CN1268583A - Chrome-free passivating solution for protecting galvanized layer and its coating method - Google Patents
Chrome-free passivating solution for protecting galvanized layer and its coating method Download PDFInfo
- Publication number
- CN1268583A CN1268583A CN 00114178 CN00114178A CN1268583A CN 1268583 A CN1268583 A CN 1268583A CN 00114178 CN00114178 CN 00114178 CN 00114178 A CN00114178 A CN 00114178A CN 1268583 A CN1268583 A CN 1268583A
- Authority
- CN
- China
- Prior art keywords
- coating
- solution
- molybdate
- chrome
- passivation
- 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.)
- Granted
Links
Landscapes
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present invention relates to chrome free passivation liquid for protecting galvanized layer and its coating method. Said invention uses non-poisonous water soluble acrylate resin and chrome free buffering agent molybdenum salt to prepare colorless, transparent passivation liquid with pH value 6-9, and adopts dipping coating, spray coating or rolling wating to uniformly coat the passivation liquid on the object surface to be galvanized. The galvanized layer using the invented method is strong in anti corrosion property and the invented method can substitute prior art passivation method using poisonous chromate so that it is advantages to environmentel protection.
Description
The present invention relates to the passivation of zinc coating, specifically be meant a kind of be used to protect Unchromium Passivation of Galvanized Zinc Layer liquid and coating method thereof, be applicable to electro-galvanizing, pot galvanize, thermospray zinc and mechanical zinc-plating etc., be particularly suitable for the aftertreatment of hot galvanizing piece.
Zinc-plated is the effective ways that improve the iron and steel weather-resistance.But in a humid environment, zinc coating corrodes easily, forms the corrosion product of white loose and will white bright coating becomes gloomy unglazedly at coating surface, influences outward appearance.Most popular anti-white rust method is the chromating method at present, and this passivating method technology is simple, cost is low, etch resistant properties good.But form chromium/matrix metal mixed oxide rete behind chromate treating, chromium mainly exists with sexavalence and trivalent form in the rete.Because sexavalent chrome is a carcinogenic substance, and human body and environment are all had serious harm.Along with the enhancing of people's Environmental awareness, use, the discharging of government's strict restriction chromic salt.Thereby must a kind of method that can replace poisonous chromating of research.
The objective of the invention is to overcome the deficiencies in the prior art part, provide a kind of zinc coating chromium-free passivation liquid and coating method thereof that anti-white rust is used, to replace deleterious chromating method.
The objective of the invention is to realize by following measure:
Be used to protect the preparation of the chromium-free passivation liquid of zinc coating:
(1) by the water soluble acrylate resin: the volume ratio dilution of water=1: 1～4;
(2) the water soluble acrylate resin's solution after every liter of dilution adds 1～5g molybdate;
(3) passivating solution of colourless, transparent, pH=6～9 of gained.
Molybdate refers to potassium molybdate, Sodium orthomolybdate, ammonium molybdate.
Be used to protect the coating processes of the Chrome-free refined solution of zinc coating: can adopt dip-coating or spraying or roller coating method; passivating solution of the present invention evenly is coated in the galvanized workpiece surface of cleaning; when the workpiece water that it is characterized in that just finishing the pot galvanize operation is cooled to 80～90 ℃, promptly carry out the coating of passivating solution.
The present invention selects nontoxic soluble molybdenum hydrochlorate to make the chromium-free passivation liquid that inhibiter and non-toxic water soluble acrylate resin solution are mixed with; be to utilize the easy film forming characteristics of resin; add again and have the passivator of corrosion inhibition to play crosslinked action, form the passivation protection layer that densification has " self-healing " ability again.Colourless, transparent passivating solution is coated on the plating piece of cleaning with methods such as dip-coating, spraying, roller coating, after the solution film drying, promptly generates the protective membrane that one deck has anti-" white rust " ability, adopt drying effect better.
For hot galvanizing piece, in the time of can after zinc-plated, being water-cooled to 80～90 ℃, promptly immerse in the passivating solution of this invention; unplated piece is mentioned after fully immersing passivating solution; can utilize the waste heat of plating piece itself like this, make the passivation layer substantially dry, form the water white thinfilm protective coating of one deck.
