CN101487116A - Steel surface passivation film forming liquid and use method thereof - Google Patents
Steel surface passivation film forming liquid and use method thereof Download PDFInfo
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- CN101487116A CN101487116A CNA2009100211139A CN200910021113A CN101487116A CN 101487116 A CN101487116 A CN 101487116A CN A2009100211139 A CNA2009100211139 A CN A2009100211139A CN 200910021113 A CN200910021113 A CN 200910021113A CN 101487116 A CN101487116 A CN 101487116A
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Abstract
The invention discloses a steel surface passivation film-forming liquid and a usage method thereof; the prepared steel metal surface passivation film-forming liquid is aqueous solution with the pH value of 0.1-5 and the use temperature of 1-40 DEG C; the time for contacting with the steel metal surface is 5-60 minutes; and according to mass concentration, one liter of aqueous solution is prepared together with 0.01-1% of titanium salt, 5-20% of fluoride and 1-10% of nitric acid. An anti-corrosive film with uniform color is generated on the surface of the steel under a normal temperature state; the anti-corrosive film mainly consists of fluorine ferrite which is friendly to the environment, and has continuous and compact film layer, and excellent anti-corrosion and bonding performances. As hexavalent chromium and phosphate are not used in the production process, the pollution of processing production process of the steel surface and the wasted and used products on the environment is greatly lightened, and the recovery and regeneration process of the wasted and used products of the steel is more convenient.
Description
Technical field
The present invention relates to the treatment process of steel surface corrosion prevention film and steel surface, specifically a kind of iron and steel metal surface passivation film forming liquid and using method thereof.The iron and steel metal surface passivation film forming liquid that makes does not contain sexavalent chrome and phosphoric acid salt, can generate corrosion prevention film at steel surface under the normal temperature state, gives steel surface good anti-corrosion and bond properties, is a kind of environment-friendly type steel surface chemical passivation film forming liquid.
Background technology
Iron and steel accounts for more than 90% of metallic substance usage quantity, yet is general the easiest most widely used corrosive metal in the daily life, and the annual steel products of producing in the whole world have nearly 30% corrosion that is subjected in various degree, wherein has 10% steel products to scrap approximately.About 7,000 hundred million dollars of the financial loss that causes because of corrosion in whole world every year accounts for the 2%-4% of various countries' national economy output value.Steel equipment also descends because of corrosion causes equipment performance, makes production safety be subjected to serious threat, production efficiency descends significantly.
Steel anti-corrosive erosion treatment technology has many, and to carry out that chromating (chemical conversion) handles be two kinds of the most frequently used methods at present in the steel corrosion protection again but steel surface bonderizing and iron and steel metallic surface are zinc-plated.
The steel surface bonderizing is a kind of technology that forms phosphatize phosphate coat by steel substrate with the conversion fluid generation chemical reaction that contains compositions such as phosphoric acid salt, heavy metal ion, fluorion, nitrate, nitrite at steel surface.One of characteristics of phosphatize phosphate coat are porousness, and the solidity to corrosion of film itself is limited, the just rapid scale that produces in drying process that has.Therefore, the purpose of phosphorization treatment technology normally strengthens the bonding force of steel surface and organic coating, and the steel products after it is handled are general only in indoor use.In order to improve the antiseptic power of phosphatize phosphate coat, also must make the further sealing Passivation Treatment of filling, oxygenizement usually after the phosphatization to phosphatize phosphate coat, phosphatize phosphate coat can be stable in the atmosphere.Through the phosphate layer of sealing treatment, can be used as the corrosion resistant coating of iron and steel metallic matrix.However, the phosphatize phosphate coat that produces of this technology still exists the phosphoric acid salt, the heavy metal ion that contain in the relatively poor and phosphatization liquid of corrosion resisting property and environment is caused shortcomings such as eutrophication, heavy metal contamination.
Be used for the steel products and the equipment of outdoor environment for great majority, people adopt zinc-plated iron-steel chromating treatment technology usually, and promptly steel surface is earlier zinc-plated, carry out chromating again on the zinc coating surface and handle.
