CN103305824A - Hot-galvanizing chromate-free passivator and production technology thereof - Google Patents
Hot-galvanizing chromate-free passivator and production technology thereof Download PDFInfo
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- CN103305824A CN103305824A CN2013101912486A CN201310191248A CN103305824A CN 103305824 A CN103305824 A CN 103305824A CN 2013101912486 A CN2013101912486 A CN 2013101912486A CN 201310191248 A CN201310191248 A CN 201310191248A CN 103305824 A CN103305824 A CN 103305824A
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- passivator
- chrome
- tungstic acid
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- chromate
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Abstract
The invention discloses a hot-galvanizing chromate-free passivator. The passivator comprises the following ingredients in percentage by mass: 20-40% of tungstophosphoric heteropoly acid, 5-15% of hydroxyethylidene diphosphonic acid, 3-5% of sodium nitrate, 0.1-0.2% of water-based silane coupling agent, 5-10% of polyethylene glycol, and the balance of water. The production technology of the hot-galvanizing chromate-free passivator comprises the steps of: adding sodium dihydrogen phosphate and sodium tungstate into an acidic water solution according to any one mass ratio of 1:1,1:2 and 1:3, heating and reacting to produce tungstophosphoric heteropoly acid, mixing the tungstophosphoric heteropoly acid with hydroxyethylidene diphosphonic acid, the sodium nitrate, water-based silane coupling agent and polyethylene glycol, and then carrying out constant volume to obtain the hot-galvanizing chromate-free passivator. The passivator doe not contain toxic and harmful substances such as hexavalent chromium, trivalent chromium and the like, the production technology of the passivator is simple and easy to operate, and a passivation membrane formed on the zinc layer has excellent physical property and anti-corrosion property.
Description
Technical field
The present invention relates to a kind of chemical processing agent for the hot dip surface passivating treatment, is a kind of novel environment friendly passivator that can substitute the passivation of traditional chromium hydrochlorate, relates in particular to a kind of pot galvanize chrome-free tanning agent.Belong to field of metal surface treatment.
The invention still further relates to a kind of production technique of pot galvanize chrome-free tanning agent.
Background technology
Because iron and steel is easy to get rusty in air, water or soil, even damages fully, the annual iron and steel loss that causes because of corrosion accounts for 1/10 of whole iron and steel output; so, needing to adopt to be coated with, the way of protective layer plating is protected iron and steel; avoid corrosion, pot galvanize is exactly a kind of method wherein.Zinc-plated is to improve the weather-resistant effective ways of iron and steel, but in wet environment, the easy corrosion of zinc coating, the surface forms the corrosives of white loose or becomes gloomy color, has a strong impact on the performance of galvanized workpiece.Therefore thereby zinc coating will carry out Passivation Treatment at zinc layer surface coverage layer protecting film.
Traditional Passivation Treatment adopts chromating more.Chromating is divided into sexavalent chrome passivation and trivalent chromium passivation, and wherein the sexavalent chrome passivation is because price is low, and performance is good, and is most widely used general.But sexavalent chrome is highly toxic substance, and can be carcinogenic.From the angle of protection of the environment and human health, countries in the world all begin restriction even ban use of sexavalent chrome to carry out passivation at present, come into effect the ROHS environmental protection act of non-hexavalent chromium from July, 2006 such as European Union.The another kind of passivation technology of chromating is trivalent chromium passivation, chromic toxicity approximately is chromic 1/100, but have very strong toxicity, use the passive film corrosion resistance of trivalent chromium passivation poorer than sexavalent chrome, and the trivalent chromium passivation film does not have self-healing properties.Therefore, develop the demand of a kind of nontoxic, environmental protection, efficient chrome-free tanning agent very urgent.
Summary of the invention
The present invention is according to the environmental requirement of present zinc-plated industry to passivator, and purpose provides a kind of a kind of pot galvanize chrome-free tanning agent that does not contain the hazardous and noxious substances such as chromium.
Another object of the present invention provides a kind of production technique of pot galvanize chrome-free tanning agent simple to operation.
A kind of pot galvanize chrome-free tanning agent, this passivator is grouped into by the one-tenth of following quality percentage composition:
Phosphorus heteropoly tungstic acid 20～40%;
1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 5～15%;
SODIUMNITRATE 3～5%;
Aqueous silane coupling agent 0.1～0.2%;
Polyoxyethylene glycol 5～10%;
Water surplus.
