WO2017202891A1 - Procédé de phosphatation anticorrosion d'une surface métallique à réduction de matière décapée - Google Patents

Procédé de phosphatation anticorrosion d'une surface métallique à réduction de matière décapée Download PDF

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Publication number
WO2017202891A1
WO2017202891A1 PCT/EP2017/062505 EP2017062505W WO2017202891A1 WO 2017202891 A1 WO2017202891 A1 WO 2017202891A1 EP 2017062505 W EP2017062505 W EP 2017062505W WO 2017202891 A1 WO2017202891 A1 WO 2017202891A1
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WO
WIPO (PCT)
Prior art keywords
composition
compound
formula
range
diol
Prior art date
Application number
PCT/EP2017/062505
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German (de)
English (en)
Inventor
Anna Verena MOHR
Carola Komp
Thomas Kolberg
Olaf Dahlenburg
Lisa SCHMEIER
Original Assignee
Chemetall Gmbh
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Publication of WO2017202891A1 publication Critical patent/WO2017202891A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • 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
    • 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
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • the invention relates to a process for the corrosion-protective phosphating of a metallic surface and to an aqueous composition for the reduction of pickling in the corrosion-protective phosphating of metallic surfaces.
  • aqueous cleaning and phosphating solutions which have a pH in the clearly acidic or alkaline range or in the clearly acidic range.
  • the acidic or alkaline pH initially serves to remove oxide films and impurities from the metallic surface.
  • the oxidative proton attack on the metallic surface itself causes the metal cations necessary for the formation of the phosphate coating to be dissolved out of it (so-called anodic metal dissolution).
  • the object of the invention was therefore to provide a method for corrosion-protective phosphating a metallic surfaces with reduced pickling and a composition for reducing the pickling in the corrosion-protective phosphating metallic surfaces available.
  • compositions comprising a (meth) acrylate and / or epoxide-based KTL, wherein the activating composition i) an activating agent is added and / or wherein the metallic surface between the contacting with the first rinsing composition ii) or optionally the second rinsing composition iii) and the phosphating composition iv) is brought into contact with an aqueous activating composition vii), wherein at least one of the compositions i) to v) comprises at least one compound of the formula I
  • R 1 is O- (CH 2 ) x Z- (CH 2 ) y-OR 2 (I), and wherein R 1 and R 2 are each independently H or an HO- (CH 2 ) w group with w> 2, x and y are each independently 1 to 4, and Z is an S atom or a CC triple bond ,
  • an "aqueous composition” is to be understood to mean one which contains water, for the most part, ie more than 50% by weight, as the solvent / dispersant,
  • the aqueous composition is a solution, more preferably about A solution containing only water as a solvent,
  • the fact that the metallic surface is sequentially contacted with the aqueous compositions i) to vi) does not preclude contacting them with one or more further compositions before and / or after this sequence It is also not excluded that the metallic surface is brought into contact with one or more further compositions between the contacting with the different compositions i) to vi).
  • the at least one compound of formula I acts as a physical corrosion inhibitor which is adsorbed by van der Waals forces on the metallic surface, forming a monomolecular, homogeneous, densely packed layer thereon.
  • the metallic surface is physically shielded from a proton or hydroxide ion attack and thus the pickling of the surface is prevented or at least reduced.
  • the detergent composition i) contains at least one compound of the formula I.
  • concentration of the at least one compound of the formula I in the detergent composition i) is preferably in the range from 6 to 625 mg / l, particularly preferably in the range from 31 to 313 mg / L (calculated as 2-butyne-1,4-diol).
  • the first rinsing composition ii), the second rinsing composition iii) and / or the third rinsing composition v) comprises at least one compound of the formula I.
  • the use of the at least one compound of formula I in one or more of the rinse compositions has the advantage of reducing the formation of flash rust on steel and / or galvanized steel.
  • the concentration of the at least one compound of the formula I is in the first rinsing composition ii), in the second rinsing composition iii) and in the third rinsing composition v) preferably in the range from 1 to 100 mg / l, particularly preferably in the range from 6 to 60 mg / L (calculated as 2-butyne-1,4-diol).
  • the phosphating composition iv) comprises at least one compound of the formula I.
