CN1231706A - Method for phosphating a steel band - Google Patents
Method for phosphating a steel band Download PDFInfo
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- CN1231706A CN1231706A CN97198236A CN97198236A CN1231706A CN 1231706 A CN1231706 A CN 1231706A CN 97198236 A CN97198236 A CN 97198236A CN 97198236 A CN97198236 A CN 97198236A CN 1231706 A CN1231706 A CN 1231706A
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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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
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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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
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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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
- C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
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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
- C23C22/364—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
- C23C22/365—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 containing also zinc and nickel cations
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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)
- Laminated Bodies (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The invention concerns a method for phosphating a steel band or a steel band galvanized or alloy-coated on one side or both sides by spraying or dipping for a period ranging from 2 to 15 seconds using an acid, zinc and manganese-containing phosphating solution at a temperature ranging from 40 to 70 DEG C. Said method is characterized by a phosphating solution containing 1 to 4 g/l zinc ions, 0.8 to 3.5 g/l manganese ions, 10 to 30 g/l phosphate ions, 0.1 to 3 g/l free, ionic or bound hydroxylamine, and no more than 1 g/l nitrate ions, a free acid content ranging from 0.4 to 4 points and a total acid content ranging from 12 to 50 points. The phosphating solution contains optionally 0.8 to 3.5 g/l nickel or 0.002 to 0.2 g/l copper.
Description
The present invention relates to carry out phosphated method through the steel band of zinc-plated or galvanized alloy to steel band or to single or double.Wherein, according to the travelling speed of steel band, carry out the 2-15 spraying or the dip treating in second.
To iron, steel, zinc and alloy thereof, and to carry out the prior art of method of bonderize known already on the surface of aluminium and alloy thereof.The purpose of this surface being carried out bonderize is to improve the adhesion strength of enamelled coating and improves Corrosion Protection.The metallic surface can be immersed in the phosphating solution or with phosphating solution and be sprayed on the metallic surface, to implement the phosphatization method.The method that both combine also is known.Not only the metal parts that has been shaped bonderize can be carried out as body of a motor car, and the metal strip on the belt supply line of operation fast bonderize can be carried out.The present invention just relates to the bonderize of this metal strip.The bonderize of band is the bonderize that is different from parts, because bonderize is to carry out under high belt speed operation.That is to say, must be in the very short treatment time, for example 2-15 forms the phosphatization coating of whole metal in second.
To metal strip, the phosphatization process that galvanized steel band particularly electro-galvanizing or the fusing dipping carries out also is known in the prior art.Patent documentation WO91/02829 described a kind of to electro-galvanizing and/or the galvanized steel band of fusing dipping carry out the method for bonderize.Wherein, except containing zine ion, outside the phosphate ion, also have the manganese positively charged ion, nickel cation and the solution of anionic acid phosphatase salinization with oxygen acid of booster action carry out fast processing.Above-mentioned oxygen acid ion especially can be understood as nitrate ion.Germany Patent document DE-A-3537108 has also described a kind of method of bonderize of the steel band to electro-galvanizing.Contain outside dezincification, manganese, the phosphatic ion by use, also have other metallic cation, as nickel ion and/or have negatively charged ion, the especially nitrate ion of the oxygen acid of booster action, acid phosphatase salinization solution carries out bonderize.The content of zinc cation is in the low scope of 0.1-0.8 grams per liter in this method.The zinc coating that Germany Patent document DE-A-4228470 has described a kind of steel band to its electro-galvanizing carries out the method for bonderize, wherein with the zinc cation that contains the 1.0-6.0 grams per liter, 0.5-5.0 grams per liter nickel cation and 14-25 grams per liter phosphate anion, acid phosphatase salinization solution carries out bonderize.By above-mentioned document susceptible of proof, promptly can use this cationic water-soluble salt, nitrate for example is as the raw material of preparation phosphating solution.Usually, can use above-mentioned cationic nitrate form, nitrate content wherein can not influence the phosphatization result.
