chloride | 100g/L |
| Ammonium sulfamate | 80g/L |
| Boric acid | 65g/L |
| Sodium malonate | 40g/L |
| Cobalt chloride | 10g/L |
| Iron(ic) chloride | 1.2g/L |
| Sodium sulfo-succinate | 6g/L |
Embodiment 8
It is as shown in table 8 to form black coating electroplate liquid ingredient:
Table 8: black coating electroplate liquid ingredient
| The material title | Concentration |
| Gelucystine | 11g/L |
| Halfcystine | 11g/L |
| Chromium chloride | 105g/L |
| Repone K | 65g/L |
| Sodium-chlor | 75g/L |
| Ammonium sulfamate | 105g/L |
| Boric acid | 55g/L |
| Trisodium Citrate | 130g/L |
| Manganous chloride tetrahydrate | 16g/L |
| Iron(ic) chloride | 0.85g/L |
| The OT aerosol | 7.5g/L |
The formed coating of embodiment 1-8 is carried out test of hundred lattice cuttves and blackness test.
Hundred lattice cuttves test: sample is placed on the test board, using cutting knife to draw length on the same direction of sample surfaces is that 20 millimeters, spacing are 11 lines of 1 millimeter, intersecting in 90 degree directions then, to draw length be that 20 millimeters, spacing are 11 lines of 1 millimeter, the adhesive tape centre of 75 millimeters long carefully is placed on draws on the good grid and ruling direction level, make adhesive tape cover grid fully, wipe examination with eraser then, adhesive tape is well contacted fully with grid; After 60 seconds, monolateral with the quick pull-up adhesive tape of 180 degree horizontal directions from adhesive tape, the area that comes off on surface calculates expulsion rate per sample, and the formed coating expulsion rate of the plating bath of embodiment 1-8 has good adhesion property all less than 10%.
The blackness test: the MN-B blackness instrument that the blackness of sample adopts its upright Science and Technology Ltd. of Tianjin to produce is measured, sample is placed on the desktop, the blackness instrument is close to sample, pressing the button reading gets final product, the formed coating blackness of the plating bath of embodiment 1-8 is respectively 52.5,50.8,53.7,54.6,54.2,53.2,52.8,53.5, all greater than 50, blackness is darker.
Claims (7)
1. trivalent chromium plating liquid that can form black coating, it is characterized in that: it contains following raw material: open the cobalt chloride of stablizer, 10-20g/L of cylinder agent, 20-150g/L or Manganous chloride tetrahydrate, the iron(ic) chloride of 0.6-1.5g/L, the wetting agent of 1-10g/L, wherein, opening the cylinder agent is made up of blackening agent for surface, 90-140g/L chromic salt, 180-300g/L conducting salt, the 25-90g/L pH buffer reagent of 5-30g/L.
2. a kind of trivalent chromium plating liquid that forms black coating according to claim 1 is characterized in that: blackening agent for surface is at least a in halfcystine, the Gelucystine.
3. a kind of trivalent chromium plating liquid that forms black coating according to claim 1, it is characterized in that: chromic salt is a chromium chloride.
4. a kind of trivalent chromium plating liquid that forms black coating according to claim 1 is characterized in that: conducting salt is at least a in Repone K, sodium-chlor, magnesium chloride, ammonium chloride, Sodium tetrafluoroborate, potassium fluoborate, the Ammonium sulfamate.
5. a kind of trivalent chromium plating liquid that forms black coating according to claim 1 is characterized in that: the pH buffer reagent is at least a in boric acid, the aluminum chloride.
6. a kind of trivalent chromium plating liquid that forms black coating according to claim 1 is characterized in that: stablizer is at least a in sodium formiate, potassium formiate, ammonium formiate, sodium acetate, potassium acetate, ammonium acetate, sodium oxalate, potassium oxalate, ammonium oxalate, sodium malonate, propanedioic acid potassium, propanedioic acid ammonium, sodium tartrate, ammonium tartrate, Trisodium Citrate, Tripotassium Citrate, ammonium citrate, sodium glycolate, oxyacetic acid potassium, alcohol acid phosphate, glycine, L-Ala, the aspartic acid.
