EP0327153A2 - Procédé pour former des couches de phosphates sur des métaux - Google Patents

Procédé pour former des couches de phosphates sur des métaux Download PDF

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Publication number
EP0327153A2
EP0327153A2 EP89200142A EP89200142A EP0327153A2 EP 0327153 A2 EP0327153 A2 EP 0327153A2 EP 89200142 A EP89200142 A EP 89200142A EP 89200142 A EP89200142 A EP 89200142A EP 0327153 A2 EP0327153 A2 EP 0327153A2
Authority
EP
European Patent Office
Prior art keywords
individual parts
solution
phosphate
phosphating
contact
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.)
Granted
Application number
EP89200142A
Other languages
German (de)
English (en)
Other versions
EP0327153B1 (fr
EP0327153A3 (en
Inventor
Horst Dr. Gehmecker
Werner Dr. Rausch
Peter Jörns
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.)
GEA Group AG
Continentale Parker Ste
Continentale Parker SA
Original Assignee
Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker 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 Metallgesellschaft AG, Continentale Parker Ste, Continentale Parker SA filed Critical Metallgesellschaft AG
Publication of EP0327153A2 publication Critical patent/EP0327153A2/fr
Publication of EP0327153A3 publication Critical patent/EP0327153A3/de
Application granted granted Critical
Publication of EP0327153B1 publication Critical patent/EP0327153B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/34Chemical 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
    • C23C22/36Chemical 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
    • C23C22/362Chemical 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 zinc cations
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/78Pretreatment of the material to be coated