  • the concentration of the at least one compound of the formula I in the phosphating composition iv) is in the range from 1 to 100 mg / l, preferably in the range from 1 to 10 mg / l (calculated as 2-butyne-1,4-diol).
  • the metallic surface must be activated for the phosphating. This can be done by adding to the detergent composition i) an activating agent and / or bringing the metallic surface into contact with the first rinsing composition ii) or optionally the second rinsing composition iii) and the phosphating composition iv) with an aqueous activating composition vii) ,
  • the activation serves to deposit a multiplicity of the finest phosphate particles as seed crystals on the metallic surface. These help in the process step of phosphating, ie in contact with the phosphating iv) - preferably without intermediate rinsing - form a particular crystalline phosphate layer with the highest possible number of densely arranged fine phosphate crystals or a largely closed phosphate layer.
  • the cleaning composition is added to an activating agent, in particular titanium phosphate or zinc phosphate, ie purification and activation are carried out in one step.
  • the metallic surface is contacted with the first rinsing composition ii) or optionally the second rinsing composition iii) and the phosphating composition iv) with an aqueous rinse
  • Activation composition vii) Particularly suitable as activating compositions are acidic or alkaline compositions based on titanium phosphate or zinc phosphate.
  • the metallic surface is brought into contact with the first rinsing composition ii) or optionally the second rinsing composition iii) and the phosphating composition iv) with an aqueous pickling composition viii) and then with a fourth rinsing composition ix).
  • contacting with the pickling composition viii) is in any case preceded by contacting with the activating composition vii).
  • the pickling composition viii) preferably contains at least one compound selected from the group consisting of phosphonates, condensed phosphates and citrate and / or at least one mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid, more preferably it contains at least one mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid, most preferably it contains sulfuric acid.
  • the pickling composition viii) contains at least one compound of the formula I.
  • the concentration of the at least one compound of the formula I in the mordant composition viii) is in the range from 31 to 620 mg / l, preferably in the range from 31 to 310 mg / l (calculated as 2-butyne-1, 4-diol).
  • the use of the at least one compound of the formula I in the pickling composition has the advantage of particularly effectively reducing pickling.
  • the fourth rinsing composition ix may also contain at least one compound of the formula I.
  • the detergent composition is i) alkaline, more preferably has a pH of 9.5 or greater.
  • the first rinsing composition ii), the second rinsing composition iii) and the third rinsing composition v) preferably have a pH in the range from 2 to 10, more preferably in the range from 3 to 10.
  • the first rinse composition is preferably weakly acidic, slightly alkaline or neutral. Particularly preferably, it has a pH in the range from 6 to 9.
  • the second rinse composition is preferably weakly weakly alkaline or neutral. Most preferably, it has a pH in the range of 7 to 9.
  • the third rinse composition preferably has a pH in the range of 4 to 9, more preferably it is slightly acidic, slightly alkaline or neutral. Most preferably, it has a pH in the range of 6 to 8.
  • the phosphating composition iv) may be zinc phosphate (so-called zinc phosphating) or an alkali metal phosphate (so-called Iron phosphating). It preferably contains zinc phosphate and optionally manganese phosphate and / or nickel ions.
  • the phosphating composition iv) contains zinc phosphate and manganese phosphate and is substantially nickel-free, i. it contains less than 0.3 g / l of nickel ions.
  • the phosphating composition iv) is a substantially nickel-free phosphating composition containing zinc phosphate and manganese phosphate
  • the molybdenum ions are preferably added as molybdate, more preferably as ammonium heptamolybdate and particularly preferably as ammonium heptamolybdate x 7 H 2 O of the third rinsing composition v).
  • the molybdenum ions can also be added as sodium molybdate.
  • molybdenum ions can also be added, for example, in the form of at least one salt containing molybdenum cations, such as molybdenum chloride, to the third rinse composition v) and then oxidized to molybdate by a suitable oxidizing agent.
  • the third rinse composition v) itself contains a corresponding oxidizing agent.
  • the third rinse composition contains v) molybdenum ions and / or zirconium ions, most preferably molybdenum ions in combination with zirconium ions, wherein the content of molybdenum ions and zirconium ions is in the range of 10 to 500 mg / l each (calculated as metal).