As a kind of traditional metallic surface processing treatment technology; though the iron and steel metallic surface is zinc-plated and carry out chromating and learn conversion processing and can provide fabulous corrosion protection to iron and steel; but because zinc resource is day by day in short supply; and the use of carcinogenic chromic salt in hypertoxic prussiate, the chromating treating processes in the galvanizing process; especially the product of chromate treating is because conversion film contains the carcinogens sexavalent chrome, and the electronic waste that loses use value discarded back generation pollutes and human environment caused huge harm.Along with the fast development of global information industry, the quickening of model change speed, the annual electronic waste that produces in countries in the world reaches 1,000,000, ten million tons, and this numeral is also soaring year by year.The toxic gas that produces when Toxic seepage, incineration process during the electronic waste landfill disposal has been subjected to global concern to the very big harm that environment and human health cause.Therefore, this traditional technology with one-hundred-year history of metallic surface chromate conversion treatments technology has been faced with the destiny that is cancelled.RoHS (the The Restriction of theUse of Certain Hazardous Substances in Electrical and ElectricEquipment) instruction of " using some objectionable impurities " that European Union implemented on July 1st, 2006 about restriction in electronic and electrical equipment, regulation was from July 1st, 2006, the new electric equipment products that enters European Union market should contain six kinds of objectionable impuritiess such as comprising sexavalent chrome, and its purpose is to improve recovery and the recirculation rate of scrapping electric equipment products, reduce the secondary pollution that the electric equipment products waste material causes water source and soil, ensure the Sustainable development of society.China also carries out the RoHS of European Union instruction on March 1st, 2007, forbids using in the metal surface treatment process process objectionable impuritiess such as sexavalent chrome.
At present, in order to increase the antiseptic property of iron and steel metal, people have proposed various parkerizing methods.As Chinese patent (application number: 03113780.6) disclose a kind of zinc, ferrous metal and assembly thereof with the groove method for bonderizing, the phosphatization liquid that this method adopts metal-salts such as containing phosphoric acid salt and zinc, nickel, manganese and fluorochemical etc. to become to be grouped into, in temperature is under 15 ℃～60 ℃ conditions, bonderizing 3～15 minutes makes zinc, ferrous metal surface obtain the to be up to state standards even phosphatize phosphate coat of performance requriements.Disclosed a kind of chromate composite used for passivation of zine plated layer on metal body of Chinese patent application and application (application number 91102396.8) thereof are adopted by CrO
3, NaHSO
4, NaH
2PO
4, AgNO
3, the passivating solution formed of alkyl polyoxyethylene ether, Passivation Treatment zine plated layer on metal body surface under pH 1.5～1.9 conditions makes zine plated layer on metal body obtain excellent corrosion resistance.
Though the disclosed passivating solution of above-mentioned patent, on iron and steel or zinc coating surface after above-mentioned passivating solution is handled, its surface anticorrosion performance improves greatly, but contain phosphoric acid salt in the passivating solution, heavy metal ion and sexavalent chrome, but human health and environmental ecology are caused serious destruction and influence.
Summary of the invention
At defective that exists in the above-mentioned background technology or deficiency, the objective of the invention is to, a kind of steel surface chemical passivation film forming liquid and using method thereof are provided, this conversion fluid does not contain sexavalent chrome and phosphoric acid salt, the fine and close corrosion prevention film that generates at steel surface under the normal temperature condition has good anti-corrosion and organic coating bond properties, is a kind of environment-friendly type steel surface chemical passivation film forming liquid.
In order to realize above-mentioned task, the present invention adopts following technical solution:
A kind of iron and steel metal surface passivation film forming liquid, it is characterized in that, this iron and steel metal surface passivation film forming liquid that makes is the aqueous solution, this pH value of aqueous solution is 0.1～5, the use temperature of the aqueous solution is 1 ℃～40 ℃, with the duration of contact of iron and steel metallic surface be 5 minutes～60 minutes, prepare in every premium on currency solution and contain:
Titanium salt: its mass concentration is 0.01%～1%; Fluorochemical: its mass concentration is 5%～20%; Nitric acid: its mass concentration is 1%～10%.
The preferred version of above-mentioned iron and steel metal surface passivation film forming liquid is:
Described pH value of aqueous solution is 0.5～4, and the use temperature of the aqueous solution is 5 ℃～30 ℃, with duration of contact of iron and steel metallic surface be 10 minutes～40 minutes, prepare in every premium on currency solution and contain:
Titanium salt: its mass concentration is 0.05%～0.5%; Fluorochemical: its mass concentration is 10%～15%; Nitric acid: its mass concentration is 2.5%～7.5%.
Described titanium salt adopts wherein at least a of titanium chloride, titanium sulfate, titanyl sulfate, titanyl nitrate, sodium titanate, potassium titanate and titanium dioxide.
