CN105297083A - Trivalent chromium electroplating liquid for cold-rolled sheets - Google Patents
Trivalent chromium electroplating liquid for cold-rolled sheets Download PDFInfo
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- CN105297083A CN105297083A CN201510784280.4A CN201510784280A CN105297083A CN 105297083 A CN105297083 A CN 105297083A CN 201510784280 A CN201510784280 A CN 201510784280A CN 105297083 A CN105297083 A CN 105297083A
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Abstract
The invention discloses trivalent chromium electroplating liquid for cold-rolled sheets. The trivalent chromium electroplating liquid is prepared from chromium sulfate with the density of 135-145 g/L, sodium sulfate with the density of 210-230 g/L, potassium sulphate with the density of 30-40 g/L, magnesium sulfate with the density of 20-30 g/L, boric acid with the density of 65-75 g/L, formic acid with the density of 0.1-0.3 mol/L, oxalic acid with the density of 0.2-0.4 mol/L, sodium citrate with the density of 0.3-0.5 mol/L, lauryl sodium sulfate with the density of 0.001-0.002 mol/L, benzene sulfinic acid sodium salt with the density of 0.0015-0.0025 mol/L, gamma-methacryloxypropyltriethoxysilane with the density of 0.2-0.4 mol/L and methacryloxypropyltriethoxysilane with the density of 0.5-0.7 g/L.
Description
Technical field
The present invention relates to electroplating technology field, particularly relate to a kind of cold-reduced sheet trivalent chromium plating plating solution.
Background technology
Chromium coating is because having the features such as light, hard, anti-discolouring, wear-corrosion resistance be good and applying very extensive in the industry.Chrome-plated process is all adopt chromic acid as the sexavalent chrome chrome-plated process in chromium source for a long time.As a kind of electroplating technology, there are some defects in hexavalent chromium plating technically, as cathode efficiency is extremely low; Dispersion and the covering power of chromium plating are poor; And do not allow center-off etc. in chrome-plating process.The more important thing is, sexavalent chrome be in electroplating industry the most seriously, one of the most unmanageable source of pollution.
Along with the enhancing of people's environmental consciousness, sexavalent chrome is subject to more and more stricter restriction as harmful pollution source in electroplating industry.The countries and regions such as the World Health Organization, the U.S., Japan, Europe have been made strict restriction to sexavalent chrome and have been used regulation, as the U.S. changed chromic emission standard into 0.01mg/L by 0.05mg/L from 1997, and forbid before being specified in 2010 adopting hexavalent chromium plating technique; " ROHS " that European Parliament and board of management promulgate also requires from 1 day July in 2006, and the new electronics and the electric installation that are invested in market must not contain sexavalent chrome.And along with China is as the establishment of international production Central Position, the Electroplating Operations of China not only will follow the regulation (Cr of National Environment Policy Act rule about sexavalent chrome discharge
6+discharge be no more than 0.5mg/L), also to face international commodity exchange in the challenge of green barrier.
In order to replace the hexavalent chromium plating of heavily contaminated, people have carried out much research, comprise the chromium plating of lower concentration sexavalent chrome, alloy chromium replacement electroplating and trivalent chromium chrome plating etc.Wherein, development is abroad very fast owing to having the advantage such as low toxicity, low stain for trivalent chromium chrome plating technique, and many developed countries just progressively replace sexavalent chrome chromium plating by trivalent chromium chrome plating technique, and the research of domestic trivalent chromium chrome plating in recent years also becomes one of focus gradually.