With the known phosphate method, can make the phosphate coating that forms on the galvanizing surface of the galvanized steel band of single or double, its mass area ratio is less than about 2.0 gram/rice
2On ungalvanized steel surface, during the bonderize of the weak point in about 2-15 second, not phosphatization effect.Therefore when using the steel band of one side zinc coating, on its ungalvanized one side, do not form phosphate coating.This is not desired, if the steel band that these one side zinc coatings and bonderize are crossed is the parts as car body subsequently, and bonderize once more later on, then, can usually cause that the phosphatization of steel face becomes a difficult problem because above-mentioned giving handled the passivation that causes.
Task of the present invention provides one and is with fast and carries out phosphated method on the supply line, wherein, can not only make the zinc-plated face on the steel band of zinc-plated or alloy plating zinc carry out phosphatization, and can make the ungalvanized one side on the steel band of ungalvanized steel band or one side zinc coating carry out phosphatization.Therefore, present method can provide a kind of material, and it is applicable to preparation car body or household electrical appliance, for example structural part of refrigerator and washing machine.
The invention provides one and be used for steel band or single or double is zinc-plated or the phosphatization method of the steel band of alloy plating zinc.Wherein, under 40-70 ℃ of temperature, spray or dip treating 2-15 second with a kind of acid phosphatase salinization solution that contains zinc and manganese.It is characterized in that above-mentioned phosphating solution contains:
1-4 grams per liter zine ion
0.8-3.5 grams per liter mn ion
10-30 grams per liter phosphate ion
0.1-3 the grams per liter free, ionic or in conjunction with the azanol of shape
And the nitrate ion that is lower than 1 grams per liter, its free acid content is the 0.4-4 point value, and total acid content is the 12-50 point value.
Therefore, steel band can carry out electro-galvanizing or the fusing dipping is zinc-plated, and alloy plating zinc.So-called " alloy plating zinc " is meant on the steel surface and plates alloy, and this alloy also contains other metal except zinc, as iron, nickel or aluminium.For example, can carry out alloy plating zinc with iron-zinc alloy, for example, Galvanized Steel Strip be heat-treated, iron atom is diffused in the zinc layer, vice versa.Generally, the bed thickness of galvanizing coating is about 5-20 μ m.
Above-mentioned so-called " free acid " and " total acid " are known in the phosphatization technical field.They are determined by laxative remedy: with the sodium hydroxide solution titration tart liquor sample of 0.1N, and measure its consumption.The milliliter number that is consumed is as point value.The milliliter number of the 0.1N caustic lye of soda that is consumed when the point value of the described free acid 10ml groove solution that is equivalent to be diluted to 50ml with complete deionized water is titrated to pH=3.6 herein.Similarly, the point value of described total acid is to be equivalent to, the milliliter number that sodium hydroxide solution consumed when being titrated to pH=8.2.
The method according to this invention, making does not have fully in the phosphatization groove or only contains very small amount of nitrate, contains the compound that azanol maybe can produce azanol simultaneously.Can implement task of the present invention, promptly can on the steel surface of coating not, form metal tripolyphosphate salinization coating as a whole.Especially for only containing the nitrate that is not higher than 0.1 grams per liter in the phosphating solution of zinc coating steel band phosphorylation or particularly not having nitrate fully.And during to the bonderize of ungalvanized steel band, the nitrate content in the phosphating solution can contain maximum 1 grams per liters, it in addition may be more favourable.
