CN104357822A - Environment-friendly steel surface treating fluid - Google Patents
Environment-friendly steel surface treating fluid Download PDFInfo
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- CN104357822A CN104357822A CN201410573862.3A CN201410573862A CN104357822A CN 104357822 A CN104357822 A CN 104357822A CN 201410573862 A CN201410573862 A CN 201410573862A CN 104357822 A CN104357822 A CN 104357822A
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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
- 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
- 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
- C23C22/34—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 fluorides or complex fluorides
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses an environment-friendly steel surface treating fluid which comprises the following components: titanium salt with the mass concentration of 0.1% to 1.5%, vanadium compound with the mass concentration of 2% to 15%, fluoride with the mass concentration of 5% to 20%, acid used for regulating the pH value of passivation solution to be 3 to 4, sodium phytate with the mass concentration of 2% to 15%, surfactant with the mass concentration of 0.5% to 3.5%, and the balance of water and other inevitable impurities. When used for treating steel material, the surface treating fluid provided by the invention is simple in process, easy to implement and relatively low in cost; chrome-free surface treatment can be absolutely carried out on a traditional chrome processing production line made of steel plates only by adding a small amount of auxiliary instruments or equipment, and then waste water treatment can be relatively simple, so that the cost can be reduced, and obvious economic benefits can be brought.
Description
Technical field
The present invention relates to Steel surface modification processing technology field, particularly a kind of environment-friendly type treating liquid for surface of iron or steel.
Background technology
Iron and steel accounts for more than 90% of metallic substance usage quantity, is most widely used general but but hold most corrosion-prone metal in daily life, the corrosion that the steel products that the whole world produces every year have nearly 30% to be subject in various degree, wherein about has the steel products of 10% to scrap.The whole world is every year because corroding the financial loss about 7,000 hundred million dollars caused, and the 2%-4% steel equipment accounting for various countries' national economy output value, also because corrosion causes equipment performance to decline, makes production safety be subject to serious threat, production efficiency significantly declines.
Anticorrosion of iron and steel treatment technology has many, but iron and steel table and bonderizing and chromating process are two kinds of methods the most frequently used at present in steel corrosion protection.
Steel surface bonderizing is a kind of technology being formed phosphatize phosphate coat by steel substrate and the conversion fluid generation chemical reaction containing compositions such as phosphoric acid salt, heavy metal ion, fluorion, nitrate, nitrite at iron and steel table.One of feature of phosphatize phosphate coat is porousness, and the solidity to corrosion of film itself is limited, and what have just produces scale rapidly in drying process.Therefore, the object of phosphorization treatment technology normally strengthens the bonding force of steel surface and organic coating, and the steel products after its process are general only in indoor use.In order to improve the antiseptic power of phosphatize phosphate coat, usually also must make the closed Passivation Treatment of filling, oxygenizement further after phosphatization to phosphatize phosphate coat, phosphatize phosphate coat is stable in air.Through the phosphate layer of sealing treatment, can as the corrosion resistant coating of ferrous metal matrix.However, the phosphatize phosphate coat that this technology produces still also exists the phosphoric acid salt, the heavy metal ion that contain in the poor and Phosphating Solution of corrosion resisting property and causes the shortcoming such as eutrophication, heavy metal contamination to environment.
Chromating process is as a kind of traditional metallic surface Treatment technique for processing, widely used by as anticorrosion of iron and steel treatment process always, traditionally steel plate is carried out flooding or electrolysis treatment in the treatment solution containing chromium such as chromic acid or chromic salt, thus form chromic salt tunicle on surface.More preferably a kind of method then carries out chromic salt chemical conversion treatment at ferrous metal surface galvanizing.Such as number of patent application is 91102396.8, denomination of invention is the patent of chromate composite used for passivation of zine plated layer on metal body and application thereof, disclose a kind of chromate metal surface treatment solution composition and make etch-proof olive colour passivation technology with described liquid to zine plated layer on metal body surface, this liquid is containing CrO
3, NaHSO
4, NaH
2pO
4passivating solution in, add AgNO
30.08-0.2g/l, alkyl polyoxyethylene ether 0.04-0.1g/l, through this liquid make the corrosion resistance of the zine plated layer on metal body tool excellence after Passivation Treatment, larger passivation thickness and sticking power, beautiful, thick and heavy olive-green color and luster, extend the work-ing life of passivating solution simultaneously and expand the use range of passivation technology, thus can use in harsh environment.