7. a kind of trivalent chromium plating liquid that forms black coating according to claim 1 is characterized in that: wetting agent is at least a in OP emulsifying agent, sodium sulfo-succinate, OT aerosol, the sodium lauryl tri(oxyethyl) sulfate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912387A (en) * | 2012-10-26 | 2013-02-06 | 南京大地冷冻食品有限公司 | Chloride type trivalent chromium black chromium plating solution |
| CN105696028A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院金属研究所 | Trivalent chromium electroplating solution and electroplating method |
| CN107099824A (en) * | 2017-06-19 | 2017-08-29 | 四维尔丸井(广州)汽车零部件有限公司 | A kind of black chromium plating bath, composite deposite and preparation method thereof |
| CN111349952A (en) * | 2020-03-06 | 2020-06-30 | 广州三孚新材料科技股份有限公司 | Trivalent black chromium electroplating solution for solar heat collector |
| CN111465719A (en) * | 2017-12-13 | 2020-07-28 | 株式会社杰希优 | Trivalent chromium plating solution and chromium plating method using the same |
| CN112368421A (en) * | 2018-07-03 | 2021-02-12 | 株式会社杰希优 | Trivalent chromium plating bath and chromium plating method using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0323683A1 (en) * | 1988-01-05 | 1989-07-12 | Council of Scientific and Industrial Research | Improved black chromium plating bath useful for solar selective coatings |
| CN101092721A (en) * | 2006-06-19 | 2007-12-26 | 比亚迪股份有限公司 | Solution in use for plating trivalent chromium, and plating method for using the plating solution |
-
2010
- 2010-10-26 CN CN 201010521853 patent/CN101967662A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0323683A1 (en) * | 1988-01-05 | 1989-07-12 | Council of Scientific and Industrial Research | Improved black chromium plating bath useful for solar selective coatings |
| CN101092721A (en) * | 2006-06-19 | 2007-12-26 | 比亚迪股份有限公司 | Solution in use for plating trivalent chromium, and plating method for using the plating solution |
Non-Patent Citations (1)
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| 《电镀与精饰》 20100930 黄恩礼 三价铬电解液电镀黑铬工艺及市场现状 25-26，30 1-7 第32卷, 第9期 2 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912387A (en) * | 2012-10-26 | 2013-02-06 | 南京大地冷冻食品有限公司 | Chloride type trivalent chromium black chromium plating solution |
| CN105696028A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院金属研究所 | Trivalent chromium electroplating solution and electroplating method |
| CN107099824A (en) * | 2017-06-19 | 2017-08-29 | 四维尔丸井(广州)汽车零部件有限公司 | A kind of black chromium plating bath, composite deposite and preparation method thereof |
| CN107099824B (en) * | 2017-06-19 | 2019-05-17 | 四维尔丸井(广州)汽车零部件有限公司 | A kind of black chromium plating bath, composite deposite and preparation method thereof |
| CN111465719A (en) * | 2017-12-13 | 2020-07-28 | 株式会社杰希优 | Trivalent chromium plating solution and chromium plating method using the same |
| JPWO2019117178A1 (en) * | 2017-12-13 | 2020-12-17 | 株式会社Ｊｃｕ | Trivalent chrome plating solution and chrome plating method using this |
| CN112368421A (en) * | 2018-07-03 | 2021-02-12 | 株式会社杰希优 | Trivalent chromium plating bath and chromium plating method using the same |
| JPWO2020009096A1 (en) * | 2018-07-03 | 2021-07-08 | 株式会社Ｊｃｕ | Trivalent chromium plating solution and chrome plating method using this |
| JP7349427B2 (en) | 2018-07-03 | 2023-09-22 | 株式会社Jcu | Trivalent chromium plating solution and chrome plating method using the same |
| CN111349952A (en) * | 2020-03-06 | 2020-06-30 | 广州三孚新材料科技股份有限公司 | Trivalent black chromium electroplating solution for solar heat collector |
| CN111349952B (en) * | 2020-03-06 | 2021-06-08 | 广州三孚新材料科技股份有限公司 | Trivalent black chromium electroplating solution for solar heat collector |
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Application publication date: 20110209 |