Contain azanol or its compound by use, and contain a small amount of nitrate or do not have the phosphating solution of nitrate to carry out the bonderize of belt conveying line fast, this is also can make ungalvanized steel surface carry out bonderize by spraying or dipping method for the first time.Use azanol will use the long treatment time as accelerator with the phosphatization process of carrying out parts, this is well-known already.For example, patent documentation EP-A-315059 and WO93/03198.Azanol can maybe can produce the compound of azanol with free alkali, and for example the azanol mixture as ketoxime or ethylidenehydroxylamine, perhaps with the form of hydroxyl ammonium salt, uses.According to the acidity of phosphatization tank liquor, in the concentrated solution of phosphatization tank liquor or phosphatization groove, add free hydroxylamine then its major part exist with the azanol cationic form.Under situation about using with the hydroxyl ammonium salt form, then vitriol and phosphoric acid salt are specially suitable.Under phosphatic situation, owing to have better solvability, preferably acid-salt.On the one hand in order to reduce cost, on the other hand in order in the phosphatization tank liquor, not add too much sulfate ion.The preferred composition that uses free hydroxylamine and sulfuric acid hydroxyl ammonium salt.The azanol that adds in phosphating solution or the amount of its compound will make the calculating concentration of the free hydroxylamine in the phosphating solution be about the 0.1-3 grams per liter, are preferably the 0.15-0.8 grams per liter and are advisable.
For phosphate concn is described, the whole phosphorus contents in the phosphatization tank liquor all should be considered as phosphate ion PO
4 3-Form.Therefore, when concentration is calculated or is measured, the very important known like this fact, promptly when the pH value in the phosphatization tank liquor was the acid range of about 2.0-3.6, in fact having only very small amount of phosphoric acid salt was to exist with the anionic form with three negative charges.Or rather, in this pH value scope, phosphoric acid salt mainly is to exist with the dihydrogen orthophosphate anionic form with a negative charge, and undecomposed phosphoric acid and a spot of hydrophosphate negatively charged ion existence with two negative charges.
When also containing other positively charged ion in the phosphating solution,, therefore can improve the lacquer adhesivity and the non-corrosibility of this phosphoric acid coating because it also can be mixed in the phosphate coating.For example, when containing the nickel ion of the 0.8-3.5 grams per liter of having an appointment in the phosphatization tank liquor of the present invention, the lacquer adhesivity had advantageous effects.Also can replace problematic nickel on the toxicology with copper with similar effect.Thereby the cupric ion of 0.002～0.2 grams per liter of can having an appointment in the preferred phosphatization tank liquor that uses is preferably the cupric ion of 0.003-0.06 grams per liter.
Except the positively charged ion of described formation coating, phosphating solution also has alkali metal cation and/or ammonium cation.So that its free acid point value reaches desired scope.
For the ungalvanized steel of phosphatization, in phosphating solution, do not need to contain fluorion usually.Yet fluorion is more prone to the phosphatization process of the galvanized steel band of fusing dipping, and the existence of fluorion, also helps forming uniform phosphate coating in the phosphatization process of Galvanized Steel Strip.Therefore, in another preferable embodiment of the present invention, employed phosphating solution has and is lower than about 0.8 grams per liter, the fluorochemical of free or complex form.For example, in the phosphatization to the electro-galvanizing steel band, content of fluoride is preferably the 0.0-0.5 grams per liter, is preferably the 0.1-0.2 grams per liter.
Usually, can prepare phosphating solution by the known method of those skilled in the art.Phosphoric acid salt is to add phosphating solution with phosphoric acid.Positively charged ion is with acid soluble compound form, carbonate for example, and perhaps the oxide compound of phosphoric acid or hydroxide form add, and make its part neutralization.In order further to neutralize, preferably add sodium hydroxide or yellow soda ash to reach desired pH value scope.Employed in case of necessity cupric ion can add in the phosphating solution with copper sulfate or neutralized verdigris form.Sodium Fluoride or Potassium monofluoride are the free fluorochemical negative ion sources that suits, and employed complex fluoride can be for example a tetrafluoro borate or hexafluorosilicate.