The present invention compared with prior art has following outstanding advantage:
1, this law is utilized water soluble acrylate resin's good film-forming property and the nontoxic advantage of molybdate, and it is crosslinked that inhibiter and organism are produced, and constitutes screen layer, therefore adopts this deactivation method to improve the resistance to corrosion of galvanized workpiece effectively.Each embodiment products obtained therefrom examination result is listed by subordinate list.Effect against corrosion by the approaching present poisonous chromating method of subordinate list effect against corrosion of the present invention as can be seen.
2, the present invention discloses the chromium-free deactivation method that is used for zinc-plated material surface, a kind of chromium-free passivation liquid is provided, the method that has replaced present widely used poisonous chromating, realized the target of galvanized workpiece Chrome-free, nontoxic passivation, help environmental protection, have broad application prospects and good social benefit.
3, adopt water soluble acrylate resin's solution and aluminate, low price, the preparation method is simple, easy to use, the scope of application is wide, applicable to galvanized pipe, iron tower, microwave communication tower, freeway guardrail etc., therefore has good popularizing application prospect and economic benefit.
4, when the present invention is used to handle hot galvanizing piece, utilize the waste heat of plating piece itself, make the passivation layer seasoning fast.
The present invention is described in further detail by following embodiment 1～18:
Subordinate list is the prescription of each embodiment and the zinc-plated sample corrosion experiment assay after the coating of employing this law.In the present embodiment, select for use the hard reddening plant produced in Guangzhou, the trade mark is water soluble acrylate resin and the commercially available molybdate of WS-1A, and press the prescription shown in the subordinate list and modulates pH=6～9, molybdate concentration is 0.1～0.5% colourless, transparent passivating solution.The passivating solution coating processes is as follows:
At first that the galvanized workpiece surface cleaning is clean, passivating solution of the present invention is evenly coated on the plating piece of cleaning with methods such as dip-coating, spraying, roller coating, treat the solution seasoning after, promptly generate the protective membrane that one deck has anti-" white rust " ability, adopt drying effect better.For electroplating and hot galvanizing piece, should passivation immediately after zinc-plated.When hot galvanizing piece can be water-cooled to 80～90 ℃ after galvanizing; promptly hot galvanizing piece is coated with full passivating solution with methods such as dip-coating, spraying, rolling are coated with; can utilize the waste heat of plating piece like this; make that the passivation liquid film that is attached to plating piece is very fast to be done, and form even, transparent, have anti-" white rust " ability thinfilm protective coating.
Estimating the resistance to corrosion on zinc coating of the present invention surface, is to check by accelerated corrosion test.The subordinate list test-results obtains according to following experiment content:
(1) neutral salt spray corrosion test (NSS)
Sample through passivation is placed in the YC-40 type salt fog cabinet, with reference to the ISO3768 standard, adopts 5%NaCl solution, PH6.5～7.2, temperature are 35 ± 2 ℃, adopt spraying 3,6h continuously, observe and " white rust " area, the percentage ratio (being preferably 0) of surface measurements " white rust " area occur.
(2) humid heat test
The passivation sample is placed on relative humidity 100%, and temperature is under 45 ± 2 ℃ the condition, to make regular check on sample loses metalluster in hygrothermal environment area.
(3) saline soak test
The passivation sample is immersed in respectively in the 5%NaCl aqueous solution, observes the area that " scales " appears in its surface through certain hour.
Embodiment 1～18 corrosion experiment assay for details see attached table.