Definitions

  • the invention relates to a process for the production of phosphate coatings on at least partially iron or steel surfaces having individual parts made of metal by means of aqueous phosphating solutions which contain zinc, phosphate, nitrate and autocatalytically formed nitrite ions and are practically free of iron II ions.
  • Another type of zinc phosphate process which usually works with high nitrate contents and at higher temperatures, is characterized in that the phosphating solutions used are practically free of iron II ions. In them, nitrite, which contains the iron II ions, forms autocatalytically Iron III ions are transferred, which in turn form poorly soluble iron phosphate with phosphate ions (DE-A-25 40 684).
  • the object of the invention is to provide a method for producing phosphate coatings on at least partially iron or steel surfaces having individual parts, which does not have the disadvantage of the long treatment time, but leads in a short time to phosphate coatings which are nevertheless of high quality.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the individual parts are in contact with a phosphating solution at a temperature in the range from 60 to 100 ° C. for a period of 3 to 30 seconds brings that 10 to 80 g / l zinc 12 to 80 g / l Phosphate (calculated as P2O5) 40 to 150 g / l Nitrate as well as additional 0.1 to 5 g / l fluoride 0.01 to 10 g / l nickel 0.001 to 0.1 g / l copper contains, in which the ratio of free acid to total acid is set to (0.1 to 0.3): 1 and which has at least 80 points total acid.
  • nitrite is formed autocatalytically, it may be necessary to add nitrite to the phosphating solution, for example in an amount of 0.03 to 0.2 g / l, in the initial phase of the process.
  • the method according to the invention is used in particular for the treatment of individual parts whose iron or steel surface has alloy additions of up to a maximum of 5% by weight.
  • the individual components of the phosphating solution such as zinc, phosphate, nitrate, etc.
  • the individual components are usually, as is customary in phosphating technology, pre-dissolved together as an acidic phosphating concentrate and introduced into the phosphating solution in this form.
  • the individual components are dimensioned in such a way that the required concentration ranges result in the phosphating solution.
  • additional cations from the alkali and / or ammonium group may have to be used.
  • titrate 10 ml bath sample with n / 10 NaOH against the first or second change in phosphoric acid using the color change of dimethyl yellow (free acid) or phenolphthalein (total acid), for example, as an indicator.
  • the ml of n / 10 NaOH consumed correspond to the free acid or the total acid in points.
  • the content of nitrite points is usually determined using the saccharometer method. For this, 50 ml of bath solution are mixed with 2 to 5 g of sulfamic acid. The amount of gas generated in ml is equal to the number of points. A gas point corresponds to a content of 46 mg / l NO2 in the phosphating solution.
  • the contact of the individual parts with the phosphating solution is preferably carried out by dipping or flooding.
  • the phosphate coatings produced by the process according to the invention have a layer weight of 2.0 to 10 g / m2.
  • a preferred embodiment of the invention consists in bringing the individual parts into contact with a phosphating solution 30 to 60 g / l zinc 30 to 50 g / l Phosphate (calculated as P2O5) 65 to 100 g / l nitrate 0.5 to 3.0 g / l Fluoride and 0.02 to 0.5 g / l nickel contains.
  • the rate of formation of the phosphate coating can be increased if, in accordance with a further advantageous embodiment of the invention, the individual parts are brought into contact with a phosphating solution which contains further accelerating additives.
  • accelerating additives can be, for example, chlorate, bromate, peroxide, m-nitrobenzenesulfonate, nitrophenol or combinations thereof.
  • a further improvement in the properties of the phosphate coating can be achieved if, according to a further advantageous embodiment of the invention, the individual parts are brought into contact with a phosphating solution which contains an additional 0.1 to 10 g / l, preferably 1 to 5 g / l, of manganese.
  • a phosphating solution which additionally contains 0.05 to 3 g / l tartaric acid and / or citric acid.
  • Another advantageous embodiment of the invention is to clean the individual parts before phosphating, if necessary to free them of rust, scale and phosphate layer and to activate them, and to passivate them with a rinse solution after phosphating, each of the process steps lasting from 3 to 30 sec is carried out.
  • an alkaline cleaning solution at a temperature in the range between 60 and 100 ° C. and a concentration in the range from 20 to 200 g / l for cleaning.
  • cleaners those based on sodium hydroxide, gluconate, phosphate with an additional content of carbonate, silicate and borate and surfactant.
  • the cleaner is preferably used in spraying.
  • Sulfuric acid or phosphoric acid solutions at a temperature in the range from 60 to 100 ° C. and a concentration in the range from 5 to 50% by weight have proven to be advantageous for the removal of rust, scale and phosphate layers that may be required.
  • a sulfuric or phosphoric acid is used which additionally contains iron II and / or iron III ions in a concentration in the range from 1 to 50 g / l.
  • the phosphating treatment After the phosphating treatment, it is usually rinsed with water, rinsed if necessary and dried if necessary.
  • a further advantageous embodiment of the invention provides for the individual parts to be passivated with a chrome-containing or chrome-free rinse solution. Possibly. can also be treated with an emulsion of an anti-corrosion oil, or it can be painted with or without passivation. In the event that cold forming is intended, an aftertreatment with a soap bath can also be carried out.
  • the phosphate coatings produced by the process according to the invention can be used advantageously in all fields in which phosphate coatings are used.
  • the phosphating process according to the invention is particularly favorable in improving the corrosion protection in the case of a subsequent painting.
  • the phosphate coating produced after this operation had a basis weight of 4 to 5 g / m2.
  • the phosphate coating was uniformly opaque and fine crystalline.

Landscapes

  • 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)
EP89200142A 1988-02-03 1989-01-24 Procédé pour former des couches de phosphates sur des métaux Expired - Lifetime EP0327153B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3803068 1988-02-03
DE3803068 1988-02-03

Publications (3)

Publication Number Publication Date
EP0327153A2 true EP0327153A2 (fr) 1989-08-09
EP0327153A3 EP0327153A3 (en) 1990-04-25
EP0327153B1 EP0327153B1 (fr) 1993-08-04

Family

ID=6346467

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89200142A Expired - Lifetime EP0327153B1 (fr) 1988-02-03 1989-01-24 Procédé pour former des couches de phosphates sur des métaux

Country Status (6)