The invention still further relates to the application of above-mentioned phosphatization method, it can form the per unit area quality and be about 0.4-2.0 gram/rice on the single or double of the steel band of steel band two sides or or alloy plating zinc zinc-plated at single or double
2The phosphatization coating.The mass area ratio of this phosphatization coating is preferably about 0.9-1.8 gram/rice
2Above-mentioned mass area ratio (" coating wt "), the sample plate that can cross by the weighing bonderize by the known method of those skilled in the art is dissolved in phosphate layer in 5% chromic acid solution then, then this sample plate of weighing and measuring again.This measuring method is described among the DIN 50942.In order to obtain to have the phosphatization coating of desired mass area ratio, the preferred phosphating solution that uses the total acid of free acid with 1.5-2.5 point value and 20-35 point value.The temperature of treatment soln is preferably at 50-70 ℃, and particularly 55-65 ℃, the preferred bonderize time is about 5-10 second.
Before application of phosphoric acid salinization solution, should make metallic surface water complete wetting.This normally carries out on the belt supply line of operation continuously.If but when on the steel surface greasy dirt being arranged, must before bonderize, remove degreasing with suitable stain remover.Suitable method is to be to know in the prior art.Usually, before carrying out bonderize, carry out activation treatment with known activator.Usually use solution or the suspension that contains titanium phosphate and sodium phosphate.After the activated processing, re-use phosphatization process of the present invention, preferably then carry out the post-flush process of a passivation.Usually, water carries out an intermediary flushing between the post-flush of above-mentioned bonderize and passivation.Wherein, use contains the treatment soln of chromic acid to carry out the post-flush of above-mentioned passivation.But consider from aspects such as labour protection and environment protection and waste discharge processing, preferably use the processing tank liquor of Chrome-free to replace the above-mentioned passivation tank liquor that contains chromium.Use pure inorganic tank liquor for this reason,, perhaps also can use the tank liquor of organic reaction, for example based on the tank liquor of the polyvinyl phenol that replaces particularly based on the tank liquor of fluorozirconate.In addition, also can use the one or more following positively charged ion that contains the 0.001-10 grams per liter: the post-flush solution of lithium ion, cupric ion, silver ions and/or bismuth ion.
Phosphated metal strip of the present invention can directly be coated with organic coating.Yet they also can be, through cutting, be shaped with the structural part that engages parts into such as car body or household electrical appliance after unvarnished initial conditions.By phosphate coating relevant forming process is more prone to.If when the corrosion of the structural part of completion required to hang down, for example household electrical appliance then can will directly be painted by the device that metal produced of pre-bonderize.The structural part higher to requirement for anticorrosion, for example the car body member preferably with after the car body equipment completion, carries out bonderize once more.
Be described in further detail the present invention with the following example:
Table: phosphatization process and coating wt
| Parameter | Example 1 | Example 2 | Example 3 | Example 4 | Reference examples |
| Free acid (ml) | 1.7 | 2.1 | 2.1 | 2.4 | 2.5 |
| Total acid (ml) | 25 | 33.0 | 33.0 | 35.0 | 35.0 |
| Zinc (g/l) | 1.8 | 1.9 | 2.2 | 2.1 | 2.0 |
| Nickel (g/l) | 2.0 | 2.2 | 2.2 | 2.3 | 2.2 |
| Manganese (g/l) | 2.0 | 2.2 | 2.2 | 2.3 | 2.2 |
| Phosphoric acid salt (g/l) | 11.0 | 16.0 | 16.0 | 17.0 | 17.0 |
| Nitrate (g/l) | -- | -- | 0.3 | -- | 15.0 |
| Oxammonium sulfate (mg/l) | 300 | 400 | 400 | 600 | -- |
| Fluorochemical (mg/l) | -- | 200 | 200 | 300 | -- |
| Temperature (℃) | 55 | 64 | 65 | 65 | 60 |
| Treatment time (second) | 6 | 7 | 6 | 4 | 8 |
| Coating wt (g/m 2) | On the ZE 1.7 on ZNE 1.4 | On CRS 1.4 | On CRS 1.6 | On CRS 1.0 | On the ZE 1.5 on CRS 0.2 |
*ZE: electro-galvanizing steel; ZNE: electro-galvanizing/nickel steel material; CRS: cold-rolled steel St 1405.