Described fluorochemical adopts at least a in Neutral ammonium fluoride, ammonium acid fluoride, Sodium Fluoride, sodium hydrogen fluoride, Potassium monofluoride, the potassium bifluoride.
Described nitric acid can be obtained by concentrated nitric acid dilution, also can be by water-soluble nitrate, as, ammonium nitrate, SODIUMNITRATE or saltpetre, regulator solution pH obtains.
The using method of above-mentioned iron and steel metal surface passivation film forming liquid is characterized in that, comprises the following steps:
1) earlier the iron and steel metallic surface is carried out using rinsed with deionized water after the skimming treatment;
2) again the iron and steel metallic surface is carried out using rinsed with deionized water after the processing of rust removing;
3) adopt iron and steel metal surface passivation liquid to carry out conversion processing, this aqueous solution in use, temperature is controlled at 1 ℃～40 ℃, pH is 0.1～5, with duration of contact of iron and steel metallic surface be 5 minutes～60 minutes;
4) the iron and steel metal after the conversion processing is cleaned with deionization after, seasoning promptly forms the uniform passive film of color and luster in the iron and steel metallic surface.
Iron and steel metal surface passivation film forming liquid of the present invention, owing to do not contain phosphoric acid salt, the carcinogens six chromium valency (chromic salt) and the deleterious metal ions that can cause body eutrophication, not only the pollution to environment alleviates greatly, and cost reduces significantly.
The present invention has made full use of the oxidisability and the strongly-acid of rare nitric acid, with the iron of iron and steel metallic surface be oxidized to ferric ion or at a low price ferriferous oxide be oxidized to the ferric oxide that can be dissolved in acid and become ferric ion, after fluorion in the conversion fluid and ferric ion complexing form fluorine iron complex ion, to generate fluorine wustite precipitation with ammonium ion in the conversion fluid or potassium ion or sodium ion reaction, the result form in the iron and steel metallic surface with indissoluble be that the densification of main component transforms rete with the fluorine wustite, the erosion resistance of iron and steel metal is greatly enhanced.The passive film that is generated owing to utilized the dissolved composition in iron and steel metallic surface own--ferric ion forms the characteristics of conversion film, makes that fine and close conversion film is easy to form at steel surface, and the conversion film corrosion resisting property is good, with the organic coating strong adhesion.
Description of drawings
Fig. 1 is the analysis of A3 steel surface conversion coating X-ray energy spectrum.
The present invention is described in further detail below in conjunction with embodiment that accompanying drawing and contriver provide.
Embodiment
The iron and steel metal surface passivation film forming liquid that the present invention makes is the aqueous solution that contains nitric acid, fluorochemical, titanium salt.
1, nitric acid
The nitric acid that adopts is obtained by the concentrated nitric acid dilution, and concentration is preferably in 2.5%～7.5% scope at 1%～10% (massfraction, down together).Concentration of nitric acid is too high or too low, is difficult to generate in the iron and steel metallic surface densification conversion rete of fluorine wustite.Nitric acid also can be by water-soluble nitrate, for example, ammonium nitrate, SODIUMNITRATE or saltpetre, regulator solution pH obtains.
2, fluorochemical
As fluorochemical, for example can enumerate Neutral ammonium fluoride (NH
4F), ammonium acid fluoride (NH
4HF
2), Sodium Fluoride (NaF), Potassium monofluoride (KF), sodium hydrogen fluoride (NaHF
2) and potassium bifluoride (KHF
2) etc.In the treatment solution of present embodiment, the fluorochemical of adding is wherein at least a of above-mentioned fluorochemical, and the fluorochemical massfraction of adding is 5%～20%, is preferably in 10%～15%.Fluoride concn is lower than 5% or be higher than 20%, all is difficult to transform rete generating the fluorine wustite in the iron and steel metallic surface.
3, titanium salt
As titanium salt, for example can enumerate titanium oxide (TiCl
4), titanium sulfate (Ti (SO
4)
2), titanyl sulfate (TiOSO
4), titanyl nitrate (TiO (NO
3)
2), sodium titanate (Na
2TiO
3), potassium titanate (K
2TiO
3), titanium dioxide (TiO
2) wait at least a.The titanium salt concentration that adds is 0.01%～1%, is preferably in 0.05%～0.5%.Titanium salt generates the titanium hydroxide precipitation in reaction process makes fluorine wustite rete fine and close more.When titanium salt concentration is too low, can not produce the titanium salt precipitation.On the other hand, in treatment solution, when the concentration of titanium salt in treatment solution was too high, even add titanium salt, effect did not increase, and therefore, titanium salt concentration is advisable with interior 1%.