Country Link
US (1) US4950339A (fr)
EP (1) EP0327153B1 (fr)
JP (1) JP2713334B2 (fr)
CA (1) CA1330515C (fr)
DE (1) DE58905074D1 (fr)
ES (1) ES2058464T3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19639597A1 (de) * 1996-09-26 1998-04-09 Henkel Kgaa Phosphatierverfahren für schnellaufende Bandanlagen

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3913089A1 (de) * 1989-04-21 1990-10-25 Henkel Kgaa Chlorat- und nitritfreies verfahren zur herstellung von nickel- und manganhaltigen zinkphosphatschichten
DE4433946A1 (de) * 1994-09-23 1996-03-28 Henkel Kgaa Phosphatierverfahren ohne Nachspülung
US5954892A (en) * 1998-03-02 1999-09-21 Bulk Chemicals, Inc. Method and composition for producing zinc phosphate coatings on metal surfaces
JP3479609B2 (ja) * 1999-03-02 2003-12-15 日本パーカライジング株式会社 スラッジ発生のないリン酸亜鉛処理液およびリン酸亜鉛処理方法
JP4630326B2 (ja) * 1999-08-09 2011-02-09 新日本製鐵株式会社 加工性に優れたリン酸塩処理亜鉛系めっき鋼板の製造方法
JP2001170557A (ja) * 1999-12-21 2001-06-26 Nisshin Steel Co Ltd めっき鋼板用表面処理液およびその処理方法
DE10010355A1 (de) * 2000-03-07 2001-09-13 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
CA2358625A1 (fr) 2000-10-10 2002-04-10 Henkel Corporation Revetement de conversion au phosphate
TWI224629B (en) * 2002-07-31 2004-12-01 Nippon Steel Corp Resin-lined steel pipe and method for manufacturing same
MX368832B (es) 2013-03-06 2019-10-18 Quaker Chem Corp Recubrimiento de conversión a alta temperatura sobre sustratos de acero y hierro.
CN105603406A (zh) * 2015-12-31 2016-05-25 芜湖市金宇石化设备有限公司 一种用于汽车车门涂装前磷化处理的处理液的制备方法
CN105543822A (zh) * 2015-12-31 2016-05-04 芜湖市金宇石化设备有限公司 一种用于汽车车门涂装前磷化处理的处理液
CN105463422A (zh) * 2015-12-31 2016-04-06 芜湖市金宇石化设备有限公司 一种汽车车门涂装前磷化处理方法
CN111197163A (zh) * 2018-11-20 2020-05-26 天津市银丰钢绞线股份有限公司 一种钢绞线的前处理工艺

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1469134A (fr) * 1965-12-28 1967-02-10 Sharples France Procédé de traitement par phosphatation au manganèse de pièces ayant subi un décapage chimique préalable, et bain permettant de mettre en oeuvre ledit procédé
US3355330A (en) * 1964-03-03 1967-11-28 Hooker Chemical Corp Metal treating processes
FR2235203A1 (fr) * 1973-06-29 1975-01-24 Parker Ste Continentale
US3939014A (en) * 1974-11-20 1976-02-17 Amchem Products, Inc. Aqueous zinc phosphating solution and method of rapid coating of steel for deforming
EP0186823A2 (fr) * 1984-12-20 1986-07-09 HENKEL CORPORATION (a Delaware corp.) Procédé pour faciliter la déformation à froid
EP0269138A1 (fr) * 1986-10-25 1988-06-01 Metallgesellschaft Ag Procédé pour produire des revêtements de phosphate sur des métaux

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AT282285B (de) * 1965-12-22 1970-06-25 Plaut Fa J Zinkphosphatüberzüge
US3516875A (en) * 1966-06-11 1970-06-23 Hooker Chemical Corp Process for coating ferrous surfaces
DE1521879B2 (de) * 1966-07-12 1975-08-28 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zum Aufbringen von Phosphatüberzügen auf Eisen und Stahl
US3432270A (en) * 1966-07-25 1969-03-11 Amchem Prod Method for determining nitrite concentration in acidic accelerated phosphating solutions
DE1911972A1 (de) * 1969-03-10 1970-10-01 Metallgesellschaft Ag Verfahren zur Tauchphosphatierung von Eisen und Stahl
US3617393A (en) * 1969-10-08 1971-11-02 Dainippon Toryo Kk Pretreatment before electrophoretic painting
US3647568A (en) * 1969-10-28 1972-03-07 Macdermid Inc Colored phosphate coatings and method of application
US3676224A (en) * 1970-10-16 1972-07-11 Lubrizol Corp Phosphating solution with scale suppressing characteristics
DE2100021A1 (de) * 1971-01-02 1972-09-07 Collardin Gmbh Gerhard Verfahren zum Aufbringen von Phos phatschichten auf Stahl, Eisen und Zinkoberflachen
US3767476A (en) * 1971-08-31 1973-10-23 Us Army Method and composition for phosphatizing steel under pressure
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JPS52141439A (en) * 1976-04-27 1977-11-25 Nippon Paint Co Ltd Method of managing chemicallconversion treating liquid for acidic phosphate coating
DE2736874A1 (de) * 1977-08-16 1979-03-01 Metallgesellschaft Ag Verfahren zur erleichterung der kaltumformung von metallen
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JPS5811514B2 (ja) * 1979-05-02 1983-03-03 日本ペイント株式会社 金属表面の保護方法
GB2080835B (en) * 1980-07-25 1984-08-30 Pyrene Chemical Services Ltd Prevention of sludge in phosphating baths
DE3101866A1 (de) * 1981-01-22 1982-08-26 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
DE3108484A1 (de) * 1981-03-06 1982-09-23 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur herstellung von phosphatueberzuegen auf metalloberflaechen
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US4719038A (en) * 1983-12-27 1988-01-12 Nippon Paint Co., Ltd. Corrosion resistant, coated metal laminate, its preparation and coating materials
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US4596607A (en) * 1985-07-01 1986-06-24 Ford Motor Company Alkaline resistant manganese-nickel-zinc phosphate conversion coatings and method of application
US4717431A (en) * 1987-02-25 1988-01-05 Amchem Products, Inc. Nickel-free metal phosphating composition and method for use

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3355330A (en) * 1964-03-03 1967-11-28 Hooker Chemical Corp Metal treating processes
FR1469134A (fr) * 1965-12-28 1967-02-10 Sharples France Procédé de traitement par phosphatation au manganèse de pièces ayant subi un décapage chimique préalable, et bain permettant de mettre en oeuvre ledit procédé
FR2235203A1 (fr) * 1973-06-29 1975-01-24 Parker Ste Continentale
US3939014A (en) * 1974-11-20 1976-02-17 Amchem Products, Inc. Aqueous zinc phosphating solution and method of rapid coating of steel for deforming
EP0186823A2 (fr) * 1984-12-20 1986-07-09 HENKEL CORPORATION (a Delaware corp.) Procédé pour faciliter la déformation à froid
EP0269138A1 (fr) * 1986-10-25 1988-06-01 Metallgesellschaft Ag Procédé pour produire des revêtements de phosphate sur des métaux

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19639597A1 (de) * 1996-09-26 1998-04-09 Henkel Kgaa Phosphatierverfahren für schnellaufende Bandanlagen
DE19639597C2 (de) * 1996-09-26 2000-01-20 Henkel Kgaa Verfahren zur Phosphatierung von laufenden Bändern aus kalt- oder warmgewalztem Stahl in schnellaufenden Bandanlagen

Also Published As

Publication number Publication date
JPH01259180A (ja) 1989-10-16
CA1330515C (fr) 1994-07-05
EP0327153B1 (fr) 1993-08-04
US4950339A (en) 1990-08-21
JP2713334B2 (ja) 1998-02-16
DE58905074D1 (de) 1993-09-09
EP0327153A3 (en) 1990-04-25
ES2058464T3 (es) 1994-11-01

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