Subordinate list:
| The embodiment sequence number | Prescription | Corrosion test result (in corroded area %) | ||||||||||
| Acrylate resin (ml) | Water (mg) | Molybdate (gram) | ??pH | Salt fog | Damp and hot | Saline soak | ||||||
| ??3h | ??6h | 4 days | 9 days | 13 days | 4 days | 9 days | 13 days | |||||
| ??1 ??2 ??3 | ????50 ????33 ????50 | ??50 ??67 ??50 | Sodium orthomolybdate 0.1 Sodium orthomolybdate 0.2 Sodium orthomolybdate 0.5 | ??8.0 ??8.0 ??8.5 | ??0 ??4 ??0 | ??5 ??6 ??4 | ??10 ??5 ??10 | ??10 ??10 ??10 | ??15 ??10 ??15 | ??5 ??5 ??5 | ??10 ??20 ??10 | ??20 ??20 ??30 |
| ??4 ??5 ??6 | ????25 ????25 ????25 | ??75 ??75 ??75 | Sodium orthomolybdate 0.2 Sodium orthomolybdate 0.3 Sodium orthomolybdate 0.5 | ??6.0 ??6.0 ??6.5 | ??5 ??0 ??0 | ??6 ??5 ??3 | ??8 ??6 ??5 | ??10 ??10 ??10 | ??20 ??15 ??15 | ??5 ??3 ??0 | ??10 ??10 ??15 | ??30 ??15 ??25 |
| ??7 ??8 ??9 | ????50 ????33 ????50 | ??50 ??67 ??50 | Potassium molybdate 0.1 potassium molybdate 0.2 potassium molybdate 0.5 | ??8.5 ??8.5 ??9.0 | ??5 ??0 ??0 | ??6 ??0 ??2 | ??5 ??6 ??10 | ??10 ??10 ??10 | ??15 ??10 ??10 | ??0 ??4 ??0 | ??5 ??10 ??5 | ??8 ??15 ??20 |
| ??10 ??11 ??12 | ????25 ????25 ????25 | ??75 ??75 ??75 | Potassium molybdate 0.2 potassium molybdate 0.4 potassium molybdate 0.5 | ??6.5 ??6.5 ??6.5 | ??6 ??0 ??0 | ??8 ??4 ??5 | ??10 ??10 ??5 | ??10 ??15 ??10 | ??25 ??20 ??15 | ??4 ??5 ??0 | ??15 ??20 ??20 | ??20 ??30 ??25 |
| ??13 ??14 ??15 | ????50 ????33 ????50 | ??50 ??67 ??50 | Ammonium molybdate 0.1 ammonium molybdate 0.2 ammonium molybdate 0.5 | ??8.5 ??8.5 ??8.5 | ??0 ??0 ??0 | ??5 ??3 ??0 | ??10 ??10 ??5 | ??10 ??15 ??10 | ??15 ??10 ??5 | ??4 ??0 ??0 | ??20 ??20 ??0 | ??25 ??30 ??5 |
| ??16 ??17 ??18 | ????25 ????25 ????25 | ??75 ??75 ??75 | Ammonium molybdate 0.2 ammonium molybdate 0.4 ammonium molybdate 0.5 | ??6.5 ??6.5 ??6.5 | ??0 ??0 ??0 | ??6 ??4 ??2 | ??10 ??5 ??3 | ??15 ??10 ??5 | ??15 ??10 ??5 | ??5 ??0 ??0 | ??15 ??8 ??10 | ??30 ??8 ??10 |
Claims (3)
1, be used to protect the chromium-free passivation liquid of zinc coating, it is characterized in that: preparation of passivation solution and compound method are as follows:
(1) by the water soluble acrylate resin: the volume ratio dilution of water=1: 1～4;
(2) the water soluble acrylate resin's solution after every liter of dilution adds 1～5g molybdate;
(3) passivating solution of colourless, transparent, pH=6～9 of gained.
2, the Chrome-free refined solution that is used to protect zinc coating according to claim 1, it is characterized in that: molybdate refers to potassium molybdate, Sodium orthomolybdate, ammonium molybdate.