Although the above surface treatment liquid and surface treatment method can provide fabulous corrosion protection to iron and steel; but day by day in short supply due to zinc resource; and the use of carcinogenic chromic salt in hypertoxic prussiate, chromating treating processes in galvanizing process; especially the product of chromic salt process contains carcinogens sexavalent chrome due to conversion film; lose electronic waste that use value discards rear generation to pollute and cause huge harm to human environment, and the chromate waste water handling procedure that produces in production process is complicated and cost is higher.Along with the fast development of global information industry, the quickening of model change speed, the electronic waste that countries in the world produce every year reaches 1,000,000, ten million ton, and this numeral several is also riseing year by year.The high risks that the toxic gas produced when Toxic seepage, incineration process during electronic waste landfill disposal causes environment and human health, receives global concern.Therefore, this traditional technology with one-hundred-year history of metallic surface chromate conversion treatments technology has been faced with the destiny be cancelled.Implement in European Union on July 1st, 2006 (use some objectionable impurities about restriction in electronic and electrical equipment " RoHS (The Restriction of the Use of Certain Hazardous Substances in Electrical and ElcctricEquipmcnt) instruction, regulation was from 1 day July in 2006, the new electric equipment products entering EU market should containing comprising six kinds of objectionable impuritiess such as sexavalent chrome, its object is to improve the recovery and recirculation rate of scrapping electric equipment products, reduce the secondary pollution that electric equipment products waste material causes water source and soil, ensure the Sustainable development of society.China is execution RoHS Directive in 1 day March in 2007 also, forbids using the objectionable impuritiess such as sexavalent chrome in metal surface treatment process process.
At present, in order to increase the antiseptic property of ferrous metal, there has been proposed various parkerizing method.Such as application number is 01806287.3; denomination of invention is the patent of surface treatment tin plate and chemical synthesis treatment liquid; provide a kind of containing phosphate ion, tin ion and silane coupling agent and pH is the chemical synthesis treatment liquid of 1.5 ~ 5.5; the surface treatment liquid of this invention is not containing the chromium being unfavorable for environment protection, and process after steel plate paint adaptation, japanning after solidity to corrosion, rust-resisting property and processibility all very excellent.
Although the passivating solution disclosed in above-mentioned patent, at iron and steel or Several Thiourea Derivatives on Zinc Plate Surface after above-mentioned passivating solution process, its surface anticorrosion performance improves greatly, but containing phosphoric acid salt, heavy metal ion and sexavalent chrome in passivating solution, causes serious destruction and impact to human health and environmental ecology.
Summary of the invention
The technical problem to be solved in the present invention is for above-mentioned the deficiencies in the prior art, and provides a kind of surface treatment liquid of not phosphorous, chromium.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of environment-friendly type treating liquid for surface of iron or steel, comprises following composition:
The mass concentration of titanium salt is 0.1 ~ 1.5%;
The mass concentration of vanadium compound is 2 ~ 15%;
The mass concentration of fluorochemical is 5 ~ 20%;
For the pH value of surface treatment liquid being adjusted to the acid of 3 ~ 4;
The mass concentration of sodium phytate is 2 ~ 5%;
The mass concentration of tensio-active agent is 0.5 ~ 3.5%;
Surplus is water and other inevitable impurity.
Acid of the present invention is salpeter solution.
Titanium salt of the present invention adopts at least one in titanium chloride, titanium sulfate, titanyl sulfate, titanyl nitrate, sodium titanate, potassium titanate.