Below, the step of using this iron and steel metal surface passivation film forming liquid to handle iron and steel metallic surface method is listed below:
1, earlier iron and steel metallic surface grease is removed the back rinsed with deionized water;
2, again the iron and steel metallic surface is carried out using rinsed with deionized water after the processing of rust removing;
3, adopt iron and steel metal surface passivation film forming liquid to carry out conversion processing, this aqueous solution in use, temperature is controlled at 1～40 ℃, the pH value is 0.1～5, with duration of contact of iron and steel metallic surface be 5～60 minutes;
4, last, after the iron and steel metallic surface after the conversion processing cleaned with deionization, seasoning promptly formed the uniform passive film of color and luster in the iron and steel metallic surface.
Below be the embodiment that the contriver provides, need to prove that this embodiment is more excellent example, the invention is not restricted to this embodiment.
Embodiment: A3 steel immersion temperature is 80 ℃～90 ℃ contains 40% sodium hydroxide (mass concentration, down together), the alkaline cleaner of 80% yellow soda ash, 10% water glass carried out skimming treatment in 20 minutes, after the deionization washing this metal immersed at ambient temperature and contain in 5% hexamethylenetetramine, 20% the hydrochloric acid soln 30～40 minutes and carry out processing of rust removing, after rinsed with deionized water, immerse iron and steel metal surface passivation film forming liquid again and carry out chemical passivation and handle.The composition that mainly contains of iron and steel metal surface passivation film forming liquid is: nitric acid 4%, titanyl sulfate 0.5%, Potassium monofluoride 10%.The pH value of iron and steel metal surface passivation film forming liquid is 2, is under 18 ℃～20 ℃ conditions in temperature, reacts after 20 minutes the A3 steel is taken out the after washing drying.
Formed passive film is made up of the close particle of many sizes, and neutral salt spray test (ASTMB117) can reach 2 hours, and adopting hundred lattice cuttves to draw the lattice experiment test, to show that conversion film and colored paint or varnish combine sticking power good.Fig. 1 is the X-ray energy spectrum analysis (EDAX) on the A3 steel surface after the conversion processing.Analytical results shows that this passive film is mainly elementary composition by K, Na, Fe, F and a spot of Ti.The weight content of K, Na, Fe, F and Ti is respectively 11.82%, 4.63%, and 45.66%, 36.64% and 1.25%.According to this ratio, passive film mainly is made up of fluorine potassium ferrite sodium, and the iron ion that promotor KF and dissolving produce has participated in the formation of passive film.
Claims (8)
1, a kind of iron and steel metal surface passivation film forming liquid, it is characterized in that, this iron and steel metal surface passivation film forming liquid that makes is the aqueous solution, this pH value of aqueous solution is 0.1～5, use temperature is 1 ℃～40 ℃, with the duration of contact of iron and steel metallic surface be 5 minutes～60 minutes, contain in every premium on currency solution of preparation:
Titanium salt: its mass concentration is 0.01%～1%; Fluorochemical: its mass concentration is 5%～20%; Nitric acid: its mass concentration is 1%～10%.
2, iron and steel metal surface passivation film forming liquid as claimed in claim 1, it is characterized in that described pH value of aqueous solution is 0.5～4, the use temperature of the aqueous solution is 5 ℃～30 ℃, with the duration of contact of iron and steel metallic surface be 10 minutes～40 minutes, prepare in every premium on currency solution and contain:
Titanium salt: its mass concentration is 0.05%～0.5%; Fluorochemical: its mass concentration is 10%～15%; Nitric acid: its mass concentration is 2.5%～7.5%.
3, iron and steel metal surface passivation film forming liquid as claimed in claim 1 or 2 is characterized in that, described titanium salt adopts wherein at least a of titanium chloride, titanium sulfate, titanyl sulfate, titanyl nitrate, sodium titanate, potassium titanate and titanium dioxide.
4, iron and steel metal surface passivation film forming liquid according to claim 1 and 2 is characterized in that: described fluorochemical adopts wherein at least a of Neutral ammonium fluoride, ammonium acid fluoride, Sodium Fluoride, sodium hydrogen fluoride, Potassium monofluoride and potassium bifluoride.
5, iron and steel metal surface passivation film forming liquid according to claim 1 and 2 is characterized in that, described nitric acid is obtained by the concentrated nitric acid dilution, is perhaps obtained by water-soluble nitrate regulator solution pH.
