EP1042533A1 - Procede de phosphatation de feuillard d'acier galvanise d'un seul cote - Google Patents

Procede de phosphatation de feuillard d'acier galvanise d'un seul cote

Info

Publication number
EP1042533A1
EP1042533A1 EP98966286A EP98966286A EP1042533A1 EP 1042533 A1 EP1042533 A1 EP 1042533A1 EP 98966286 A EP98966286 A EP 98966286A EP 98966286 A EP98966286 A EP 98966286A EP 1042533 A1 EP1042533 A1 EP 1042533A1
Authority
EP
European Patent Office
Prior art keywords
phosphating
ions
phosphating solution
galvanized
components
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98966286A
Other languages
German (de)
English (en)
Inventor
Jörg Riesop
Klaus-Peter Mohr
Walter Jansen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Isorel Sa SA
Isorel SA
Original Assignee
Henkel AG and Co KGaA
Isorel Sa SA
Isorel SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA, Isorel Sa SA, Isorel SA filed Critical Henkel AG and Co KGaA
Publication of EP1042533A1 publication Critical patent/EP1042533A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C23C22/12—Orthophosphates containing zinc 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
    • C23C22/07—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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions

Definitions

  • the invention relates to a method for phosphating the galvanized side of steel strip galvanized on one side, the non-galvanized side not being phosphated.
  • the selective phosphating of the galvanized side is achieved by adding suitable components to the phosphating solution, which inhibit phosphating of the non-galvanized steel side, but do not impair the phosphating of the galvanized side. This eliminates the need for constructive measures to cover the steel side if only the galvanized side is to be phosphated.
  • steel strip is galvanized on one side, this is understood to mean electrolytically galvanized or alloy galvanized steel strip.
  • the zinc layer contains additional alloy components such as iron, nickel and / or aluminum.
  • phosphating surfaces made of iron, steel, zinc and their alloys as well as aluminum and its alloys have long been state of the art.
  • the phosphating of the surfaces mentioned serves to increase the adhesive strength of paint layers and to improve corrosion protection.
  • the phosphating is carried out by immersing the metal surfaces in the phosphating solutions or by spraying the metal surfaces with the phosphating solutions. Combined methods are also known.
  • Shaped metal parts such as automobile bodies can be phosphated, but also metal strips in high-speed conveyor systems.
  • the present invention is concerned with such a band phosphating.
  • Band phosphating differs from partial phosphating in that due to the high belt speeds, the phosphating, ie the growth of a closed metal phosphate layer, must take place within a short period of time, for example from about 2 to about 20 seconds.
  • phosphating metal strips in particular electrolytically galvanized or hot-dip galvanized steel strips
  • WO 91/02829 describes a process for the phosphating of electrolytically and / or hot-dip galvanized steel strip by brief treatment with acidic phosphating solutions which, in addition to zinc and phosphate ions, contain manganese and nickel cations and anions of oxygen-containing acids with accelerating action.
  • acidic phosphating solutions which, in addition to zinc and phosphate ions, contain manganese and nickel cations and anions of oxygen-containing acids with accelerating action.
  • the latter term is to be understood in particular as nitrate ions.
  • DE-A-35 37 108 likewise describes a process for the phosphating of electrolytically galvanized steel strips by treatment with acidic phosphating solutions which, in addition to zinc, manganese and phosphate ions, contain further metal cations such as, for example, nickel ions and / or anions of oxygen-containing acids with accelerating action, in particular nitrate ions. contain.
  • the contents of zinc cations are in the relatively low range of 0.1 to 0.8 g / 1.
  • DE-A-197 40 953 describes a method for phosphating steel strip or steel strip galvanized on one or both sides or alloy galvanized by spray or dip treatment for a period in the range from 2 to 20
  • Phosphating solution with a temperature in the range of 50 to 70 ° C, characterized in that the phosphating solution is free of nitrate ions and that it
  • 0.1 to 3 g / 1 hydroxylamine in free, ionic or bound form contains, has a free acid content in the range of 0.4 to 4 points and a total acid content in the range of 15 to 45 points.
