CN101078131A - Method for electrodepositing ornamental chromium coating in trivalency chromium coating solution - Google Patents

Method for electrodepositing ornamental chromium coating in trivalency chromium coating solution Download PDF

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Publication number
CN101078131A
CN101078131A CN 200610042897 CN200610042897A CN101078131A CN 101078131 A CN101078131 A CN 101078131A CN 200610042897 CN200610042897 CN 200610042897 CN 200610042897 A CN200610042897 A CN 200610042897A CN 101078131 A CN101078131 A CN 101078131A
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China
Prior art keywords
plating
chromium
chromium coating
chrome
coating
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Pending
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CN 200610042897
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Chinese (zh)
Inventor
张俊彦
曾志翔
梁爱民
王立平
胡丽天
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Priority to CN 200610042897 priority Critical patent/CN101078131A/en
Publication of CN101078131A publication Critical patent/CN101078131A/en
Pending legal-status Critical Current

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Abstract

The invention discloses a method to produce the decorated chrome plating layer in trivalence chrome electroplate liquid. The invention is to select the proper additive and control the condition in the base electrolyte containing the chromium chloride to produce the non-crystal chrome plate with smooth surface and no crack, also which is the light and anti-corrosion as same as the sexivalent chrome plating. The process is stable, the operation condition is wide and the energy cost is low; also the ability of disperse, covering and current flow effect are high than sexivalent chrome plating process. The thickness of plating chrome is 0.5-1 mu m. So the invention can instead of the sexivalent process and be used in all anticorrosion and decorated field.

