CN104357821A - Steel surface treatment liquid - Google Patents
Steel surface treatment liquid Download PDFInfo
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- CN104357821A CN104357821A CN201410573754.6A CN201410573754A CN104357821A CN 104357821 A CN104357821 A CN 104357821A CN 201410573754 A CN201410573754 A CN 201410573754A CN 104357821 A CN104357821 A CN 104357821A
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- mass concentration
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- iron
- steel
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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
- C23C22/34—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
- C23C22/36—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 containing also phosphates
- C23C22/361—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 containing also phosphates containing titanium, zirconium or hafnium compounds
-
- 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
- C23C22/36—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 containing also phosphates
- C23C22/364—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 containing also phosphates containing also manganese cations
-
- 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
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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 a steel surface treatment liquid comprising titanium salt with the mass concentration of 0.1-1.5%, vanadium compound with the mass concentration of 2-15%, fluoride with the mass concentration of 5-20%, water soluble resin with the mass concentration of 1-2%, acid used for adjusting the pH value of a passive solution to be 3-4, phosphorus compound with the mass concentration of 5-25%, molybdenum, zirconium, manganese or tungsten metallic compound or the combination thereof with the mass concentration of 0.1-1.5%, and water and other inevitable impurities. The surface treatment process has the advantages of simple method, easy implementation and low cost. Only a small number of auxiliary instruments or equipment are required to completely perform the chrome free surface treatment on the traditional chrome treatment production line of steel plates, thereby simplifying wastewater treatment, lowering cost and achieving remarkable economic benefits.
Description
Technical field
The present invention relates to steel surface treatment technology, particularly a kind for the treatment of 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 because corroding the financial loss about 7,000 hundred million dollars caused, accounts for the 2%-4% of various countries' national economy output value every year, and steel equipment also causes equipment performance to decline because of corrosion, 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.
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.
Such as application number is 94112157.7 again, denomination of invention is the multielement reaction passivating treatment agent of electrogalvanizing steel plate, disclose a kind of multielement reaction passivating treatment agent of electrogalvanizing steel plate, mainly contain dichromate, metal chloride and nitrate and a certain proportion of water formed.Treatment agent preparation is simple, and Composition Control is easy, is particularly useful for continuous belt steel and produces unit.Owing to utilizing NO3-as purification reaction promotor, therefore the treatment process time is short, rapidly dry, and can, according to processing requirement, make the chromium content on the electrogalvanizing steel plate surface after process at 10 ~ 60mg/m
2between flexible.When the chromium content of surface of steel plate is at 45 ~ 50mg/m
2time, its solidity to corrosion (SST) was more than 96 hours.
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.
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 the heavy metal ion contained in passivating solution and sexavalent chrome, serious destruction and impact are caused on 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 not containing the treating liquid for surface of iron or steel of chromium.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind for the treatment of 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%;
The mass concentration of water soluble resin is 1 ~ 2%;
For the pH value of surface treatment liquid being adjusted to the acid of 3 ~ 4;
The mass concentration of phosphorus compound is 5 ~ 25%;
Be selected from one or more compounds in molybdenum, zirconium, manganese or tungsten metallization compound, its mass concentration is 0.1 ~ 1.5%;
Surplus is water and other inevitable impurity.
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.
Titanium salt of the present invention adopts titanium chloride, titanium sulfate, titanyl sulfate, titanyl nitrate, sodium titanate, potassium titanate at least one wherein.
Water soluble resin of the present invention comprises one or more in cationic acrylate analog copolymer, cationic styrene-acrylic emulsion polymkeric substance, cationic epoxy acrylic copolymer, polyurethane/cationic ester polymer.
Acid of the present invention is phosphoric acid.
After the present invention adopts technique scheme, there is following technique effect:
Treating liquid for surface of iron or steel of the present invention, due to not containing carcinogens six chromium valency (chromic salt) and poisonous metal ion, not only greatly alleviate the pollution of environment, and cost also significantly reduces.
Wood invention takes full advantage of oxidisability and the strongly-acid of phosphoric 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 treatment solution and ferric ion complexing form fluorine iron complex ion, reaction is generated fluorine wustite precipitation, 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.Titanium salt generates titanium hydroxide precipitation and makes fluorine wustite rete finer and close in reaction process.