3, be used to protect the coating method of the Chrome-free refined solution of zinc coating; can adopt dip-coating or spraying or roller coating method; passivating solution of the present invention evenly is coated in the galvanized workpiece surface of cleaning; it is characterized in that: when the workpiece water that will just finish the pot galvanize operation is cooled to 80～90 ℃, promptly carry out the coating of passivating solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001141783A CN1158407C (en) | 2000-04-04 | 2000-04-04 | Chrome-free passivating solution for protecting galvanized layer and its coating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001141783A CN1158407C (en) | 2000-04-04 | 2000-04-04 | Chrome-free passivating solution for protecting galvanized layer and its coating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1268583A true CN1268583A (en) | 2000-10-04 |
| CN1158407C CN1158407C (en) | 2004-07-21 |
Family
ID=4583891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001141783A Expired - Fee Related CN1158407C (en) | 2000-04-04 | 2000-04-04 | Chrome-free passivating solution for protecting galvanized layer and its coating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1158407C (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005068683A1 (en) * | 2004-01-08 | 2005-07-28 | China International Marine Containers(Group) Co., Ltd. | Chrome-free passivating solution |
| CN101220473B (en) * | 2007-01-11 | 2010-07-14 | 沈阳宏迪科技有限公司 | Chromium-free passivation liquid for galvanized sheet |
| WO2011020328A1 (en) * | 2009-08-21 | 2011-02-24 | 攀钢集团钢铁钒钛股份有限公司 | Passivation treatment agent for hot-dip aluminum-zinc plated sheet and production method and use thereof |
| CN101215701B (en) * | 2007-12-28 | 2011-03-30 | 中国钢研科技集团公司 | Nontoxic inactivating liquid for continuous galvanizing and alloy plating coat thereof |
| CN102337532A (en) * | 2011-07-11 | 2012-02-01 | 武汉迪赛高科技研究发展有限公司 | Chromium-free passivation liquid applied to surface of zinc-coated layer |
| DE112009001790T5 (en) | 2009-05-18 | 2012-05-31 | Pangang Group Co. Ltd. | Coating agent and passivated, galvanized material |
| CN103031554A (en) * | 2012-11-29 | 2013-04-10 | 桐乡市铁盛线路器材有限公司 | Formula of hot dip organic low acid chromate-free passivator |
| CN103360916A (en) * | 2012-03-31 | 2013-10-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective paint and application thereof, and hot-dip metal material |
| CN103360911A (en) * | 2012-03-31 | 2013-10-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective paint and application thereof, and hot-dip metal material |
| CN103911609A (en) * | 2013-12-20 | 2014-07-09 | 华南理工大学 | Environment-friendly silicate passivation solution for galvanization, and preparation method and application thereof |
| CN104060257A (en) * | 2014-05-26 | 2014-09-24 | 安徽红桥金属制造有限公司 | Chromium-free passivator for zinc coating and preparation method of chromium-free passivator |
| CN106245020A (en) * | 2016-06-16 | 2016-12-21 | 江苏江电电力设备有限公司 | Novel environment friendly passivating solution |
| CN106399995A (en) * | 2016-11-30 | 2017-02-15 | 淄博传能新材料科技有限公司 | Non-chrome hot galvanizing passivation solution and preparing method thereof |
| CN107829082A (en) * | 2017-11-07 | 2018-03-23 | 北京安邦之星科技有限公司 | Environment-friendly galvanizing layer film agent, preparation method and the rust-preventing film comprising the film agent |
-
2000
- 2000-04-04 CN CNB001141783A patent/CN1158407C/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7699926B2 (en) | 2004-01-08 | 2010-04-20 | China International Marine Containers (Group) Co., Ltd. | Chrome-free passivating solution |
| WO2005068683A1 (en) * | 2004-01-08 | 2005-07-28 | China International Marine Containers(Group) Co., Ltd. | Chrome-free passivating solution |
| CN101220473B (en) * | 2007-01-11 | 2010-07-14 | 沈阳宏迪科技有限公司 | Chromium-free passivation liquid for galvanized sheet |
| CN101215701B (en) * | 2007-12-28 | 2011-03-30 | 中国钢研科技集团公司 | Nontoxic inactivating liquid for continuous galvanizing and alloy plating coat thereof |
| DE112009001790T5 (en) | 2009-05-18 | 2012-05-31 | Pangang Group Co. Ltd. | Coating agent and passivated, galvanized material |
| US8742000B2 (en) | 2009-05-18 | 2014-06-03 | Pangang Group Steel Vanadium and Titanium Co., Ltd. | Preparation method of hot dip galvanized sheet anti-corrosive treatment agent of environmental protective |
| US8728628B2 (en) | 2009-08-21 | 2014-05-20 | Pangang Group Steel Vanadium and Titanium Co., Ltd. | Passivant for hot-dip Al-Zn-coated sheet and preparation method and use thereof |
| WO2011020328A1 (en) * | 2009-08-21 | 2011-02-24 | 攀钢集团钢铁钒钛股份有限公司 | Passivation treatment agent for hot-dip aluminum-zinc plated sheet and production method and use thereof |
