CN101173354B - Method for preparing trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts - Google Patents
Method for preparing trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts Download PDFInfo
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- CN101173354B CN101173354B CN2007101781234A CN200710178123A CN101173354B CN 101173354 B CN101173354 B CN 101173354B CN 2007101781234 A CN2007101781234 A CN 2007101781234A CN 200710178123 A CN200710178123 A CN 200710178123A CN 101173354 B CN101173354 B CN 101173354B
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- sub
- passivating solution
- passivation
- trivalent chromium
- zinc
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
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- Chemical Treatment Of Metals (AREA)
Abstract
The invention relates to a colorized passivating solution of Nd-Fe-B galvanized normal temperature trivalent chromium, and the preparation technique and the passivation method, belonging to the deposition field of metal material. The passivating solution comprises the contents as following: Cr (NO<SUB>3</SUB>) <SUB>3</SUB> 0.5 to 4 g/L, Ce (NO<SUB>3</SUB>) <SUB>3</SUB> 1 to 3 g/L, CoSO<SUB>4</SUB>0.5 to 4 g/L and Cr<SUP>3+</SUB> 6 to 12 g/L. The preparation method of Cr<SUP>3+</SUB> 6 to 12 g/L is the following: dissolve one share of CrO<SUB>3</SUB> is in water, then add 1.5 shares of tartaricacid slowly and stir the mixture constantly until reacting completely; and then dilute Cr<SUP>3+</SUP> 6 to 12 g/L by adding water; finally add Cr (NO<SUB>3</SUB>) <SUB>3</SUB> 0.5 to 4 g/L, Ce (NO<S UB>3</SUB>) <SUB>3</SUB> 1 to 3 g/L and CoSO<SUB>4</SUB> 0.5 to 4 g/L and stir the mixture until dissolving completely. Barrel-plating or hang-plating can be adopted on the alkaline and acidic galvanized layers. The passivating solution does not comprise hexavalent chrome and fluoride. The invention has the advantages of low cost and high operability, and can improve the working conditions and meet the requirements of environment protection.
Description
Technical field
The present invention relates to the plating field of metallic substance, particularly a kind of trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts in normal temperature and preparation method and passivating method.
Background technology
In the prior art; electro-galvanizing is the most frequently used coating for protection against corrosion of NdFeB material; it has beautiful appearance, simple to operate, characteristics such as cost is cheap; the necessary means that zinc coating passivation is handled as protection zinc layer is the indispensable aftertreatment technology of electro-galvanizing product, and traditional passivating dip is to contain the passivating dip of hexavalent chromium.The sexavalent chrome colorful passivating process has many good qualities, as very high solidity to corrosion, and the corrosion proof self-healing ability of self-repairability, raw material is cheap.But sexavalent chrome has severe toxicity and be carcinogens, and along with society and expanding economy, from preserving the ecological environment and the angle of human health, the sexavalent chrome colorful passivating process is to eliminate.
European Union has signed a decree in 2003 in Brussels, and regulation forbade using sexavalent chrome vehicle material and the parts from January 1st, 2003, and according to this decree, the content of 6-valence Cr ions of each automobile is no more than 2g.On August 14th, 2004, European Union's " electronic waste facture " is formal to put into effect, and on August 13rd, 2005, these rules formally come into effect.This decree is to finish according to two instructions of European Union in 2002.These two instructions are respectively " about scrapping the electronic and electrical equipment instruction " and " about ban use of some objectionable impurities instruction in electronic and electrical equipment ", require EU member country to guarantee from July 1st, 2006, new electronics of putting on market and electrical equipment do not comprise 6 kinds of objectionable impuritiess such as lead, mercury, cadmium, sexavalent chrome, poly-dibromodiphenyl ether and poly-bromo biphenyl.Decree is also stipulated, all are production and selling notebook computer, desktop PC, printer, CPU, motherboard, mouse, keyboard, mobile phone etc. on European Union market, must be before 13 days Augusts in 2005, set up the using system of intactly classifying, reclaim, restore, regenerate, and the burden product reclaims responsibility.The enterprise that China produces exported product must stop using the sexavalent chrome passivation technology on August 13rd, 2004 later on.
Along with European Union to chromic restriction, the use of trivalent chromium colorful passivation liquid will get more and more.Simultaneously, China more and more payes attention to environmental protection, believes in the near future and also can cancel chromic use.When the time comes, zinc-plated industry will all be used trivalent chromium passivator.Can imagine that trivalent chromium colorful passivation liquid and preparation method's potential market will be how huge, its importance is not say and pre-.
There is following defective in the preparation method of present trivalent chromium colorful passivation liquid:
(1) poor operability
In the passivating process, controlling factor is many, and span of control is narrow, and the use difficulty of passivating solution is big, the passivating solution poor controllability.The workman often is difficult to the product that passivation goes out the outward appearance unanimity, often has that color is inconsistent, irregular colour even, even therefore the salt mist experiment result also can be affected.
(2) temperature height
The temperature height is unfavorable for workman's operation when using passivating solution.In case the reduction temperature, passivation does not go out color and due thickness again, influences the quality of product.
(3) appearance color is poor
Appearance color is less than sexavalent chrome passivation color even and bright-coloured.Secondly, the control difficulty of appearance color is big, and consistence is poor, directly influences quality product.
(4) passivation time is long
There is not Cr in the passivating solution
6+The strong oxidizer that ion is such, film forming speed obviously reduces, and passivation time is elongated, makes workman's operating time increase, and working efficiency reduces.
(5) cost height
Summary of the invention
The object of the present invention is to provide a kind of trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts in normal temperature and preparation method and passivating method, can realize the purpose that reduces cost and improve operability, improve work situation and compliance with environmental protection requirements.
In order to achieve the above object, the present invention is achieved in that
A kind of chemical ingredients of trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts in normal temperature is: Cr (NO
3)
35-10g/L, Ce (NO
3)
31-3g/L, CoSO40.5-4g/L, wherein Cr
3+6-12g/L.
Passivating solution also comprises Ti, Ni, Mo, Re, SO
4 2-, Co, F
-Deng positively charged ion and negatively charged ion.
PH value is 2-3.
A kind of preparation method of trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts in normal temperature may further comprise the steps:
(1) gets 1 part of CrO
3Be dissolved in water, add 1.5 parts tartrate, constantly be stirred to complete reaction, at this moment Cr
6-Be reduced to Cr fully
3+, thin up is to Cr
3+6-12g/L;
(2) add Cr (NO
3)
35-10g/L, Ce (NO
3)
31-3g/L, CoSO
40.5-4g/L be stirred to dissolving fully.
The chemical ingredients of the passivating solution that obtains is: Cr (NO
3)
35-10g/L, Ce (NO
3)
31-3g/L, CoSO
40.5-4g/L, Cr wherein
3+6-12g/L.
The pH value of passivating solution is 2-3.
A kind of passivating method of trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts in normal temperature, passivating solution composition are Cr (NO
3)
35-10g/L, Ce (NO
3)
31-3g/L, CoSO
40.5-4g/L, Cr wherein
3+6-12g/L;
Galvanizing production after the bright dipping, is immersed in the above-mentioned passivating solution and contacts 30-60s in 3% salpeter solution, flushing with clean water, hot water wash, oven dry at last.
Passivation temperature is 20-40 ℃, and the pH value of passivating solution is 2-3.
The described passivating solution way of contact is barrel plating or rack plating.
The trivalent chromium passivating process is that the dissolving by zinc forms zine ion, and the dissolving of zine ion simultaneously causes the pH value of zinc surface solution to rise, trivalent chromium directly with reactions such as zine ion, hydroxide radical, form insoluble compound and be deposited on the zinc surface, and the formation passive film.Concrete reaction formula 1-3 is as follows:
1. molten zinc process: Zn+O
x(oxygenant) → Zn
2++ O
x -
Zn+2H
-→Zn
2++H
2↑
2. film process: Zn
2++ xCr (III)+yH
2O → ZnCr
xO
y+ 2yH
+
3. the molten process of film: ZnCr
xO
y+ 2yH
+→ Zn
2++ xCr (III)+yH
2O
Obviously in order to obtain the passivating solution that passivation speed is fast and passivation temperature is low, just need to improve the film forming speed of reaction 2.Reaction 1 and reaction 3 are mainly by H
-Concentration decision, i.e. pH value size decision.And react 2 mainly by composition influences such as the main salt components decision of passivating solution and secondary film formers.
The present invention improves the passivating solution performance by the following aspects:
(1) adopts new complexing agent
Selected the complexing agent of excellent property in the passivating solution, as sexavalent chrome and tartrate reaction gained trivalent chromium complex, shape film speed is greatly improved, and the passive film of formation is fine and close more, and solidity to corrosion is greatly improved.Novel complexing agent combines stable with trivalent chromium, guaranteed the stability of passivating solution.
(2) add secondary film formers
Secondary film formers CoSO
4Can be evenly distributed in passivating process in the framework of the passive film that trivalent chromium forms, the effectively generation and the expansion of tissue erosion point further improved the solidity to corrosion of rete.
(3) add film forming accelerating
Film forming accelerating Ce (NO
3)
3Improve the anti-H of passive film
-Solvability, the speed of response of reduction reaction 3 makes the formation of passive film be more prone to.
Passivating solution prepares route
The screening of the screening → film forming accelerating of the screening → oxygenant of the screening → complexing agent of main membrane-forming agent → determine passivation technology and PASSIVATION MECHANISM.
(1) screening of main salt component
The passivation effect of obtaining, the Cr that need choose
3+Chromium complex is as the main salt component of trivalent chromium deactivating liquid.At traditional Cr (NO
3)
3, CrCl
3In the aqueous solution Deng medicine, Cr
3+Form with hydrated ion exists, Cr
3+Ion is very stable, is difficult to obtain the ideal passive film.Owing to seek a kind of good Cr
3+Chromium complex is the key of the outstanding passivating solution of preparation performance.Therefore, select various reductive agents, be used for reducing CrO
3, to obtain the Cr of four kinds of needs
3+Chromium complex is as the main membrane-forming agent of trivalent chromium deactivating liquid.
(2) main salt concentration determines
The passivation effect of different main salt concentrations is different, by the comparison of four kinds of main salt concentrations, determines suitable main salt concentration scope.Four kinds of concentration master salt are respectively 3g/L, 6g/L, 9g/L, 12g/LCr
3+Content.
The result shows: the scope of main salt concentration is 6-12g/L Cr
3+Content, wherein 9g/L Cr
3+Content is optimum concn, and in this scope, outward appearance that passivation goes out and salt-fog test be obviously difference not, mainly is the difference on the passivation time, that is to say that concentration is high more, and passivation time is long more.3g/LCr
3+The passivation time of content is long, illustrates that passivation speed is slow because concentration is low.
(3) content of oxygenant
Nitrate radical is during as oxygenant, and for the nitrate radical of different content, passivation effect has Different Effects.Select four kinds of nitrate concentrations, be respectively 5g/L, 10g/L, 15g/L, 20g/L nitrate; The main salt concentration of passivating solution is 9g/L Cr
3+Content, pH value are 3.The product that passivation is good is determined the nitrate radical scope by outward appearance and salt-fog test result.
The result shows: the nitrate scope is 5-10g/L, and it is little to the passivation influence to improve nitrate concentration again.
(4) influence of pH value
Different PH is very big to the passivation influence, therefore, and to passivating solution 9g/L Cr
3+Content, 7.5g/L nitrate are regulated pH value from 1-5 by nitric acid and NaOH, carry out passivation respectively, determine best pH value in conjunction with outward appearance and salt fog.
The result shows: the pH value optimum range is between the 2-3.When pH value was too low, outward appearance was sent out crow, almost Achromatic color.PH value is too high, and passive film is thin, and passivation speed is too slow.
(5) other ion pair passivating solution performance impact
These ions comprise negatively charged ion and positively charged ion, to passivating solution be formed with promoter action and booster action, the formation of passive film and the compactness of passive film are had no small influence.In the experiment to Ti, Ni, Mo, Re, SO
4 2-, Co, F
-Plasma is studied, and in conjunction with outward appearance and salt-fog test result, selects useful ion again.Then ionic concn is further studied, finally determined concrete passivating solution composition.
According to above-mentioned purpose and principle of work, the concrete technical scheme of the present invention is:
The passivating solution process for preparation:
(1) gets 1 part of CrO
3After being dissolved in water, gradual slow adds 1.5 parts tartrate again, constantly stirs until reacting completely, at this moment Cr
6-Be reduced to Cr fully
3+, thin up is to Cr
3+Content be the 6-12g/L scope.
(2) add Cr (NO
3)
35-10g/L, Ce (NO
3)
31-3g/L, CoSO
40.5-4g/L be stirred to dissolving fully.
The passivating solution passivation technology:
Galvanizing production bright dipping in 3% salpeter solution earlier is dipped into required time again in passivating solution, flushing with clean water then, and hot water wash, oven dry gets final product.Concrete processing parameter is as follows:
Passivation temperature: 20-40 ℃
Passivation time: 30-60 second
PH scope: 2-3
The ultimate constituent of passivating solution is: Cr
3+6-12g/L, Cr (NO
3)
35-10g/L, Ce (NO
3)
31-3g/L, CoSO
40.5-4g/L.
Compared with prior art, beneficial effect of the present invention is:
(1) passivating solution and passive film do not contain sexavalent chrome and fluorochemical, compliance with environmental protection requirements, and wastewater treatment is simple.
(2) the passive film rete is thick, is multicolored color, and neutral salt spray test (SST) was greater than 120 hours.
(3) passivation is carried out at ambient temperature, and save energy makes things convenient for the workman to operate, and has also reduced solution evaporation, helps workers ' health and environment protection.
(4) the passivating solution use range is wide, and operability is big.
(5) the passivating solution film forming speed is fast, and the operating time is short.
(6) the passivation product purchasing is convenient, and cost is low, is beneficial to batch process.
(7) be fit on alkalescence and the acid zinc plating layer, barrel plating and rack plating all can.
Claims (3)
1. the preparation method of a trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts in normal temperature is characterized in that: may further comprise the steps:
(1) gets 1 part of CrO
3Be dissolved in water, add 1.5 parts tartrate, constantly be stirred to complete reaction, at this moment Cr
Be reduced to Cr fully
3+, thin up is to Cr
3+6-12g/L;
(2) add Cr (NO
3)
35-10g/L, Ce (NO
3)
31-3g/L, CoSO
40.5-4g/L be stirred to dissolving fully.
2. preparation method according to claim 1 is characterized in that: the chemical ingredients that obtains passivating solution is: Cr (NO
3)
35-10g/L, Ce (NO
3)
31-3g/L, CoSO
40.5-4g/L, Cr wherein
3+6-12g/L.
3. preparation method according to claim 1 and 2 is characterized in that: the pH value of passivating solution is 2-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101781234A CN101173354B (en) | 2007-11-27 | 2007-11-27 | Method for preparing trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101781234A CN101173354B (en) | 2007-11-27 | 2007-11-27 | Method for preparing trivalent chromium colorful passivation liquid for NdFeB Zinc-plated parts |
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| CN101173354A CN101173354A (en) | 2008-05-07 |
| CN101173354B true CN101173354B (en) | 2010-04-14 |
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| CN102560456A (en) * | 2012-03-16 | 2012-07-11 | 广西民族大学 | Preparation method of aluminium alloy trivalent chromium and trivalent cerium composite conversion film, and film formation liquid of composite conversion film |
| CN104005013A (en) * | 2014-06-11 | 2014-08-27 | 廊坊京磁精密材料有限公司 | Method for passivating galvanized neodymium iron boron magnet |
| CN108486557A (en) * | 2018-02-27 | 2018-09-04 | 浙江康盛股份有限公司 | A kind of bright blue passivation liquid with high antiseptic property |
| CN108385095A (en) * | 2018-02-27 | 2018-08-10 | 浙江康盛股份有限公司 | A kind of bright blue passivation liquid and its configuration method with high antiseptic property |
| CN108239770A (en) * | 2018-02-27 | 2018-07-03 | 浙江康盛股份有限公司 | A kind of bright blue passivation liquid and its application method with high antiseptic property |
| CN113667968B (en) * | 2021-10-25 | 2022-02-18 | 天津三环乐喜新材料有限公司 | Chromium-free passivation method for zinc-plated product of neodymium-iron-boron permanent magnet |
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