  • the invention relates to a method for phosphating steel strip galvanized on one side with a phosphating solution which contains 1 to 6 g / 1 zinc ions and 10 to 30 g / 1 phosphate ions, characterized in that the phosphating solution additionally contains one or more of the components a) to c) contains: a) 60 to 1000 mg / 1 of one or more mono- or polyhydric alcohols with at least one triple bond between two carbon atoms, b) 10 to 160 mg / 1 of one or more alkyl or alkenyl nitrogen compounds with at least 5 C atoms, c) 10 to 250 mg / 1 alkali metal iodide.
  • the process is characterized in that the phosphating solution contains one or more of components a) to c) in the following concentrations: a) 200 to 400 mg / l of one or more mono- or polyhydric alcohols with at least one triple bond between two Carbon atoms, b) 30 to 60 mg / 1 of one or more alkyl or alkenyl nitrogen compounds with at least 5 C atoms, c) 40 to 100 mg / 1 alkali metal iodide.
  • the individual components a), b) and c) hinder or prevent the pickling reaction of the phosphating solution with the non-galvanized steel surface, so that it is not or not significantly phosphated. However, the pickling reaction on the galvanized surface is not hindered, so that the desired closed crystalline zinc phosphate layer with the desired layer weight is formed here.
  • layer weight is common in the field of phosphating metal surfaces.
  • layer weight or detailed “phosphate layer weight”
  • area-related mass is also used. This is understood to mean the mass of the metal phosphate layer produced on the metal surface by the phosphating, based on a unit area. It is usually given in g / m 2 . It can be determined by weighing a phosphated metal sheet with a known surface, detaching the metal phosphate layer and weighing the metal sheet again. The mass of the metal phosphate layer based on m can be calculated from the determined weight difference, taking into account the surface of the metal sheet. A 0.5% by weight chromic acid solution can be used, for example, to detach the metal phosphate layer. The method of determining the layer weight is described in more detail in the German standard DIN 50942.
  • the layer weight represents an essential parameter for checking the phosphating result. Depending on the intended use of the phosphated metal parts, layer weights are sought in different areas.
  • the present invention is preferably concerned with sheet metal, which in Automotive engineering is used. Layer weights of above 0.8 g / m 2 but at most about 4 g / m 2 are aimed for.
  • the layer weights should preferably be below 3 g / m 2 and in particular be about 1 to about 2 g / m 2 .
  • Components a), b) and c) complement each other in their action as inhibitors against pickling attack on the non-galvanized steel side. Therefore, the phosphating of the non-galvanized steel side is prevented more effectively and reliably if the phosphating solution contains at least 2 of components a), b) and c).
  • the phosphating solution preferably contains all 3 components a), b) and c).
  • Component a) can be selected, for example, from acetylenically unsaturated diols.
  • a preferred example of this is butyne-2-diol-1,4.
  • component b) examples are alkylamines or alkenylamines.
  • Alkyl or alkenyl-substituted nitrogen-containing heterocycles, in particular unsaturated heterocycles, are also particularly suitable. These can carry, for example, one, two or three nitrogen atoms in the heterocycle.
  • An alkyl group is preferably as far away from the nitrogen atom or atoms.
  • a particularly preferred example is mono- and dialkylpyridines having 1 to 22, preferably 1 to 12, carbon atoms in each alkyl group, an alkyl group preferably being in the 4-position to the N atom. These alkylated pyridines are usually available as technical mixtures.
  • Potassium iodide is preferably used as component c) due to its easy technical availability.
  • the phosphating solution can contain up to 250 mg / 1, preferably about 40 to about 80 mg / 1, of a nonionic surfactant. In combination with at least one of components a), b) and / or c) this surfactant supports the inhibiting effect on the non-galvanized steel side.
  • the nonionic surfactant used is preferably ethoxylated, propoxylated and / or ethoxylated / propoxylated alcohols having 10 to 18 carbon atoms in the alkyl radical.
  • the phosphating solution can contain a solubilizer for the surfactant. This can be present in a concentration of up to 750 mg / 1, preferably from about 150 to about 300 mg / 1. Examples of possible solubilizers are cumene sulfonate.