| CN102337532A (en) * | 2011-07-11 | 2012-02-01 | 武汉迪赛高科技研究发展有限公司 | Chromium-free passivation liquid applied to surface of zinc-coated layer |
| CN103360911A (en) * | 2012-03-31 | 2013-10-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective paint and application thereof, and hot-dip metal material |
| CN103360916A (en) * | 2012-03-31 | 2013-10-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Metal protective paint and application thereof, and hot-dip metal material |
| CN103360911B (en) * | 2012-03-31 | 2015-10-28 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of metal protection coating and uses thereof and hot-dip metal plated material |
| CN103360916B (en) * | 2012-03-31 | 2015-10-28 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of metal protection coating and uses thereof and hot-dip metal plated material |
| CN103031554A (en) * | 2012-11-29 | 2013-04-10 | 桐乡市铁盛线路器材有限公司 | Formula of hot dip organic low acid chromate-free passivator |
| CN103911609A (en) * | 2013-12-20 | 2014-07-09 | 华南理工大学 | Environment-friendly silicate passivation solution for galvanization, and preparation method and application thereof |
| CN103911609B (en) * | 2013-12-20 | 2016-03-02 | 华南理工大学 | A kind of environmentally friendly zinc-plated silicate passivation solution and preparation method thereof and application |
| CN104060257A (en) * | 2014-05-26 | 2014-09-24 | 安徽红桥金属制造有限公司 | Chromium-free passivator for zinc coating and preparation method of chromium-free passivator |
| CN106245020A (en) * | 2016-06-16 | 2016-12-21 | 江苏江电电力设备有限公司 | Novel environment friendly passivating solution |
| CN106399995A (en) * | 2016-11-30 | 2017-02-15 | 淄博传能新材料科技有限公司 | Non-chrome hot galvanizing passivation solution and preparing method thereof |
| CN107829082A (en) * | 2017-11-07 | 2018-03-23 | 北京安邦之星科技有限公司 | Environment-friendly galvanizing layer film agent, preparation method and the rust-preventing film comprising the film agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1158407C (en) | 2004-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1158407C (en) | Chrome-free passivating solution for protecting galvanized layer and its coating method | |
| CN100585004C (en) | The chromium-free passivation liquid that is used for galvanized steel sheet surface | |
| US3132055A (en) | Antirusting surface treating method for iron and steel products | |
| CN101886259A (en) | Zinc coat environmental-friendly passivation solution and use method thereof | |
| CN105088208A (en) | Trivalent chrome complex for hot dip aluminum-zinc plate and preparation method of trivalent chrome complex | |
| EP0038122A1 (en) | Forming corrosion-resistant coatings upon the surfaces of metals, especially zinc | |
| CN87103418A (en) | Process for coating metal surfaces and all compositions | |
| JPH04276087A (en) | Method for after-cleaning of formed layer | |
| US5843338A (en) | Water-soluble composition for water-repellent treatments of zinc and zinc alloy and method for water repellent treatment | |
| CN102864447B (en) | Compound passivating fluid for mechanical zinc coating | |
| US5846342A (en) | Surface treatment agent for zinciferous-plated steel | |
| AU767115B2 (en) | Galvanized steel for use in vehicle body | |
| CN110079795B (en) | Galvanized part surface treating agent and preparation method thereof | |
| CN111155077B (en) | Chromium-free passivation solution for electrogalvanizing and passivation process thereof | |
| CN112813425A (en) | Trivalent chromium passivation solution for zinc plating and preparation method and application thereof | |
| CN103924228A (en) | Metal material with excellent corrosion resistance | |
| JP3475908B2 (en) | Method for improving the weather resistance of zinc-based plating materials | |
| CN104388913A (en) | Hot galvanizing chromate-free passivation liquid and preparation method thereof | |
| CN104328421A (en) | Aviation aluminium alloy chromium-free passivation process | |
| Lin et al. | Self-healing performance of composite coatings prepared by phosphating and cerium nitrate post-sealing | |
| CN115896769B (en) | Inter-sequence protection passivation treatment liquid for production of coated steel plates, preparation method thereof and film forming process | |
| CN102560307A (en) | Production process of multiple aluminum zinc alloy hot-dipped on surface of carbon steel | |
| KR100428838B1 (en) | Manufacturing method of anti-finger treatment steel sheets | |
| CN106756947A (en) | A kind of preparation method of Chrome-free bright blue passivation film | |
| CN1037199C (en) | Pre-treating zinciferous surfaces before conventional chromating to improve rust resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |