EP3879003A1 - Procédé amélioré pour augmenter la concentration d'ions de fer(ii) dans des systèmes de phosphatation côté fer et installation de phosphatation associée - Google Patents

Procédé amélioré pour augmenter la concentration d'ions de fer(ii) dans des systèmes de phosphatation côté fer et installation de phosphatation associée Download PDF

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Publication number
EP3879003A1
EP3879003A1 EP20162034.1A EP20162034A EP3879003A1 EP 3879003 A1 EP3879003 A1 EP 3879003A1 EP 20162034 A EP20162034 A EP 20162034A EP 3879003 A1 EP3879003 A1 EP 3879003A1
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EP
European Patent Office
Prior art keywords
iron
phosphating
magnet
bath container
ions
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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.)
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Application number
EP20162034.1A
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German (de)
English (en)
Inventor
Ralf Schneider
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Chemetall GmbH
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Chemetall GmbH
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Publication date
Application filed by Chemetall GmbH filed Critical Chemetall GmbH
Priority to EP20162034.1A priority Critical patent/EP3879003A1/fr
Publication of EP3879003A1 publication Critical patent/EP3879003A1/fr
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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
    • C23C22/12—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
    • C23C22/18—Orthophosphates containing 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
    • C23C22/07—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
    • C23C22/73—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 characterised by the process

Definitions

  • the present invention refers to an improved method for increasing the concentration of iron(II) ions in iron side phosphating systems as well as to an accordingly modified iron side phosphating plant.
  • iron side phosphating systems are used to phosphatize steel substrates, in particular steel wires or construction elements, and exhibit a content of iron(II) ions.
  • iron side phosphating systems manganese phosphate systems as well as heavy zinc phosphate systems additionally containing iron(II) ions are particularly suitable.
  • the phosphate layers being formed on the substrates usually consist of Phosphophyllite and/or Hureaulite crystals including a significant amount of iron atoms in their structure and/or of Hopeite crystals. By such phosphate layers, the corrosion resistance of the substrates as well as the adhesion of subsequent paint layers on the substrates is enhanced effectively.
  • iron(II) ions Due to the integration of iron(II) ions into the phosphate layer, a continuous consumption of iron(II) ions in the phosphating system takes place during the phosphating process. Thus, in order to maintain the necessary concentration, replenishment of iron(II) ions is required - especially in times of low throughput of iron-containing substrates, this means when the amount of iron(II) ions dissolved out of said substrates is correspondingly low.
  • iron(II) ions Another common option to achieve the required concentration of iron(II) ions is to put steel-containing scrap into the phosphating bath. Due to the acidic aqueous milieu, iron(II) ions are dissolved out of the scrap into the phosphating composition. However, steel-containing scrap has an unknown content of chromium which is poisonous for the phosphating process and is dissolved out into the phosphating composition as well. In addition, oxide layers on the surface of the scrap may prevent the iron(II) ions from being dissolved.
  • iron(II) phosphate solution is rather limited as after a short period of time iron(III) ions are formed by oxidation leading to a precipitation of iron(III) phosphate.
  • iron-containing means that an according body contains iron in such a way, preferably in its surface, that iron(II) ions are dissolved out of the body when the latter is immersed in an aqueous acidic medium.
  • iron-containing body should also encompass two or more or even a multitude of iron-containing bodies.
  • the iron-containing body may be a powder as an assembly of a multitude of particles.
  • aqueous is to be understood such that water makes up more than 50 wt.-% of the solvent/s and dispersing medium/a of an according composition.
  • composition is preferably a solution or dispersion, more preferably a solution.
  • a preferred order of steps i) to iii) is: First step iii), then step ii) and finally step i).
  • a preferred order of steps i) to iii) is: First step i), then step ii) and finally step iii).
  • the temperature of phosphating composition usually lies in the range of from 50 to 95 °C, preferably in the range of from 60 to 80 °C.
  • the time required to increase the concentration of iron(II) ions to a concentration in the range of from 0.5 to 1.0 g/l usually lies in the range of from 10 to 60 minutes, preferably in the range of from 10 to 20 minutes.
  • the present method preferably comprises the following additional step: v) At least one optionally pickled and/or cleaned metal substrate is immersed into the phosphating composition and phosphatized by an iron side phosphating process, wherein a concentration of iron(II) ions in the phosphating composition of up to 5 g/l or even up to 7 g/l is obtained.
  • the coating weights and the grain sizes of the phosphate layers formed in step v) are comparable to or even better than those of phosphate layers formed when using soluble steel wool just thrown into the phosphating bath, steel-containing scrap or iron(II) phosphate solution as described herein above.
  • the temperature of phosphating composition usually lies in the range of from 50 to 95 °C, preferably in the range of from 60 to 80 °C.
  • the time required to phosphatize an according metal substrate usually lies in the range of from 3 to 20 minutes, preferably in the range of from 5 to 10 minutes.
  • the at least one metal substrate is preferably at least one iron-containing substrate, more preferably at least one steel-containing substrate, even more preferably at least one substrate made of steel, in particular at least one wire or construction element made of steel. According construction elements may be used in the construction of aircrafts for example.
  • the aqueous acidic phosphating composition preferably comprises, beside phosphate ions, manganese and/or zinc ions.
  • manganese phosphate systems comprising manganese, iron(II) and nickel ions, as well as heavy zinc phosphate systems comprising zinc, iron(II) and nickel ions or zinc, manganese, nickel and iron(II) ions.
  • no air is blown into the phosphating composition nor is an oxidizing agent such as nitrite or chlorate added as this may cause precipitation of iron(III) phosphate, this means formation of so-called sludge.
  • an oxidizing agent such as nitrite or chlorate added as this may cause precipitation of iron(III) phosphate, this means formation of so-called sludge.
  • permanent magnets as well as electromagnets may be used, wherein permanent magnets are preferred due to the dangers linked to the use of electrical current.
  • the bath container is commonly made of stainless steel being non-magnetic.
  • a strength of the magnet/s is required which is high enough to effectively attach the at least one iron-containing body on the inside wall of the bath container.
  • neodymium magnets i.e. so-called super magnets, are especially preferred.
  • At least one magnet may be attached onto the inside wall of the bath container, in particular by means of screwing or clamping. Due to the contact with the phosphating composition, the magnet/s need/s to have sufficient heat as well as acid resistance. The same applies to the following case: Alternatively, or even additionally, it is possible to hang at least one magnet, for example at least one spherical magnet, each one by means of at least one holder element, into the inside room of the bath container.
  • the at least one magnet is attached onto the outside wall of the phosphating bath container, wherein the at least one magnet is more preferably at least two magnets and even more preferably exactly two magnets.
  • the at least one magnet is hung, each one by means of at least one holder element, into the inside room of the bath container, wherein the at least one magnet is more preferably one magnet, for example one spherical magnet, which is more preferably hung into the inside room of the bath container by means of exactly one holder element.
  • the at least one iron-containing body is preferably selected from the group consisting of iron powder, iron wool, steel powder and steel wool, more preferably from the group consisting of iron powder and iron wool. Most preferably, the at least one iron-containing body is iron powder.
  • Iron powder and iron wool have the advantage that they are free or at least essentially free of toxic chromium.
  • iron/steel powder is advantageous because it can more effectively be attached to the at least one magnet such that the risk of undissolved portions of iron-containing body swimming around in the bath and settling down on the surface of the substrates to be phosphatized is even more reduced.
  • Iron powder having an average particle size of less than 90 ⁇ m is especially preferred as the iron(II) ions are more effectively dissolved out into the acidic aqueous phosphating composition.
  • the iron-containing body/ies is/are at least partially immersed in the phosphating composition.
  • complete immersion is preferred as the iron(II) ions can be dissolved out more effectively then.
  • the present invention also refers to a modified iron side phosphating plant according to claim 10, namely a phosphating plant which is characterized by comprising
  • the at least one magnet is attached onto the outside wall of the phosphating bath container, wherein the at least one magnet is more preferably at least two magnets and even more preferably exactly two magnets.
  • the at least one magnet is hung, each one by means of at least one holder element, into the inside room of the bath container, wherein the at least one magnet is more preferably one magnet, for example one spherical magnet, which is more preferably hung into the inside room of the bath container by means of exactly one holder element.
  • iron powder (1a, 1b) is attached to two permanent magnets (2a, 2b; grey sections) which are attached on the outside wall (3) of the phosphating bath container (4) below the surface (5; dotted line) of the phosphating composition.
  • a corresponding phosphating plant is shown in Fig. 1 .
  • the walls of the bath container (4) as well as the first magnet (2a) are depicted as being transparent.
  • iron powder (1) is attached to a spherical permanent magnet (2; grey disc) which, by means of a holder element (3), is immersed in the phosphating bath, this means below the surface (5; dotted line) of the phosphating composition in the phosphating bath container (4).
  • a corresponding phosphating plant is shown in Fig. 2 .
  • the walls of the bath container (4) are depicted as being transparent.