Preferably, described phosphorus heteropoly tungstic acid reacts generation by SODIUM PHOSPHATE, MONOBASIC and sodium wolframate in acidic aqueous solution.
Preferably, the described phosphorus heteropoly tungstic acid reaction employed SODIUM PHOSPHATE, MONOBASIC of generation and sodium wolframate mass ratio are any one ratio among 1:1,1:2, the 1:3.
A kind of production technique of pot galvanize chrome-free tanning agent, in acidic aqueous solution, any one ratio among 1:1,1:2, the 1:3 adds SODIUM PHOSPHATE, MONOBASIC and sodium wolframate in mass ratio, reacting by heating generates phosphorus heteropoly tungstic acid, and constant volume obtained after phosphorus heteropoly tungstic acid and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, SODIUMNITRATE, aqueous silane coupling agent and the polyoxyethylene glycol that obtains mixed.
Advantage of the present invention:
1, do not contain the hazardous and noxious substances such as sexavalent chrome, trivalent chromium, meet the ROHS environmental protection act that European Union carries out-ban use of sexavalent chrome.
2, passivator production technique of the present invention is simple to operation, forms passive film on zinc layer surface and has good physicals and corrosion resistance.
Embodiment
The following examples can make the present invention of those skilled in the art comprehend, but do not limit the present invention in any way.
Embodiment 1
A kind of pot galvanize chrome-free tanning agent, this passivator is grouped into by the one-tenth of following quality percentage composition:
Phosphorus heteropoly tungstic acid 20%;
1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 5%;
SODIUMNITRATE 3%;
Aqueous silane coupling agent 0.1%;
Polyoxyethylene glycol 5%;
Water surplus.
Above-mentioned said phosphorus heteropoly tungstic acid reacts generation by SODIUM PHOSPHATE, MONOBASIC and sodium wolframate in acidic aqueous solution; Wherein, SODIUM PHOSPHATE, MONOBASIC and sodium wolframate mass ratio are 1:1.
Embodiment 2
A kind of pot galvanize chrome-free tanning agent, this passivator is grouped into by the one-tenth of following quality percentage composition:
Phosphorus heteropoly tungstic acid 30%;
1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 10%;
SODIUMNITRATE 4%;
Aqueous silane coupling agent 0.15%;
Polyoxyethylene glycol 7.5%;
Water surplus.
Above-mentioned said phosphorus heteropoly tungstic acid reacts generation by SODIUM PHOSPHATE, MONOBASIC and sodium wolframate in acidic aqueous solution; Wherein, SODIUM PHOSPHATE, MONOBASIC and sodium wolframate mass ratio are 1:2.
Embodiment 3
A kind of pot galvanize chrome-free tanning agent, this passivator is grouped into by the one-tenth of following quality percentage composition:
Phosphorus heteropoly tungstic acid 40%;
1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 15%;
SODIUMNITRATE 5%;
Aqueous silane coupling agent 0.2%;
Polyoxyethylene glycol 10%;
Water surplus.
Above-mentioned said phosphorus heteropoly tungstic acid reacts generation by SODIUM PHOSPHATE, MONOBASIC and sodium wolframate in acidic aqueous solution, wherein, SODIUM PHOSPHATE, MONOBASIC and sodium wolframate mass ratio are 1:3.
Following examples 4-6 is the production technique of a kind of pot galvanize chrome-free tanning agent of the present invention.
Embodiment 4
In 20kg water, add 10kg SODIUM PHOSPHATE, MONOBASIC and 10kg sodium wolframate, reacting by heating 1 hour; With barrelling behind completely reacted phosphorus heteropoly tungstic acid and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 7kg, SODIUMNITRATE 3kg, aqueous silane coupling agent 0.1kg, polyoxyethylene glycol 8kg, the water 41.9kg mixing, get 100kg passivator.
Embodiment 5
In 30kg water, add 10kg SODIUM PHOSPHATE, MONOBASIC and 20kg sodium wolframate, reacting by heating 1 hour; With barrelling behind completely reacted phosphorus heteropoly tungstic acid and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 8kg, SODIUMNITRATE 5kg, aqueous silane coupling agent 0.2kg, polyoxyethylene glycol 6kg, the water 20.8kg mixing, get 100kg passivator.