Vanadium compound of the present invention is be selected from least one in metavanadic acid, partially vanadium compound ammonium vanadate, ammonium poly-vanadate, sodium metavanadate, oxygen base vanadium trichloride, dichloro oxygen vanadium solution, vanadylic sulfate, Vanadosulfuric acid, vanadous chloride, sodium orthovanadate and poly ammonium vanadate.
Fluorochemical of the present invention adopts at least one in Neutral ammonium fluoride, ammonium acid fluoride, Sodium Fluoride, sodium hydrogen fluoride, Potassium monofluoride and fluorine ammonium potassium.
A kind of environment-friendly type treating liquid for surface of iron or steel of the present invention is used for the method for steel surface process, comprises the following steps:
The first step, steel surface to be carried out after skimming treatment by rinsed with deionized water;
Second step, steel surface to be carried out after processing of rust removing by rinsed with deionized water;
3rd step, carry out Passivation Treatment with surface treatment liquid of the present invention at steel surface, during use, temperature controls at 10 DEG C-40 DEG C, and pH value is 1 ~ 5, and is the duration of contact of steel surface 5 minutes ~ 60 minutes;
4th step, the surface passivated membrane that the 3rd step obtains is spent Ion Cleaning after, seasoning, namely forms the passive film of uniform color at steel surface.
After the present invention adopts technique scheme, there is following technique effect:
In the present invention, surface treatment liquid is not due to containing causing the phosphoric acid salt of body eutrophication, carcinogens six chromium valency (chromic salt) and poisonous metal ion, not only greatly alleviate the pollution of environment, and cost significantly reduces.
The present invention takes full advantage of oxidisability and the strongly-acid of nitric acid, by the Fe forms of steel surface be 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 conversion fluid and ferric ion complexing form fluorine iron complex ion, generate fluorine wustite precipitate reacting with the ammonium ion in treatment solution or potassium ion or sodium ion, result forms the densification conversion rete being main component with fluorine wustite with indissoluble at steel surface, and the erosion resistance of iron and steel is greatly enhanced.The passive film generated, the composition-ferric ion dissolved owing to make use of steel surface itself forms the feature of conversion film, make fine and close conversion film be easy to be formed at steel surface, and conversion film corrosion resisting property is good.
The sodium phytate contained in the present invention has huge chelating potential energy, can give the excellent erosion resistance of passive film good excellent adhesion between metal level and passivation film.
Surface treatment liquid and carry out the surface of steel plate that processes not containing to the disadvantageous chromium of environment with this treatment solution in the present invention; production and the product of steel plate all achieve Trend of Chrome-free; therefore just there is not the process problem of chromate waste water yet, thus protect environment, there is significant environmental and social benefits.
Surface treatment liquid in the present invention is simple for the treatment of technique during ferrous materials, and easy to implement, cost is lower.Only need add a small amount of supplementary instrument or equipment with regard to Trend of Chrome-free surface treatment can be carried out on traditional chromium process for producing line of steel plate completely, make wastewater treatment more simple, thus reduce costs, there is significant economic benefit.
Embodiment
For making object of the present invention and technical scheme clearly, below in conjunction with the embodiment of the present invention, technical scheme of the present invention is clearly and completely described.Obviously, described embodiment is a part of embodiment of the present invention, instead of whole embodiments.Based on described embodiments of the invention, the every other embodiment that those of ordinary skill in the art obtain under without the need to the prerequisite of creative work, all belongs to the scope of protection of the invention.
Embodiment 1
A kind of environment-friendly type treating liquid for surface of iron or steel, comprises following composition:
The mass concentration of titanium salt is 0.1%;
The mass concentration of vanadium compound is 2%;
The mass concentration of fluorochemical is 5%;
For the pH value of surface treatment liquid being adjusted to the acid of 3;
The mass concentration of sodium phytate is 2%;
The mass concentration of tensio-active agent is 0.5%;
Surplus is water and other inevitable impurity.
Above-described vanadium compound is ammonium poly-vanadate; Described titanium salt is titanium chloride; Described vanadium compound is metavanadic acid; Described fluorochemical is Neutral ammonium fluoride, and described salpeter solution is diluted by concentrated nitric acid and obtains.