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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)
EP20162034.1A 2020-03-10 2020-03-10 Procédé amélioré pour augmenter la concentration d'ions de fer(ii) dans des systèmes de phosphatation côté fer et installation de phosphatation associée Withdrawn EP3879003A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20162034.1A EP3879003A1 (fr) 2020-03-10 2020-03-10 Procédé amélioré pour augmenter la concentration d'ions de fer(ii) dans des systèmes de phosphatation côté fer et installation de phosphatation associée

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Application Number Priority Date Filing Date Title
EP20162034.1A EP3879003A1 (fr) 2020-03-10 2020-03-10 Procédé amélioré pour augmenter la concentration d'ions de fer(ii) dans des systèmes de phosphatation côté fer et installation de phosphatation associée

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0372591A1 (fr) * 1988-12-02 1990-06-13 Metallgesellschaft Ag Procédé de phosphatation de surfaces métalliques
DE3934251C1 (fr) * 1989-10-13 1991-01-24 Deutsche Forschungsanstalt Fuer Luft- Und Raumfahrt Ev, 5300 Bonn, De
DE102010042425A1 (de) * 2010-10-13 2012-04-19 Vacuumschmelze Gmbh & Co. Kg Reinigungs- und Passivierungslösung, Reinigungsverfahren und Verfahren zur Beareitung und Reinigung eines Magneten
KR102020426B1 (ko) * 2018-03-02 2019-09-10 주식회사 포스코 마찰유닛 및 이를 포함하는 표면처리장치

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0372591A1 (fr) * 1988-12-02 1990-06-13 Metallgesellschaft Ag Procédé de phosphatation de surfaces métalliques
DE3934251C1 (fr) * 1989-10-13 1991-01-24 Deutsche Forschungsanstalt Fuer Luft- Und Raumfahrt Ev, 5300 Bonn, De
DE102010042425A1 (de) * 2010-10-13 2012-04-19 Vacuumschmelze Gmbh & Co. Kg Reinigungs- und Passivierungslösung, Reinigungsverfahren und Verfahren zur Beareitung und Reinigung eines Magneten
KR102020426B1 (ko) * 2018-03-02 2019-09-10 주식회사 포스코 마찰유닛 및 이를 포함하는 표면처리장치

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