The solution system of domestic and international trivalent chromium chrome plating is various, mainly contains sulfate system and chloride system, and chloride soln system trivalent chromium bath is separated out chlorine at electroplating process Anodic and is difficult to recycling, also can to environment; And adopt sulfate liquor system to be a kind of production technique of clean environment firendly, there is great application prospect.But the method ubiquity of current trivalent chromium chrome plating can not continue the defect thickened.Such as Chinese patent CN1880512A discloses a kind of trivalent chromium bath system, and this electroplate liquid chromium sulphate, sodium sulfate, boric acid, Tai-Ace S 150, sodium lauryl sulphate, complexing agent, stablizer are formed with certain proportion, and all the other are water.It has the following disadvantages: one is adopt the plating of static plating solution, and near negative electrode, pH raises too fast, cannot obtain the coating of thickness more than 5 μm; Two is that plating solution adopts Tai-Ace S 150 as conducting salt, because its both sexes feature easily causes bath stability poor.
Summary of the invention
The object of the invention is to propose a kind of cold-reduced sheet trivalent chromium plating plating solution, by selecting solution composition and adjusting content, replace sexavalent chrome, and make electrolytic coating thicker than prior art, and bonding force is strong, corrosion resistance and good.
For reaching this object, the present invention by the following technical solutions:
A kind of cold-reduced sheet trivalent chromium plating plating solution, consisting of of described plating solution: chromium sulphate 135-145g/L, sodium sulfate 210-230g/L, potassium sulfate 30-40g/L, magnesium sulfate 20-30g/L, boric acid 65-75g/L, formic acid 0.1-0.3mol/L, oxalic acid 0.2-0.4mol/L, Trisodium Citrate 0.3-0.5mol/L, sodium lauryl sulphate 0.001-0.002mol/L, benzene sulfinic acid sodium salt 0.0015-0.0025mol/L; γ-methacryloxy Trimethoxy silane 0.2-0.4mol/L; Dibutyl tin acetate 0.5-0.7g/L.
Preferably, consisting of of described plating solution: chromium sulphate 138-142g/L, sodium sulfate 215-225g/L, potassium sulfate 33-37g/L, magnesium sulfate 23-27g/L, boric acid 68-72g/L, formic acid 0.15-0.25mol/L, oxalic acid 0.25-0.35mol/L, Trisodium Citrate 0.35-0.45mol/L, sodium lauryl sulphate 0.0013-0.0017mol/L, benzene sulfinic acid sodium salt 0.0018-0.0022mol/L, γ-methacryloxy Trimethoxy silane 0.25-0.35mol/L, dibutyl tin acetate 0.55-0.65g/L.
Most preferably, consisting of of described plating solution: chromium sulphate 140g/L, sodium sulfate 220g/L, potassium sulfate 35g/L, magnesium sulfate 25g/L, boric acid 70g/L, formic acid 0.20mol/L, oxalic acid 0.30mol/L, Trisodium Citrate 0.40mol/L, sodium lauryl sulphate 0.0015mol/L, benzene sulfinic acid sodium salt 0.0020mol/L, γ-methacryloxy Trimethoxy silane 0.3mol/L, dibutyl tin acetate 0.6g/L.
When adopting this plating solution, following electroplating technology plating can be adopted: adopt graphite anode, working temperature is about 50-55 DEG C, and pH is 3.5-4.5, and current density is 22-24A/dm
2, electroplating time is 60-90 minute, and agitator speed is 100-120 rev/min.
The present invention has following beneficial effect:
1. the invention add γ-methacryloxy Trimethoxy silane and these two kinds of components of dibutyl tin acetate in the plating solution, and determine the Optimum Contents of the two.Show through practice, increase these two kinds of components and contrast with the coating not increasing these two kinds of components, hardness improves 10-18%, and coating porosity is by 4 original holes/cm
2be reduced to is 0 substantially.Achieve unexpected technique effect.
2. the thickness of coating of the present invention can reach 25-35 μm, and under chromium coating normal temperature, hardness can reach 720HV, and after 210-230 DEG C of process, coating hardness increases to 1530HV.Adopt Hull groove electroplating experiments (electric current is 3A) to test the dispersive ability of electrolytic solution, the standard test piece obtained (length 10cm) bright district scope is 8-9cm.