6, iron and steel metal surface passivation film forming liquid as claimed in claim 5 is characterized in that described nitrate is ammonium nitrate, SODIUMNITRATE or saltpetre.
7, the using method of the described iron and steel metal surface passivation of claim 1 film forming liquid is characterized in that, comprises the following steps:
1) the iron and steel metallic surface is carried out using rinsed with deionized water after the skimming treatment;
2) the iron and steel metallic surface is carried out using rinsed with deionized water after the processing of rust removing;
3) use the described iron and steel metal surface passivation of claim 1 film forming liquid to carry out conversion processing, this aqueous solution in use, temperature is controlled at 1 ℃～40 ℃, pH is 0.1～5, with duration of contact of iron and steel metallic surface be 5 minutes～60 minutes;
4) the iron and steel metallic surface after the conversion processing is cleaned with deionization after, seasoning promptly forms the uniform passive film of color and luster in the iron and steel metallic surface.
8, method as claimed in claim 7 is characterized in that, described temperature is 5 ℃～30 ℃, and the pH value is 0.5～4, with duration of contact of iron and steel metallic surface be 10 minutes～40 minutes.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942655A (en) * | 2010-09-28 | 2011-01-12 | 武汉金泽新时代科技有限公司 | Preparation method of chromium-free passivated liquid and method for passivating electrogalvanizing or zinc alloy layer by same |
| CN102851660A (en) * | 2012-09-29 | 2013-01-02 | 西安建筑科技大学 | Phosphorus-free and chromium-free passive film-forming solution for steel surfaces and usage method thereof |
| CN104357825A (en) * | 2014-11-14 | 2015-02-18 | 无锡伊佩克科技有限公司 | Tinned steel plate surface treatment solution and preparation method thereof |
| CN104357822A (en) * | 2014-10-24 | 2015-02-18 | 无锡伊佩克科技有限公司 | Environment-friendly steel surface treating fluid |
| CN104389003A (en) * | 2014-10-24 | 2015-03-04 | 无锡伊佩克科技有限公司 | Surface treatment liquid for iron and steel |
| CN106521468A (en) * | 2016-12-02 | 2017-03-22 | 机械科学研究总院青岛分院 | Surface passivating treatment process for steel plate |
| CN107920960A (en) * | 2015-08-12 | 2018-04-17 | 义获嘉伟瓦登特公司 | For nursing one's health the medicament of dentine and enamel |
| CN108728837A (en) * | 2017-04-20 | 2018-11-02 | 昆山汉鼎精密金属有限公司 | Non-phosphate film agent, non-phosphate film processing method and products thereof |
| CN109576694A (en) * | 2018-12-28 | 2019-04-05 | 无锡铱美特科技有限公司 | A kind of steel surface blue conversion film is at film liquid and its application method |
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2009
- 2009-02-13 CN CN2009100211139A patent/CN101487116B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942655A (en) * | 2010-09-28 | 2011-01-12 | 武汉金泽新时代科技有限公司 | Preparation method of chromium-free passivated liquid and method for passivating electrogalvanizing or zinc alloy layer by same |
| CN102851660A (en) * | 2012-09-29 | 2013-01-02 | 西安建筑科技大学 | Phosphorus-free and chromium-free passive film-forming solution for steel surfaces and usage method thereof |
| CN104357822A (en) * | 2014-10-24 | 2015-02-18 | 无锡伊佩克科技有限公司 | Environment-friendly steel surface treating fluid |
| CN104389003A (en) * | 2014-10-24 | 2015-03-04 | 无锡伊佩克科技有限公司 | Surface treatment liquid for iron and steel |
| CN104357825A (en) * | 2014-11-14 | 2015-02-18 | 无锡伊佩克科技有限公司 | Tinned steel plate surface treatment solution and preparation method thereof |
| CN107920960A (en) * | 2015-08-12 | 2018-04-17 | 义获嘉伟瓦登特公司 | For nursing one's health the medicament of dentine and enamel |
| CN106521468A (en) * | 2016-12-02 | 2017-03-22 | 机械科学研究总院青岛分院 | Surface passivating treatment process for steel plate |
| CN108728837A (en) * | 2017-04-20 | 2018-11-02 | 昆山汉鼎精密金属有限公司 | Non-phosphate film agent, non-phosphate film processing method and products thereof |
| CN109576694A (en) * | 2018-12-28 | 2019-04-05 | 无锡铱美特科技有限公司 | A kind of steel surface blue conversion film is at film liquid and its application method |
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