There is desirable complexing action in the solution in the metal ion in the phosphorus compound energy metallizing thing contained in surface treatment liquid, promote that metal ion is in the deposition of steel surface, meanwhile, the phosphorus of surface of steel plate deposition can also play the effect improving iron and steel sulfuration resistant spot.
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.
Process of surface treatment in the present invention is simple, 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 for the treatment of 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%;
The mass concentration of water soluble resin is 1%;
For the pH value of surface treatment liquid being adjusted to the acid of 3;
The mass concentration of phosphate dihydrogen manganese is 5%;
The metallic compound of manganese, its mass concentration is 0.1;
Surplus is water and other inevitable impurity.
Above-described vanadium compound is ammonium poly-vanadate; Described titanium salt is titanium chloride; Described water soluble resin is cationic acrylate analog copolymer, and described fluorochemical is Sodium Fluoride.
Embodiment 2
A kind for the treatment of 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%;
The mass concentration of water soluble resin is 1.2%;
For the pH value of surface treatment liquid being adjusted to the acid of 3.5;
The mass concentration of phosphate dihydrogen manganese is 10%;
The metallic compound of manganese, its mass concentration is 1.0%;
Surplus is water and other inevitable impurity.
Above-described vanadium compound is dichloro oxygen vanadium solution; Described titanium salt is titanium sulfate; Described water soluble resin is cationic styrene-acrylic emulsion polymkeric substance, and described fluorochemical is Sodium Fluoride.
Embodiment 3
A kind for the treatment of 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%;
The mass concentration of water soluble resin is 1.5%;
For the pH value of passivating solution being adjusted to the acid of 3.5;
The mass concentration of phosphate dihydrogen manganese is 20%;
The metallic compound of manganese, its mass concentration is 1.5%;
Surplus is water and other inevitable impurity.
Above-described vanadium compound is Vanadosulfuric acid solution; Described titanium salt is sodium titanate; Described water soluble resin is cationic epoxy acrylic copolymer, and described fluorochemical is Sodium Fluoride.
The present invention, when adopting above-mentioned chromium-free passivation 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/dm2, 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.
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 (5)
1. a 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%;
The mass concentration of water soluble resin is 1 ~ 2%;
For the pH value of surface treatment liquid being adjusted to the acid of 3 ~ 4;
The mass concentration of phosphorus compound is 5 ~ 25%;
Be selected from one or more compounds in molybdenum, zirconium, manganese or tungsten metallization compound, its mass concentration is 0.1 ~ 1.5%;
Surplus is water and other inevitable impurity.
2. a kind for the treatment of 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.
3. a kind for the treatment of liquid for surface of iron or steel according to claim 1, is characterized in that: described titanium salt adopts titanium chloride, titanium sulfate, titanyl sulfate, titanyl nitrate, sodium titanate, potassium titanate at least one wherein.
4. a kind for the treatment of liquid for surface of iron or steel according to claim 1, is characterized in that: described water soluble resin comprises one or more in cationic acrylate analog copolymer, cationic styrene-acrylic emulsion polymkeric substance, cationic epoxy acrylic copolymer, polyurethane/cationic ester polymer.
5. a kind for the treatment of liquid for surface of iron or steel according to claim 1, is characterized in that: described acid is phosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410573754.6A CN104357821A (en) | 2014-10-24 | 2014-10-24 | Steel surface treatment liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410573754.6A CN104357821A (en) | 2014-10-24 | 2014-10-24 | Steel surface treatment liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104357821A true CN104357821A (en) | 2015-02-18 |
Family
ID=52525124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410573754.6A Withdrawn CN104357821A (en) | 2014-10-24 | 2014-10-24 | Steel surface treatment liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104357821A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245710A (en) * | 2017-05-11 | 2017-10-13 | 安徽省金寨县新诚机械制造有限公司 | A kind of environmentally friendly surface treatment liquid of magnesium alloy |
-
2014
- 2014-10-24 CN CN201410573754.6A patent/CN104357821A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107245710A (en) * | 2017-05-11 | 2017-10-13 | 安徽省金寨县新诚机械制造有限公司 | A kind of environmentally friendly surface treatment liquid of magnesium alloy |
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Application publication date: 20150218 |