Embodiment 2
A kind of environment-friendly type treating liquid for surface of iron or steel, comprises following composition:
The mass concentration of titanium salt is 0.5%;
The mass concentration of vanadium compound is 5%;
The mass concentration of fluorochemical is 10%;
For the pH value of surface treatment liquid being adjusted to the acid of 3.5;
The mass concentration of sodium phytate is 3%;
The mass concentration of tensio-active agent is 1.5%;
Surplus is water and other inevitable impurity.
Above-described vanadium compound is ammonium poly-vanadate; Described titanium salt is titanyl sulfate; Described vanadium compound is ammonium poly-vanadate; Described fluorochemical is sodium hydrogen fluoride, and described salpeter solution is diluted by concentrated nitric acid and obtains.
Embodiment 3
A kind of environment-friendly type treating liquid for surface of iron or steel, comprises following composition:
The mass concentration of titanium salt is 1.0%;
The mass concentration of vanadium compound is 10%;
The mass concentration of fluorochemical is 15%;
For the pH value of surface treatment liquid being adjusted to the acid of 3.5;
The mass concentration of sodium phytate is 5%;
The mass concentration of tensio-active agent is 3.5%;
Surplus is water and other inevitable impurity.
Above-described vanadium compound is ammonium poly-vanadate; Described titanium salt is titanyl nitrate; Described fluorochemical is Potassium monofluoride, and described salpeter solution is diluted by concentrated nitric acid and obtains.
The present invention, when adopting above-mentioned environment-friendly type surface treatment liquid to carry out Passivation Treatment to steel plate, adopts electrolytic passivation method or anode electrolysis passivating method.Wherein electrolytic passivation method is using pending tin plate as negative electrode, and inert material carries out electrolytic passivation as anode; Anode electrolysis passivation is using pending tin plate as anode, and inert material carries out electrolytic passivation as negative electrode.
Wherein, passivation temperature is 15 ~ 60 DEG C, preferably 25 ~ 45 DEG C.
Wherein, the density range of Faradaic current is 0.1A ~ 20A/dm
2, preferably 0.5A ~ 10A/dm
2.
Wherein, the scope of passivation time is 5 ~ 20 seconds.And consider that the speed of a motor vehicle of coil of strip on production line is very fast, generally at about 200m/min, therefore passivation time is usually all between 2s ~ 5s.Therefore preferred passivation time is 2s ~ 5s.
When adopting electrolytic passivation method, the one in DC electrolysis passivation, alternating current electrolysis passivation, pulse electrolysis passivation, double wave pulse electrolytic passivation, pulse electrolysis passivation, the overlapping electrolytic passivation of DC-AC, the overlapping electrolytic passivation of DC pulse can be adopted.
The treating liquid for surface of iron or steel technical indicator made of the present invention is as follows:
1, outward appearance: light green transparent liquid;
2, viscosity: be greater than 15;
3, shock-resistance: 50kg/cm.
4, sticking power: 1 grade.
The invention also discloses a kind of environment-friendly type treating liquid for surface of iron or steel of the present invention for the method for steel surface process, comprise the following steps:
The first step, steel surface to be carried out after skimming treatment by rinsed with deionized water;
Second step, steel surface to be carried out after processing of rust removing by rinsed with deionized water;
3rd step, use this aqueous solution to carry out Passivation Treatment at steel surface, during use, temperature controls at 10 DEG C-40 DEG C, and pH value is 1 ~ 5, and is the duration of contact of steel surface 5 minutes ~ 60 minutes;
4th step, the steel surface after the 4th step Passivation Treatment is spent Ion Cleaning after, seasoning, namely forms the passive film of uniform color at steel surface.
Those skilled in the art of the present technique are appreciated that unless otherwise defined, and all terms used herein (comprising technical term and scientific terminology) have the meaning identical with the general understanding of the those of ordinary skill in field belonging to the present invention.Should also be understood that those terms defined in such as general dictionary should be understood to have the meaning consistent with the meaning in the context of prior art, unless and define as here, can not explain by idealized or too formal implication.