Description

The method of galvanic deposit decorative chromium coating in trivalent chromium bath
Technical field
The present invention relates to the electro-deposition method of preparation decorative chromium coating in the environment-friendly type trivalent chromium bath.
Background technology
Decorative chromium coating becomes one of most widely used decorative coating of industry member owing to having good glossiness and corrosion resistance nature.But for a long time, traditional sexavalent chrome electroplating technology exists and much is difficult to the shortcoming that overcomes, poor as dispersive ability and covering power, current efficiency is low, electroplating temperature is high, electroplating process to human and environment seriously polluted and plating bath aftertreatment difficulty etc.In the sexavalent chrome electrodeposition process, contain a large amount of sexavalent chromes in waste water and the waste gas, it causes very big pollution to environment, and can cause human body renal failure, heart rate depletion, leukemia, cause cancer strongly.At present, the World Health Organization and countries in the world are more and more paid attention to the pollution problem of sexavalent chrome electroplating technology.European Union recent " about in electronics, banning use of the instruction of some objectionable impurities " (ROHS) strict regulation after 1 day July in 2006, will forbid the use of sexavalent chrome in electronic product in European whole area." the electronics and IT products pollution control management way " of China also clearly stipulated from the chromic use of control on March 1st, 2007.Therefore, the research of current alternative sexavalent chrome electro-deposition techniques has become one of the focus of electroplating industry research and difficult point.
At present, substitute the sexavalent chrome electroplating technology and mainly contain three kinds: vapour deposition chromium coating, electro-deposited alloy coating, trivalent chromium galvanic deposit.That the gas phase deposition technology advantage is to pollute is little, deposition evenly, but its cost height, covering power are poor, can not be used for the deposition of irregular workpiece and pipe fitting inner wall, also are unfavorable for large-scale industrial production.The electro-deposited alloy nickel-base alloy coating mainly comprises Zn-Sn-Co, Ni-P, Ni-W and other ternary alloys, and this kind method is polluted little, but bath stability is poor, but operational condition is narrow.By contrast, decorate trivalent chromium electrodeposition technology toxicity and have only 1% of sexavalent chrome electroplating technology, and energy consumption is little, the efficient height, but its shortcoming is that coating glossiness difference and bath stability are poor.Though the industrialization promotion of the ornamental trivalent chromium plating technology of existing external report, domestic have the ornamental trivalent chromium plating technology that independent intellectual property right also can be applied to suitability for industrialized production and yet there are no report.
In order to reduce environmental pollution, the technology that reduces Chinese foreign state aspect chromium plating relies on, and overcomes the fort of green trade, presses for domestic investigators and develops and have independent intellectual property right and can be applied to industrial ornamental trivalent chromium plating technology.We have reasonably selected some additives through in a few years research, but the ornamental trivalent chromium plating technology of having developed suitability for industrialized production of success.But simple wide, the good stability of operational condition of this mill solution composition is expected to replace with serious pollution sexavalent chrome electroplating technology comprehensively aspect decorative electroplating chromium.
Summary of the invention
The objective of the invention is to develop ornamental trivalent chromium plating technology, this technology has good dispersive ability, covering power, stability.Coating flawless and matrix have good bonding force, and its outward appearance and corrosion resistance nature are suitable with the sexavalent chrome galvanization coating.
The present invention realizes by following measure:
A kind of in trivalent chromium bath the method for galvanic deposit decorative chromium coating, it is characterized in that selecting for use the chromium chloride solution system, its solution composition is: contain chromium chloride 95-125g in every liter of electrolytic solution, urea 80~120g, brometo de amonio 40~50g, sodium-chlor 20~35g, boric acid 2~10g, methyl alcohol 180~220ml, formic acid, acetate, oxalic acid, Padil, formate, acetate or oxalate 0.1~1mol; Anode is a high purity graphite during galvanic deposit, and after pre-treatment cleaned and activate before according to the plating of routine with workpiece, the control plating temperature was at 20~30 ℃, and electrolyte ph is controlled at 1~3, and cathode current density is 5~20A/dm 2, galvanic deposit can be prepared the bright chromium coating that thickness is 0.5~1 μ m in 2~5 minutes.
The additive that the present invention selects can strengthen the polarized action of negative electrode effectively, the grain-size of coating is reduced and shows good light.The stability of plating bath mainly is subjected to positive column Cr 3+Be oxidized to Cr 2O 7 2-Influence.Cr 2O 7 2-Concentration reaches more than the 3ppm, and quality of coating descends.In the plating bath of the present invention, there is the reductibility of two kinds of materials to be better than Cr 3+, can stop Cr in the plating bath effectively 2O 7 2-Generation, make plating bath have satisfactory stability.
By technology of the present invention, plating bath is in discontinuous energising 60Ah/l, and the coating that galvanic deposit obtains is as bright as a sixpence.
By technology of the present invention, when utilizing Hull Cell experimental test dispersive ability, the bright range of cathode sample is greater than 6cm.
By technology of the present invention, when utilizing negative pole of right angle method test covering power, the fraction of coverage of workpiece is greater than 80%.
By the chromium coating flawless of the present invention's preparation, surface roughness Ra≤0.1 μ m.
By the chromium coating corrosion resistance nature of the present invention preparation near or be better than traditional sexavalent chrome galvanization coating.
The toxicity of plating bath only is 1% of sexavalent chrome plating bath among the present invention, therefore belongs to the environment-friendly type process for cleanly preparing prescription of " clean production method " regulation, and meets the requirement of " the electronics and IT products pollution control management way " of the ROHS of European Union instruction and China.
Maximum breakthrough point of the present invention is: 1. can be in operational condition scope than broad, and the chromium coating of deposit bright in trivalent chromium bath; 2. bath stability can reach the continuous production requirement.3. the employing graphite anode makes the cost of technology descend greatly.
The present invention can replace traditional sexavalent chrome electroplating technology comprehensively aspect decoration chrome plating.
Embodiment
For a better understanding of the present invention, describe by example.
Embodiment 1
At surface-area is 0.05dm 2Metal such as 45# steel or red copper workpiece surface adopt electro-deposition method plating of the present invention, pretreatment technology before the conventional plating is adopted in pre-treatment before the plating of workpiece.Trivalent chromium galvanic deposit decorative chromium coating electroplate liquid formulation is: containing chromium chloride in every liter of electrolytic solution is 95-125g, urea 80~120g, brometo de amonio 40~50g, sodium-chlor 20~35g, boric acid 6~10g, methyl alcohol 180~220ml, formic acid (or acetate, oxalic acid, Padil, formate, acetate, oxalate) 0.1~1mol.High purity graphite is an anode during plating, will make negative electrode through pretreated 45# steel or red copper workpiece before the conventional plating; Electrolyte ph is controlled at 1-3, utilizes thermostat control plating temperature at 20~30 ℃, and stirring velocity is suitable, and the control cathode electric current is between 0.25~1.0A in the deposition process, and current density is too little or too big, and the quality of coating all can descend.Electrodeposition time is 2~5 minutes, can deposit the hard chromium that thickness is 0.5~1 μ m.The coating that galvanic deposit obtains is non-crystalline state, light, flawless.