  • the phosphating solution can contain further components which are customary in the prior art and are either incorporated into the phosphating solution.
  • the phosphating solution additionally contains one or more of the following cations:
  • the phosphating solutions contain alkali metal and / or ammonium cations in order to adjust the value of the free acid to the desired range.
  • Phosphating baths usually also contain so-called accelerators. These are substances that react with the hydrogen generated on the metal surface during the pickling reaction. This prevents a so-called polarization of the metal surface by covering it with hydrogen. As a result, the accelerators improve the uniform covering of the metal surface with fine-particle phosphate crystals, which are usually one size have between about 1 and about 10 microns. Also in accordance with the invention
  • Processes are preferably used phosphating solutions that contain accelerators. Accordingly, it is preferred for the process according to the invention that the
  • Phosphating solution additionally as an accelerator one or more of the following
  • Components contains:
  • a phosphating solution which additionally contains about 0.1 to about 3 g / 1 hydroxy lamin in free, ionic or bound form as accelerator is preferred for the process according to the invention.
  • Hydroxylamine can be used as a free base, as a hydroxylamine-releasing compound such as hydroxylamine complexes and ketoximes or aldoximes or in the form of hydroxylammonium salts. If free hydroxylamine is added to the phosphating bath or a phosphating bath concentrate, it will largely exist as a hydroxylammonium cation due to the acidic nature of these solutions. When used as a hydroxylammonium salt, the sulfates and the phosphates are particularly suitable. In the case of the phosphates, the acid salts are preferred due to the better solubility.
  • a combination of free hydroxylamine and hydroxylammonium sulfate can advantageously be used in order to take economic aspects into account on the one hand and on the other hand not to burden the phosphating baths with too much sulfate ions.
  • Hydroxylamine or its compounds are added to the phosphating solution in amounts such that the calculated concentration of the free hydroxylamine is between about 0.1 to about 3 g / 1, preferably between about 0.15 and about 1 g / 1.
  • the total phosphorus content of the phosphating bath is considered to be present in the form of phosphate ions PO 4 3 " .
  • the known fact is ignored in the concentration calculation or determination that the pH values in the acidic region cause the Phosphating baths in the range from about 2.0 to about 3.6 only a very small part of the phosphate is actually in the form of the 3-fold negatively charged anions Dihydrogen phosphate anion is present, together with undisociated phosphoric acid and with smaller amounts of double negatively charged hydrogen phosphate anions.
  • a further embodiment of the invention consists in using phosphating solutions which contain up to about 0.8 g / 1 fluoride in free or complex-bound form.
  • the preferred fluoride contents are in the range from 0.0 to about 0.5 g / 1, in particular in the range from about 0.1 to about 0.2 g / 1.
  • the phosphating solutions are generally prepared in the manner known to the person skilled in the art.
  • phosphate is introduced into the phosphating solutions in the form of phosphoric acid.
  • the cations are added in the form of acid-soluble compounds such as, for example, the carbonates, the oxides or the hydroxides of phosphoric acid, so that this is partially neutralized.
  • the further neutralization to the desired pH range is preferably carried out by adding sodium hydroxide or sodium carbonate.
  • Suitable sources of free fluoride anions are, for example, sodium or potassium fluoride.
  • tetrafluoroborate or hexafluorosilicate can be used as complex fluorides.
  • phosphating solutions are preferably used which have a free acid content in the range from about 0.4 to about 4 points and a total acid content in the range from about 15 to about 45 points.
  • the terms "free acid” and “total acid” and their method of determination have already been explained above.
  • the free acid values are preferably between about 1.5 and about 3.5 and in particular between about 2.0 and about 3.0 points.
  • the total acid levels are preferably in the range of about 25 to about 35 points.