The implication of the "and/or" described in the present invention refers to respective Individual existence or both simultaneous situations include interior.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to right.
Claims (6)
1. an environment-friendly type treating liquid for surface of iron or steel, is characterized in that, comprises following composition:
The mass concentration of titanium salt is 0.1 ~ 1.5%;
The mass concentration of vanadium compound is 2 ~ 15%;
The mass concentration of fluorochemical is 5 ~ 20%;
For the pH value of surface treatment liquid being adjusted to the acid of 3 ~ 4;
The mass concentration of sodium phytate is 2 ~ 5%;
The mass concentration of tensio-active agent is 0.5 ~ 3.5%;
Surplus is water and other inevitable impurity.
2. a kind of environment-friendly type treating liquid for surface of iron or steel according to claim 1, is characterized in that: described acid is salpeter solution.
3. a kind of environment-friendly type treating liquid for surface of iron or steel according to claim 1, is characterized in that: described titanium salt adopts at least one in titanium chloride, titanium sulfate, titanyl sulfate, titanyl nitrate, sodium titanate, potassium titanate.
4. a kind of environment-friendly type treating liquid for surface of iron or steel according to claim 1, is characterized in that: described vanadium compound is be selected from least one in metavanadic acid, partially vanadium compound ammonium vanadate, ammonium poly-vanadate, sodium metavanadate, oxygen base vanadium trichloride, dichloro oxygen vanadium solution, vanadylic sulfate, Vanadosulfuric acid, vanadous chloride, sodium orthovanadate and poly ammonium vanadate.
5. a kind of environment-friendly type treating liquid for surface of iron or steel according to claim 1, is characterized in that: described fluorochemical adopts at least one in Neutral ammonium fluoride, ammonium acid fluoride, Sodium Fluoride, sodium hydrogen fluoride, Potassium monofluoride and fluorine ammonium potassium.
6. environment-friendly type treating liquid for surface of iron or steel a kind of described in claim 1 is used for the method for steel surface process, it is characterized in that: comprise the following steps:
The first step, steel surface to be carried out after skimming treatment by rinsed with deionized water;
Second step, steel surface to be carried out after processing of rust removing by rinsed with deionized water;
Described in 3rd step, the right to use 1, surface treatment liquid carries out Passivation Treatment at steel surface, and during use, temperature controls at 10 DEG C-40 DEG C, and pH value is 1 ~ 5, and is the duration of contact of steel surface 5 minutes ~ 60 minutes;
4th step, the surface passivated membrane that the 3rd step obtains is spent Ion Cleaning after, seasoning, namely forms the passive film of uniform color at steel surface.
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|---|---|---|---|
| CN201410573862.3A CN104357822A (en) | 2014-10-24 | 2014-10-24 | Environment-friendly steel surface treating fluid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410573862.3A CN104357822A (en) | 2014-10-24 | 2014-10-24 | Environment-friendly steel surface treating fluid |
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Family
ID=52525125
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105839097A (en) * | 2016-05-31 | 2016-08-10 | 无锡伊佩克科技有限公司 | Chromium-free passivating agent for pylon and preparation method of chromium-free passivating agent for pylon |
| CN106194610A (en) * | 2016-08-31 | 2016-12-07 | 常熟市强盛电力设备有限责任公司 | Wind power generator rotor |
| CN107794536A (en) * | 2017-10-25 | 2018-03-13 | 浙江星丰科技有限公司 | A kind of metal surface treating method of high-efficiency environment friendly |
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| EP0919877A1 (en) * | 1997-12-01 | 1999-06-02 | Canon Kabushiki Kaisha | Electrophotographic photosensitive member, process for producing electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
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| CN107794536A (en) * | 2017-10-25 | 2018-03-13 | 浙江星丰科技有限公司 | A kind of metal surface treating method of high-efficiency environment friendly |
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Application publication date: 20150218 |