Embodiment 6
In 20kg water, add 10kg SODIUM PHOSPHATE, MONOBASIC, 30kg sodium wolframate, reacting by heating 1 hour; With barrelling behind completely reacted phosphorus heteropoly tungstic acid and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 10kg, SODIUMNITRATE 3kg, aqueous silane coupling agent 0.1kg, polyoxyethylene glycol 5kg, the water 21.9kg mixing, get 100kg passivator.
Select the passivator of any one prescription among the embodiment 4～6, the passivation galvanized workpiece.
The passivation technology process is the cleaning oil removing → bright dipping of sample → cleaning → passivation → drying.Bright dipping is used.
Adopt the salpeter solution of mass concentration 6% to clean oil removing, the bright dipping time is 10s, and passivation temperature is 25 ℃, and passivation time is 35s, and 70 ℃ of freeze-day with constant temperature 20min carried out salt-fog test in aging 48 hours under the dry rear room temperature, measured corrosion resistance.
Claims (4)
1. pot galvanize chrome-free tanning agent, it is characterized in that: this passivator is grouped into by the one-tenth of following quality percentage composition:
Phosphorus heteropoly tungstic acid 20～40%;
1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 5～15%;
SODIUMNITRATE 3～5%;
Aqueous silane coupling agent 0.1～0.2%;
Polyoxyethylene glycol 5～10%;
Water surplus.
2. described a kind of pot galvanize chrome-free tanning agent according to claim 1, it is characterized in that: described phosphorus heteropoly tungstic acid reacts generation by SODIUM PHOSPHATE, MONOBASIC and sodium wolframate in acidic aqueous solution.
3. a kind of pot galvanize chrome-free tanning agent according to claim 2 is characterized in that: it is any one ratio among 1:1,1:2, the 1:3 that described phosphorus heteropoly tungstic acid reaction generates employed SODIUM PHOSPHATE, MONOBASIC and sodium wolframate mass ratio.
4. the production technique of a kind of pot galvanize chrome-free tanning agent as claimed in claim 1, it is characterized in that, may further comprise the steps: in acidic aqueous solution, any one ratio among 1:1,1:2, the 1:3 adds SODIUM PHOSPHATE, MONOBASIC and sodium wolframate in mass ratio, reacting by heating generates phosphorus heteropoly tungstic acid, and constant volume obtained after phosphorus heteropoly tungstic acid and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, SODIUMNITRATE, aqueous silane coupling agent and the polyoxyethylene glycol that obtains mixed.
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| CN201310191248.6A CN103305824B (en) | 2013-05-22 | 2013-05-22 | A kind of pot galvanize chrome-free tanning agent and production technique thereof |
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| CN201310191248.6A CN103305824B (en) | 2013-05-22 | 2013-05-22 | A kind of pot galvanize chrome-free tanning agent and production technique thereof |
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| CN103305824A true CN103305824A (en) | 2013-09-18 |
| CN103305824B CN103305824B (en) | 2015-08-05 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106283002A (en) * | 2016-08-29 | 2017-01-04 | 常熟市古里镇白茆新兴网印标牌厂 | Traffic mark board |
| CN112553609A (en) * | 2019-09-10 | 2021-03-26 | 天津大学 | Carbon steel surface phosphonic acid-silane composite membrane and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168840A (en) * | 2007-11-28 | 2008-04-30 | 东北大学 | Phosphor molybdenum heteropolyacid inactivating treatment liquid used for heat zinc coating plate |
-
2013
- 2013-05-22 CN CN201310191248.6A patent/CN103305824B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168840A (en) * | 2007-11-28 | 2008-04-30 | 东北大学 | Phosphor molybdenum heteropolyacid inactivating treatment liquid used for heat zinc coating plate |
Non-Patent Citations (1)
| Title |
|---|
| 张澜萃等: "磷系杂多酸的缓蚀性能研究", 《辽宁化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106283002A (en) * | 2016-08-29 | 2017-01-04 | 常熟市古里镇白茆新兴网印标牌厂 | Traffic mark board |
| CN112553609A (en) * | 2019-09-10 | 2021-03-26 | 天津大学 | Carbon steel surface phosphonic acid-silane composite membrane and preparation method and application thereof |
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| CN103305824B (en) | 2015-08-05 |
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