CN1858303B - Normal temperature passivated zinc coating trivalent chromium color passivating agent - Google Patents
Normal temperature passivated zinc coating trivalent chromium color passivating agent Download PDFInfo
- Publication number
- CN1858303B CN1858303B CN2006100358619A CN200610035861A CN1858303B CN 1858303 B CN1858303 B CN 1858303B CN 2006100358619 A CN2006100358619 A CN 2006100358619A CN 200610035861 A CN200610035861 A CN 200610035861A CN 1858303 B CN1858303 B CN 1858303B
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- CN
- China
- Prior art keywords
- trivalent chromium
- zinc coating
- normal temperature
- chromium color
- passivating agent
- 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.)
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Classifications
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- 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
Abstract
The present invention discloses trivalent chromium color zinc coating passivator for passivation at normal temperature and its preparation process. The trivalent chromium color zinc coating passivator includes Cr3+ 1-7.5g/L, molybdate 1-25g/L, cobalt sulfate 5-15, ammonium bifluoride 1-8g/L, malonic acid 1-12g/L, phosphate 1-12 g/L, and silicate 0.2-6g/L. The trivalent chromium color zinc coatingpassivator solution has pH 1.8-2.3 regulated with sodium carbonate or nitric acid, passivating temperature of 20-35deg.c, passivating time of 30-60 sec and stoving temperature of 70-80deg.c. The present invention has the advantages of being practical and good use effect.
Description
Technical field
The present invention relates to a kind of colorful passivation treatment agent that is used for behind the steel galvanization.
Background technology
Steel-iron components all will carry out Passivation Treatment usually after electro-galvanizing or pot galvanize, to prevent producing white rust in the short period of time.Colorful passivating process can form on zinc coating based on red and green, thicker iridescent passivation film, and is not only attractive in appearance but also have a splendid anticorrosion ability.Traditional sexavalent chrome color passivating agent causes serious pollution to environment, is now replaced by the trivalent chromium passivator of environmental protection gradually.The employing trivalent chromium passivation process will form chromatic passive film and be not easy on zinc coating, because trivalent chromic ion can only produce blueness or white chromating film usually, and chromatic passive film is because the effect of hexavalent chromium obtains.Generally believe that in addition chromatic passive film is thicker, trivalent chromium technology is difficult to obtain so thick passive film.There is U.S. Pat P4384902 to propose in passivating solution, to add the rare earth compound Cerium II Chloride, can on zinc coating, produces the xanchromatic passive film, contain Cr in the passivating solution
3+, ferrous ammonium sulphate, nitric acid, sodium-chlor, succsinic acid, silicate, Cerium II Chloride etc.But found sexivalent Ce afterwards
6+Might be with Cr
3+Be oxidized to Cr
6+, can not guarantee that passivating solution does not contain Cr fully
6+Also have U.S. Pat P5393354 to propose to carry out Passivation Treatment under 50 ~ 70 ℃ comparatively high temps, passivating solution is made up of chromium chloride, ammonium bifluoride, zinc chloride, SODIUMNITRATE, phosphoric acid, can obtain brightly painted 3-valance chromium contained rainbow-colour passive film.But the solidity to corrosion of passive film is relatively poor, can not satisfy need of industrial production.U.S. Pat P 6287704 has proposed the passivator formula of high density: 50g/L chromium chloride, 100g/L SODIUMNITRATE, 3g/L Xiao Suangu, 31.2g/L propanedioic acid, under 50 ~ 70 ℃ condition, can obtain thickness is the iridescent passivation film of 100 ~ 1000nm, and corrosion resistance nature is also very outstanding.But the passivating solution of this high density is the production cost height not only, and the loss that workpiece is taken out of is also very big, and the user is difficult to bear.Because operate under 50 ~ 70 ℃ comparatively high temps, not only energy consumption is big, and work under bad environment, is unfavorable for environmental protection simultaneously.
Summary of the invention
The objective of the invention is in order to solve above-mentioned deficiency, and provide a kind of have economical and practical, production cost is low, the trivalent chromium colour passivator of zinc coating under the normal temperature of corrosion resistance and good.
The technical solution that the present invention adopts in order to reach above-mentioned effect is as follows:
The zinc coating trivalent chromium color passivating agent that this is normal temperature passivated is characterized in that it includes the Cr of 1～7.5g/L
3+(by CrCl
3Provide), the molybdate of 1～25g/L, the rose vitriol of 5～15g/L, the ammonium bifluoride of 1～8g/L, the NaNO of 1～15g/L
3, the propanedioic acid of 1～12g/L, the phosphoric acid salt of 1～12g/L, 0.2～6g/L silicate.
The pH value of this passivator is 1.8～2.3, the pH value that adopts yellow soda ash or nitric acid to regulate passivating solution.Its service temperature is 20～35 ℃, and passivation time is 30～60 seconds, and bake out temperature is 70～80 ℃.
The beneficial effect that the present invention adopts above-mentioned technical solution to reach is:
Passivator concentration of the present invention is low, and production cost is low, and is comparatively economical and practical; This trivalent chromium colour passivator does not contain sexavalent chrome fully, is a kind of lower concentration zinc coating passivation agent of environment-friendly type; By adding molybdate, can on zinc coating, form irised passive film under the normal temperature.In the passivating process, the cobalt ion in the solution can deposit in the passive film, has significantly improved the corrosion resistance nature of passive film.Propanedioic acid can promote the growth of passive film, helps improving the thickness of passive film; Phosphoric acid salt and silicate can be adsorbed on the hole place of passive film, and the weakness of passive film is played a protective role.This passivator at room temperature can produce the good iridescent passivation film of solidity to corrosion on the zinc coating surface, helps environment protection, has saved the consumption of the energy simultaneously.
Embodiment
In one liter beaker, add 500 ml deionized water, under the condition of continuously stirring, the chromium chloride that adds 15.3g (contains 3.0 Cr
3+), after the dissolving, add the molybdate of 16.7g successively, the NaNO of 18g fully
3, the propanedioic acid of 8.4g, the phosphoric acid salt of 1.6g stirred one hour; The rose vitriol that adds 10.2g then stirred after two hours, added ammonium bifluoride and the 1.2g silicate of 3.2g, continued to stir 30 minutes; The volume that adds deionized water to 1 liter then, the pH value to 1.9 of regulating passivating solution with yellow soda ash or nitric acid again can be standby.
Test one: will be through the iron plate of the 10X15cm after oil removing, the rust cleaning, put into and electroplate after 10 minutes in the square groove of the acid zinc plating solution that is equipped with 2 liters, salpeter solution activation through 0.5%, immerse then in the above-mentioned passivating solution, maintain the temperature at about 30 ℃, passivation 40 seconds, 80 ℃ of oven dry down, the iron plate surface is an iridescent passivation film attractive in appearance after washing.Under all identical situation of other condition, change passivation time into 60 seconds, obtain similar iridescent passivation film.
Test two: change the acid zinc plating solution in 2 liters of square grooves into alkaline non-cyanogen galvanization solution, the step of revision test one is that the iron plate surface all obtains iridescent passivation film attractive in appearance equally under two kinds of situations of 40 seconds and 60 seconds at passivation time.
Neutral salt spray test is carried out in iron test piece after the passivation in test one and the test two, after 96 hours, tangible white rust do not occur, show excellent corrosion resisting performance.
Claims (3)
1. a normal temperature passivated zinc coating trivalent chromium color passivating agent is characterized in that, it includes the Cr of 1～7.5g/L
3+, the molybdate of 1～25g/L, the rose vitriol of 5～15g/L, the ammonium bifluoride of 1～8g/L, the NaNO of 1～15g/L
3, the propanedioic acid of 1～12g/L, the phosphoric acid salt of 1～12g/L, 0.2～6g/L silicate.
2. normal temperature passivated zinc coating trivalent chromium color passivating agent according to claim 1 is characterized in that Cr
3+By Compound C rCl
3Provide.
3. normal temperature passivated zinc coating trivalent chromium color passivating agent according to claim 1 and 2 is characterized in that, the pH value of above-mentioned passivator is 1.8～2.3, adopt yellow soda ash or nitric acid to regulate the pH value, its temperature is 20～35 ℃, and passivation time is 30～60 seconds, and bake out temperature is 70～80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100358619A CN1858303B (en) | 2006-06-09 | 2006-06-09 | Normal temperature passivated zinc coating trivalent chromium color passivating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100358619A CN1858303B (en) | 2006-06-09 | 2006-06-09 | Normal temperature passivated zinc coating trivalent chromium color passivating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1858303A CN1858303A (en) | 2006-11-08 |
| CN1858303B true CN1858303B (en) | 2010-07-21 |
Family
ID=37297259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100358619A Expired - Fee Related CN1858303B (en) | 2006-06-09 | 2006-06-09 | Normal temperature passivated zinc coating trivalent chromium color passivating agent |
Country Status (1)
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| CN (1) | CN1858303B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168840B (en) * | 2007-11-28 | 2010-06-16 | 东北大学 | Phosphor molybdenum heteropolyacid inactivating treatment liquid used for heat zinc coating plate |
| CN101805897B (en) * | 2010-05-27 | 2012-05-23 | 贵阳华科电镀有限公司 | Passivation method for zinc-plated trivalent chromium |
| CN101812681B (en) * | 2010-05-27 | 2012-02-01 | 贵阳华科电镀有限公司 | Passivation formula of zincification trivalent chromium |
| CN101906629A (en) * | 2010-08-09 | 2010-12-08 | 哈尔滨工业大学 | Blue write chromate-free passivation liquid of electrogalvanized layer and method for passivating electrogalvanized layer by adopting same |
| CN103132068A (en) * | 2011-11-29 | 2013-06-05 | 重庆点石金属表面处理有限公司 | Trivalent chromium concentrated blue and white zinc passivant and passivation method by means of blue and white zinc passivant |
| CN103866309B (en) * | 2014-04-04 | 2016-03-16 | 西南大学 | A kind of trivalent blue-white chromating liquid for the treatment of zinc die casting alloys |
| GB201407690D0 (en) * | 2014-05-01 | 2014-06-18 | Henkel Ag & Co Kgaa | Non chromate coloured conversion coating for aluminum |
| CN104191725A (en) * | 2014-08-28 | 2014-12-10 | 首钢京唐钢铁联合有限责任公司 | Fingerprint-resistant colored galvanized steel plate and manufacturing method thereof |
| CN105111807B (en) * | 2015-09-22 | 2018-01-26 | 攀钢集团攀枝花钢铁研究院有限公司 | The preparation method of high corrosion-resistant coating solution and galvanizing clad plate |
| WO2017219371A1 (en) * | 2016-06-24 | 2017-12-28 | 深圳市恒兆智科技有限公司 | Passivator, zinc plated workpiece and passivation treatment method therefor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393354A (en) * | 1993-10-07 | 1995-02-28 | Mcgean-Rohco, Inc. | Iridescent chromium coatings and method |
-
2006
- 2006-06-09 CN CN2006100358619A patent/CN1858303B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393354A (en) * | 1993-10-07 | 1995-02-28 | Mcgean-Rohco, Inc. | Iridescent chromium coatings and method |
Non-Patent Citations (3)
| Title |
|---|
| 于元春等.无铬钝化与三价铬钝化的研究进展.表面技术34 5.2005,34(5),第6-9页. |
| 于元春等.无铬钝化与三价铬钝化的研究进展.表面技术34 5.2005,34(5),第6-9页. * |
| 陈春成.镀锌层三价铬钝化工艺.2005年上海市电镀与表面精饰学术年会论文集.2005,(2005),第104-106页. * |
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| Publication number | Publication date |
|---|---|
| CN1858303A (en) | 2006-11-08 |
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Owner name: GUANGDONG ZHIZHUO PRECISION METAL TECHNOLOGY CO., Free format text: FORMER OWNER: DUOZHENG CHEMICAL SCIENCE AND TECHNOLOGY CO., LTD., GUANGDONG Effective date: 20140623 |
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Free format text: CORRECT: ADDRESS; FROM: 528139 FOSHAN, GUANGDONG PROVINCE TO: 528200 FOSHAN, GUANGDONG PROVINCE |
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Effective date of registration: 20140623 Address after: 528200 Guangdong city of Foshan province Dali Town Nanhai District Changhong Ridge Industrial Park Patentee after: Guangdong Zhizhuo Precision Metal Technology Co., Ltd. Address before: 528139 Guangdong province Foshan Sanshui Lubao Industrial Development Zone multi way Patentee before: Duozheng Chemical Science and Technology Co., Ltd., Guangdong |
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Granted publication date: 20100721 Termination date: 20160609 |