3. the alternative sexavalent chrome of chrome-plated process of the present invention, and plating solution is whole sulphate system, not halogen contained compound, is a kind of environmentally friendly plating solution.
Embodiment
Embodiment one
A kind of cold-reduced sheet trivalent chromium plating plating solution, consisting of of described plating solution: chromium sulphate 135g/L, sodium sulfate 230g/L, potassium sulfate 30g/L, magnesium sulfate 30g/L, boric acid 65g/L, formic acid 0.3mol/L, oxalic acid 0.2mol/L, Trisodium Citrate 0.5mol/L, sodium lauryl sulphate 0.001mol/L, benzene sulfinic acid sodium salt 0.0025mol/L, γ-methacryloxy Trimethoxy silane 0.2mol/L; Dibutyl tin acetate 0.7g/L.
Embodiment two
A kind of cold-reduced sheet trivalent chromium plating plating solution, consisting of of described plating solution: chromium sulphate 145g/L, sodium sulfate 210g/L, potassium sulfate 40g/L, magnesium sulfate 20g/L, boric acid 75g/L, formic acid 0.1mol/L, oxalic acid 0.4mol/L, Trisodium Citrate 0.3mol/L, sodium lauryl sulphate 0.002mol/L, benzene sulfinic acid sodium salt 0.0015mol/L, γ-methacryloxy Trimethoxy silane 0.4mol/L; Dibutyl tin acetate 0.5g/L.
Embodiment three
A kind of cold-reduced sheet trivalent chromium plating plating solution, consisting of of described plating solution: chromium sulphate 138g/L, sodium sulfate 225g/L, potassium sulfate 33g/L, magnesium sulfate 27g/L, boric acid 68g/L, formic acid 0.25mol/L, oxalic acid 0.25mol/L, Trisodium Citrate 0.45mol/L, sodium lauryl sulphate 0.0013mol/L, benzene sulfinic acid sodium salt 0.0022mol/L, γ-methacryloxy Trimethoxy silane 0.25mol/L, dibutyl tin acetate 0.65g/L.
Embodiment four
A kind of cold-reduced sheet trivalent chromium plating plating solution, consisting of of described plating solution: chromium sulphate 142g/L, sodium sulfate 215g/L, potassium sulfate 37g/L, magnesium sulfate 23g/L, boric acid 72g/L, formic acid 0.15mol/L, oxalic acid 0.35mol/L, Trisodium Citrate 0.35mol/L, sodium lauryl sulphate 0.0017mol/L, benzene sulfinic acid sodium salt 0.0018mol/L, γ-methacryloxy Trimethoxy silane 0.35mol/L, dibutyl tin acetate 0.55g/L.
Embodiment five
A kind of cold-reduced sheet trivalent chromium plating plating solution, consisting of of described plating solution: chromium sulphate 140g/L, sodium sulfate 220g/L, potassium sulfate 35g/L, magnesium sulfate 25g/L, boric acid 70g/L, formic acid 0.2mol/L, oxalic acid 0.3mol/L, Trisodium Citrate 0.4mol/L, sodium lauryl sulphate 0.0015mol/L, benzene sulfinic acid sodium salt 0.0020mol/L, γ-methacryloxy Trimethoxy silane 0.3mol/L; Dibutyl tin acetate 0.6g/L.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (3)
1. a cold-reduced sheet trivalent chromium plating plating solution, it is characterized in that, consisting of of described plating solution: chromium sulphate 135-145g/L, sodium sulfate 210-230g/L, potassium sulfate 30-40g/L, magnesium sulfate 20-30g/L, boric acid 65-75g/L, formic acid 0.1-0.3mol/L, oxalic acid 0.2-0.4mol/L, Trisodium Citrate 0.3-0.5mol/L, sodium lauryl sulphate 0.001-0.002mol/L, benzene sulfinic acid sodium salt 0.0015-0.0025mol/L; γ-methacryloxy Trimethoxy silane 0.2-0.4mol/L; Dibutyl tin acetate 0.5-0.7g/L.