Claims (1)

1, a kind of in trivalent chromium bath the method for galvanic deposit decorative chromium coating, it is characterized in that selecting for use the chromium chloride solution system, its solution composition is: contain chromium chloride 95-125g in every liter of electrolytic solution, urea 80~120g, brometo de amonio 40~50g, sodium-chlor 20~35g, boric acid 2~10g, methyl alcohol 180~220ml, formic acid, acetate, oxalic acid, Padil, formate, acetate or oxalate 0.1~1mol; Anode is a high purity graphite during galvanic deposit, and after pre-treatment cleaned and activate before according to the plating of routine with workpiece, the control plating temperature was at 20~30 ℃, and electrolyte ph is controlled at 1~3, and cathode current density is 5~20A/dm 2, galvanic deposit can be prepared the bright chromium coating that thickness is 0.5~1 μ m in 2~5 minutes.
CN 200610042897 2006-05-26 2006-05-26 Method for electrodepositing ornamental chromium coating in trivalency chromium coating solution Pending CN101078131A (en)

Priority Applications (1)

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CN 200610042897 CN101078131A (en) 2006-05-26 2006-05-26 Method for electrodepositing ornamental chromium coating in trivalency chromium coating solution

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Application Number Priority Date Filing Date Title
CN 200610042897 CN101078131A (en) 2006-05-26 2006-05-26 Method for electrodepositing ornamental chromium coating in trivalency chromium coating solution

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101397685B (en) * 2008-10-24 2012-03-21 江苏大学 Trivalent chromium plating solution, preparation thereof and method for electric plating stainless steel work piece by using the same
CN102433574A (en) * 2011-11-18 2012-05-02 吉林大学 Chloride decorative trivalent chromium plating solution
CN102443825A (en) * 2011-12-07 2012-05-09 黄石振华化工有限公司 High-concentration chromium sulfate-ammonium fluoride trivalent chromium electroplating solution and preparation method thereof
CN102660759A (en) * 2012-06-08 2012-09-12 郑州飞机装备有限责任公司 Method for chroming by using trivalent chromium
CN103014784A (en) * 2012-12-13 2013-04-03 合肥华清方兴表面技术有限公司 Constant-temperature environment-friendly trivalent chromium electroplating liquid and electroplating method thereof
CN104388989A (en) * 2014-11-14 2015-03-04 无锡信大气象传感网科技有限公司 Trivalent chromium electroplating liquid and preparation method thereof
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
CN110446801A (en) * 2017-04-04 2019-11-12 安美特德国有限公司 For depositing the controlled method of chromium or chromium alloy layer at least one substrate
CN110760900A (en) * 2019-11-29 2020-02-07 扬州大学 Method for reducing hexavalent chromium wastewater to be used as chromium electroplating source and electroplating method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101397685B (en) * 2008-10-24 2012-03-21 江苏大学 Trivalent chromium plating solution, preparation thereof and method for electric plating stainless steel work piece by using the same
CN102433574A (en) * 2011-11-18 2012-05-02 吉林大学 Chloride decorative trivalent chromium plating solution
CN102443825A (en) * 2011-12-07 2012-05-09 黄石振华化工有限公司 High-concentration chromium sulfate-ammonium fluoride trivalent chromium electroplating solution and preparation method thereof
CN102443825B (en) * 2011-12-07 2014-03-26 湖北振华化学股份有限公司 High-concentration chromium sulfate-ammonium fluoride trivalent chromium electroplating solution and preparation method thereof
CN102660759A (en) * 2012-06-08 2012-09-12 郑州飞机装备有限责任公司 Method for chroming by using trivalent chromium
CN103014784A (en) * 2012-12-13 2013-04-03 合肥华清方兴表面技术有限公司 Constant-temperature environment-friendly trivalent chromium electroplating liquid and electroplating method thereof
CN104388989A (en) * 2014-11-14 2015-03-04 无锡信大气象传感网科技有限公司 Trivalent chromium electroplating liquid and preparation method thereof
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
CN110446801A (en) * 2017-04-04 2019-11-12 安美特德国有限公司 For depositing the controlled method of chromium or chromium alloy layer at least one substrate
CN110760900A (en) * 2019-11-29 2020-02-07 扬州大学 Method for reducing hexavalent chromium wastewater to be used as chromium electroplating source and electroplating method thereof

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