The corrosion resistance test that the embodiment of the invention provides (VDA replaces climatic test 621-415, with the stone percussion test of VW P 1210) shows, on galvanized and ungalvanized surface, does not significantly distinguish.All reach car gage in each case.
Claims (7)
1. the phosphatization method that is used for the steel band of the zinc-plated or alloy plating zinc of steel band or single or double, wherein, under 40-70 ℃ of temperature, with a kind of acid phosphatase salinization solution spraying that contains zinc and manganese or dip treating 2-15 second, it is characterized in that, contain in the phosphating solution:
1-4 grams per liter zine ion
0.8-3.5 grams per liter mn ion
10-30 grams per liter phosphate ion
0.1-3 the grams per liter free, the azanol of ionic or bonding state
And the nitrate ion that is not more than 1 grams per liter, and have the free acid content of 0.4-4 point value and the total acid content of 12-50 point value.
2. according to the method for claim 1, it is characterized in that phosphating solution also contains the nickel ion of 0.8-3.5 grams per liter.
3. according to the method for claim 1, it is characterized in that phosphating solution also contains the cupric ion of 0.002-0.2 grams per liter.
4. according to one or more the method among the claim 1-3, it is characterized in that phosphating solution contains free or the compound fluorochemical that is lower than 0.8 grams per liter.
5. according to the method for claim 1-4, it is characterized in that, nitrate content at the phosphating solution of the bonderize that is used for ungalvanized steel is lower than 1 grams per liter, and the nitrate content of phosphating solution that is used for the bonderize of galvanized steel is lower than 0.1 grams per liter.
6. according to one or more the method among the claim 1-5, it is characterized in that phosphating solution contains the free of 0.15-0.8 grams per liter, the azanol of ionic or bonding state.
7. according to the purposes of one or more method among the claim 1-6, wherein can the steel band two sides or single or double is zinc-plated or the two sides of the steel band of alloy plating zinc on, produce that to have mass area ratio be 0.4-2.0 gram/rice
2Phosphate coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19639596.8 | 1996-09-26 | ||
| DE19639596A DE19639596A1 (en) | 1996-09-26 | 1996-09-26 | Process for phosphating steel strips |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1231706A true CN1231706A (en) | 1999-10-13 |
Family
ID=7806984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97198236A Pending CN1231706A (en) | 1996-09-26 | 1997-09-17 | Method for phosphating a steel band |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0931179B1 (en) |
| JP (1) | JP2001508123A (en) |
| KR (1) | KR20000048509A (en) |
| CN (1) | CN1231706A (en) |
| AT (1) | ATE197969T1 (en) |
| AU (1) | AU4459397A (en) |
| CA (1) | CA2266625A1 (en) |
| DE (2) | DE19639596A1 (en) |
| ES (1) | ES2153217T3 (en) |
| ID (1) | ID21474A (en) |
| WO (1) | WO1998013534A2 (en) |
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| CN104313579A (en) * | 2014-11-11 | 2015-01-28 | 武汉钢铁(集团)公司 | Production method of zinc-magnesium galvanized alloy steel plate |
| CN111349867A (en) * | 2020-04-10 | 2020-06-30 | 武汉钢铁有限公司 | Coating-friendly pre-phosphorized electro-galvanized automobile outer plate and preparation method thereof |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10204649A (en) * | 1997-01-24 | 1998-08-04 | Nippon Parkerizing Co Ltd | Aqueous phosphate treating solution for metallic surface and its treatment |