2. a kind of cold-reduced sheet trivalent chromium plating plating solution as claimed in claim 1, it is characterized in that, consisting of of described plating solution: chromium sulphate 138-142g/L, sodium sulfate 215-225g/L, potassium sulfate 33-37g/L, magnesium sulfate 23-27g/L, boric acid 68-72g/L, formic acid 0.15-0.25mol/L, oxalic acid 0.25-0.35mol/L, Trisodium Citrate 0.35-0.45mol/L, sodium lauryl sulphate 0.0013-0.0017mol/L, benzene sulfinic acid sodium salt 0.0018-0.0022mol/L, γ-methacryloxy Trimethoxy silane 0.25-0.35mol/L, dibutyl tin acetate 0.55-0.65g/L.
3. a kind of cold-reduced sheet trivalent chromium plating plating solution as described in claim 1-2, is characterized in that, consisting of of described plating solution: chromium sulphate 140g/L, sodium sulfate 220g/L, potassium sulfate 35g/L, magnesium sulfate 25g/L, boric acid 70g/L, formic acid 0.20mol/L, oxalic acid 0.30mol/L, Trisodium Citrate 0.40mol/L, sodium lauryl sulphate 0.0015mol/L, benzene sulfinic acid sodium salt 0.0020mol/L, γ-methacryloxy Trimethoxy silane 0.3mol/L, dibutyl tin acetate 0.6g/L.
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| CN201510784280.4A CN105297083B (en) | 2015-11-16 | 2015-11-16 | A kind of cold-reduced sheet trivalent chromium plating plating solution |
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| CN201510784280.4A CN105297083B (en) | 2015-11-16 | 2015-11-16 | A kind of cold-reduced sheet trivalent chromium plating plating solution |
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| CN105297083B CN105297083B (en) | 2018-11-02 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370245A (en) * | 2000-01-20 | 2002-09-18 | 株式会社日矿材料 | Copper electroplating bath, pre-treating liquid before copper electroplating and copdper electroplating method |
| CN1880512A (en) * | 2006-05-11 | 2006-12-20 | 武汉大学 | Trivalent chromium electroplating solution in sulfate system and method for preparing same |
| CN101643924A (en) * | 2009-08-28 | 2010-02-10 | 广州市二轻工业科学技术研究所 | Full-sulfate trivalent-chromium solution for plating thick chromium and plating method |
| CN101792917A (en) * | 2010-03-31 | 2010-08-04 | 哈尔滨工业大学 | Preparation method and electroplating method of normal-temperature environment-friendly sulfate trivalent chromium electroplating liquid |
| CN103556189A (en) * | 2013-10-29 | 2014-02-05 | 常熟市伟达电镀有限责任公司 | Electroplating liquid with good stability |
-
2015
- 2015-11-16 CN CN201510784280.4A patent/CN105297083B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370245A (en) * | 2000-01-20 | 2002-09-18 | 株式会社日矿材料 | Copper electroplating bath, pre-treating liquid before copper electroplating and copdper electroplating method |
| CN1880512A (en) * | 2006-05-11 | 2006-12-20 | 武汉大学 | Trivalent chromium electroplating solution in sulfate system and method for preparing same |
| CN101643924A (en) * | 2009-08-28 | 2010-02-10 | 广州市二轻工业科学技术研究所 | Full-sulfate trivalent-chromium solution for plating thick chromium and plating method |
| CN101792917A (en) * | 2010-03-31 | 2010-08-04 | 哈尔滨工业大学 | Preparation method and electroplating method of normal-temperature environment-friendly sulfate trivalent chromium electroplating liquid |
| CN103556189A (en) * | 2013-10-29 | 2014-02-05 | 常熟市伟达电镀有限责任公司 | Electroplating liquid with good stability |
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