  • free acid and total acid are generally known in the field of phosphating. They are determined by titrating the acid bath sample with 0.1 normal sodium hydroxide solution and measuring its consumption. The consumption in ml is given as a score.
  • the number of free acids means the consumption in ml of 0.1 normal sodium hydroxide solution in order to titrate 10 ml of bath solution, which has been diluted to 50 ml with deionized water, up to a pH of 4.0 .
  • the total acid score indicates consumption in ml up to a pH of 8.2.
  • the temperature of the phosphating solution in the process according to the invention is preferably in the range from about 50 to about 70 ° C. and in particular between 53 and 65 ° C.
  • the one-sided galvanized steel strip is brought into contact with the phosphating solution for a period of time in the range from about 2 to about 30 seconds by spraying the phosphating solution onto the galvanized steel strip or by immersing the galvanized steel strip in the phosphating solution.
  • the spray treatment is technically easier to carry out and is therefore preferred. Treatment times between 3 and 15 seconds are particularly preferred.
  • the phosphating solution is rinsed off with water from the galvanized steel strip.
  • the process according to the invention is preferably used to produce crystalline zinc phosphate layers with layer weights in the range from 1 to 2 g / m 2 on the galvanized side of the steel strip galvanized on one side.
  • the metal surface must be completely water wettable before applying the phosphating solution. This is usually the case in continuously operating conveyor systems. However, if the belt surface is oiled, this oil must be removed by a suitable cleaner before phosphating. The procedures for this are common in the art.
  • activation is usually carried out using activation agents known in the art. Solutions or suspensions are usually used which contain titanium phosphates and sodium phosphates. The activation is followed by the use of the phosphating process according to the invention, which is advantageously followed by a passivating rinse. An intermediate rinse with water usually takes place between phosphating and passivating rinsing. Treatment baths containing chromic acid are widely used for passivating rinsing.
  • the invention relates to the use of an aqueous solution comprising water and, based on the total composition a) 10 to 30% by weight of one or more mono- or polyhydric alcohols with at least one triple bond between two carbon atoms, b) 1, 6 to 4.8 wt .-% of one or more alkyl or alkenyl nitrogen compounds with at least 5 carbon atoms and c) contains 2.4 to 7.2 wt .-% alkali metal iodide, as an additive to a phosphating solution for the Phosphating of the galvanized side of steel galvanized on one side.
  • the aqueous solution for the use according to the invention preferably additionally contains 2 to 8% by weight of one or more nonionic surfactants, which were also characterized in more detail above.
  • the addition of surfactant improves the purpose intended with the use according to the invention of protecting the non-galvanized steel side of one-sided galvanized steel strip against phosphating.
  • an aqueous solution is preferably used which, together with the nonionic surfactant, contains a solubilizer for this surfactant.
  • a solubilizer for this surfactant for example, cumene sulfonate is suitable here. So much solubilizer is used that a clear surfactant solution is formed.
  • the use according to the invention is such that the aqueous solution of components a), b) and c) is added in an amount between 0.15 and 1% by volume of the phosphating solution.
  • the amount added is chosen so that the phosphating solution contains components a), b) and c) in the following concentration ranges: a) 60 to 1000 mg / l of one or more mono- or polyhydric alcohols with at least one triple bond between two carbon atoms, b ) 10 to 160 mg / 1 of one or more alkyl or alkenyl nitrogen compounds with at least 5 C atoms and c) 10 to 250 mg / 1 alkali metal iodide.
  • the method according to the invention was tested in a laboratory plant for phosphating.
  • Sample sheets galvanized on one side were activated with an activation solution containing titanium phosphate (Fixodine R 950, Henkel KGaA, batch concentration 0.5% by weight) and phosphated under the conditions given in the table.
  • an activation solution containing titanium phosphate (Fixodine R 950, Henkel KGaA, batch concentration 0.5% by weight) and phosphated under the conditions given in the table.
  • the phosphating bath had the following composition:

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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

L'invention concerne un procédé de phosphatation de feuillard d'acier galvanisé d'un seul côté, au moyen d'une solution de phosphatation qui contient 1 à 6 g/l d'ions zinc et 10 à 30 g/l d'ions phosphate. L'invention est caractérisée en ce que la solution de phosphatation contient en outre un ou plusieurs des composants suivants: a) 60 à 1000 mg/l d'un ou plusieurs alcools monovalents ou polyvalents comportant au moins une liaison triple entre deux atomes de carbone, b) 10 à 160 mg/l d'un ou plusieurs composés d'alkyle-azote ou d'alcényle-azote comportant au moins 5 atomes de carbone et c) 10 à 250 mg/l d'iodure de métaux alcalins. De préférence, la solution de phosphatation contient au moins deux des composants a), b) et c), et en particulier les trois.
EP98966286A 1997-12-19 1998-12-10 Procede de phosphatation de feuillard d'acier galvanise d'un seul cote Withdrawn EP1042533A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1997156735 DE19756735A1 (de) 1997-12-19 1997-12-19 Phosphatierung von einseitig verzinktem Stahlband
DE19756735 1997-12-19
PCT/EP1998/008047 WO1999032687A1 (fr) 1997-12-19 1998-12-10 Procede de phosphatation de feuillard d'acier galvanise d'un seul cote

Publications (1)

Publication Number Publication Date
EP1042533A1 true EP1042533A1 (fr) 2000-10-11

Family

ID=7852655

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98966286A Withdrawn EP1042533A1 (fr) 1997-12-19 1998-12-10 Procede de phosphatation de feuillard d'acier galvanise d'un seul cote

Country Status (5)

Country Link
EP (1) EP1042533A1 (fr)
AU (1) AU2269999A (fr)
CA (1) CA2315778A1 (fr)
DE (1) DE19756735A1 (fr)
WO (1) WO1999032687A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU1581700A (en) * 1998-07-21 2000-02-28 Brent International Plc Nickel-zinc phosphate conversion coatings
DE10127513A1 (de) * 2001-06-06 2002-12-12 Creavis Tech & Innovation Gmbh Antimikrobielle Vliesstoffe
DE102008004728A1 (de) 2008-01-16 2009-07-23 Henkel Ag & Co. Kgaa Phosphatiertes Stahlblech sowie Verfahren zur Herstellung eines solchen Blechs
DE102017208802A1 (de) * 2016-05-25 2017-11-30 Chemetall Gmbh Verfahren zur korrosionsschützenden Phosphatierung einer metallischen Oberfläche mit vermindertem Beizabtrag

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Publication number Priority date Publication date Assignee Title
US3773465A (en) * 1970-10-28 1973-11-20 Halliburton Co Inhibited treating acid
US4233088A (en) * 1979-03-29 1980-11-11 International Lead Zinc Research Organization, Inc. Phosphatization of steel surfaces and metal-coated surfaces
JPS6220879A (ja) * 1985-07-18 1987-01-29 Nippon Kokan Kk <Nkk> 亜鉛メツキ装置による鋼板の片面化成処理方法
DE4228470A1 (de) * 1992-08-27 1994-03-03 Henkel Kgaa Verfahren zur Phospatierung von einseitig verzinktem Stahlband
DE4241134A1 (de) * 1992-12-07 1994-06-09 Henkel Kgaa Verfahren zur Phosphatierung von Metalloberflächen
DE4326388A1 (de) * 1993-08-06 1995-02-09 Metallgesellschaft Ag Verfahren zur phosphatierenden Behandlung von einseitig verzinktem Stahlband
CN1041001C (zh) * 1993-09-06 1998-12-02 汉克尔股份两合公司 无镍的磷酸盐化处理金属表面的方法
DE4341041A1 (de) * 1993-12-02 1995-06-08 Henkel Kgaa Nickelfreies Phosphatierverfahren mit m-Nitrobenzolsulfonat

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9932687A1 *

Also Published As

Publication number Publication date
AU2269999A (en) 1999-07-12
CA2315778A1 (fr) 1999-07-01
WO1999032687A1 (fr) 1999-07-01
DE19756735A1 (de) 1999-06-24

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