| US6179934B1 (en) | 1997-01-24 | 2001-01-30 | Henkel Corporation | Aqueous phosphating composition and process for metal surfaces |
| DE19740953A1 (en) * | 1997-09-17 | 1999-03-18 | Henkel Kgaa | High speed spray or dip phosphating of steel strip |
| DE19808755A1 (en) | 1998-03-02 | 1999-09-09 | Henkel Kgaa | Layer weight control for strip phosphating |
| DE19905479A1 (en) * | 1999-02-10 | 2000-08-17 | Metallgesellschaft Ag | Process for the phosphatisation of zinc or aluminum surfaces |
| DE10110833B4 (en) * | 2001-03-06 | 2005-03-24 | Chemetall Gmbh | Process for applying a phosphate coating and use of the thus phosphated metal parts |
| DE10110834B4 (en) * | 2001-03-06 | 2005-03-10 | Chemetall Gmbh | Process for coating metallic surfaces and use of the substrates coated in this way |
| CN105568274A (en) * | 2015-12-31 | 2016-05-11 | 安徽红桥金属制造有限公司 | Environment-friendly galvanizing passivator and preparation method thereof |
| CN105925985B (en) * | 2016-07-19 | 2018-04-20 | 东莞市凯盟表面处理技术开发有限公司 | A kind of stainless iron room temperature chemical polishing solution and preparation method thereof and application method |
| CN112226755B (en) * | 2020-09-23 | 2023-06-23 | 山东大业股份有限公司 | Phosphating method and device for metal wire surface treatment |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4228470A1 (en) * | 1992-08-27 | 1994-03-03 | Henkel Kgaa | Process for phosphating steel strips galvanized on one side |
| DE4241134A1 (en) * | 1992-12-07 | 1994-06-09 | Henkel Kgaa | Process for phosphating metal surfaces |
| JP3348856B2 (en) * | 1993-09-06 | 2002-11-20 | 日本パーカライジング株式会社 | Nickel free phosphating method |
| DE19606018A1 (en) * | 1996-02-19 | 1997-08-21 | Henkel Kgaa | Zinc phosphating with low levels of nickel and / or cobalt |
-
1996
- 1996-09-26 DE DE19639596A patent/DE19639596A1/en not_active Withdrawn
-
1997
- 1997-09-17 AU AU44593/97A patent/AU4459397A/en not_active Abandoned
- 1997-09-17 CN CN97198236A patent/CN1231706A/en active Pending
- 1997-09-17 WO PCT/EP1997/005091 patent/WO1998013534A2/en not_active Application Discontinuation
- 1997-09-17 JP JP51522798A patent/JP2001508123A/en active Pending
- 1997-09-17 KR KR1019990702409A patent/KR20000048509A/en not_active Application Discontinuation
- 1997-09-17 ES ES97942941T patent/ES2153217T3/en not_active Expired - Lifetime
- 1997-09-17 EP EP97942941A patent/EP0931179B1/en not_active Expired - Lifetime
- 1997-09-17 DE DE59702741T patent/DE59702741D1/en not_active Expired - Fee Related
- 1997-09-17 CA CA002266625A patent/CA2266625A1/en not_active Abandoned
- 1997-09-17 ID IDW990112A patent/ID21474A/en unknown
- 1997-09-17 AT AT97942941T patent/ATE197969T1/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313579A (en) * | 2014-11-11 | 2015-01-28 | 武汉钢铁(集团)公司 | Production method of zinc-magnesium galvanized alloy steel plate |
| CN104313579B (en) * | 2014-11-11 | 2017-01-18 | 武汉钢铁(集团)公司 | Production method of zinc-magnesium galvanized alloy steel plate |
| CN111349867A (en) * | 2020-04-10 | 2020-06-30 | 武汉钢铁有限公司 | Coating-friendly pre-phosphorized electro-galvanized automobile outer plate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19639596A1 (en) | 1998-04-02 |
| DE59702741D1 (en) | 2001-01-11 |
| ES2153217T3 (en) | 2001-02-16 |
| EP0931179B1 (en) | 2000-12-06 |
| ID21474A (en) | 1999-06-17 |
| CA2266625A1 (en) | 1998-04-02 |
| WO1998013534A3 (en) | 1998-08-27 |
| KR20000048509A (en) | 2000-07-25 |
| ATE197969T1 (en) | 2000-12-15 |
| EP0931179A2 (en) | 1999-07-28 |
| AU4459397A (en) | 1998-04-17 |
| JP2001508123A (en) | 2001-06-19 |
| WO1998013534A2 (en) | 1998-04-02 |
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