  • the content of molybdenum ions is preferably in the range from 20 to 225 mg / l, particularly preferably from 50 to 225 mg / l and very particularly preferably from 100 to 225 mg / l and the content of zirconium ions in the range from 50 to 300 mg / l, more preferably from 50 to 150 mg / l.
  • the at least one compound of the formula I is a mixture of a compound of the formula I in which R 1 and R 2 are both H, and a compound of the formula I in which R 1 and R 2 are each independently an HO- CH 2 ) w - group with w> 2.
  • the at least one compound of formula IR 1 and R 2 are both H or an HO- (CH 2 ) 2 group, the sum of x and y is 2 to 5 and Z is a CC triple bond.
  • the at least one compound of the formula I is 2-butyne-1,4-diol and / or 2-butyne-1,4-diol bis (2-hydroxyethyl ether).
  • the at least one compound of the formula I is particularly preferably a mixture of 2-butyne-1,4-diol and 2-butyne-1,4-diol bis (2-hydroxyethyl ether), the mixing ratio based on wt Range of 0.5: 1 to 2: 1, preferably in the range of 0.75: 1 to 1, 75: 1 and particularly preferably in the range 1: 1 to 1, 5: 1.
  • the metallic surface treated with the method according to the invention is preferably the surface of a metal strip or a metallic component, for example a body.
  • the metallic surface may include bare steel, electrolytically galvanized and / or hot-dip galvanized steel, aluminum and / or an aluminum alloy. According to a preferred embodiment, in addition to bare steel and / or galvanized steel, the metallic surface also contains aluminum or an aluminum alloy (so-called multimetal capability).
  • the process according to the invention has proved to be advantageous in the case of acrylate- and / or epoxide-based cathodic electrocoating paint (EPC) in terms of improved paint adhesion and improved corrosion protection.
  • EPC cathodic electrocoating paint
  • a topcoat is optionally applied to the KTL-coated metallic surface.
  • the present invention also relates to an aqueous composition for reducing pickling in the corrosion-protective phosphating of metallic surfaces, which contains at least one compound of the formula I as described above.
  • aqueous composition according to the invention in addition, it relates to a concentrate from which the aqueous composition according to the invention can be obtained by dilution with a suitable solvent and / or dispersion medium, preferably with water, and optionally adjusting the pH.
  • the dilution factor is preferably in the range from 1:10 to 1: 10,000, particularly preferably in the range from 1:50 to 1: 200.
  • the present invention also relates to the use of the metallic surface treated by the method according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

La présente invention concerne un procédé de phosphatation anticorrosion d'une surface métallique, selon lequel la surface est mise en contact tour à tour avec les compositions aqueuses suivantes : i) une composition de nettoyage alcaline ou acide, ii) une première composition de rinçage, iii) éventuellement une deuxième composition de rinçage, iv) une composition de phosphatation acide, v) éventuellement une troisième composition de rinçage et vi) une composition contenant un vernissage à immersion par cataphorèse à base de méth(acyrlate) et/ou d'époxyde, un agent d'activation étant ajouté à la composition de nettoyage i) et/ou la surface métallique étant amenée en contact avec une composition d'activation aqueuse vii) entre la mise en contact avec la première composition de rinçage ii) ou éventuellement la deuxième composition de rinçage iii) et la composition de phosphatation iv), au moins l'une des compositions i) à v) contenant au moins un composé de formule (I) R1O-(CH2)x-Z-(CH2)y-OR2, et R1 et R2 représentant respectivement indépendamment les uns des autres H ou un groupe HO-(CH2)w avec w ≥ 2, x et y étant indépendamment les uns des autres 1 à 4, et Z étant un atome de soufre ou une liaison triple C-C. L'invention concerne également une composition aqueuse pour réduire la matière décapée lors de la phosphatation anticorrosion de surfaces métalliques.
PCT/EP2017/062505 2016-05-25 2017-05-24 Procédé de phosphatation anticorrosion d'une surface métallique à réduction de matière décapée WO2017202891A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016209096 2016-05-25
DE102016209096.8 2016-05-25

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020200838A1 (fr) * 2019-04-04 2020-10-08 Chemetall Gmbh Agent de nettoyage sans phosphate pour surfaces métalliques à enlèvement par décapage réduit
US11124884B2 (en) 2016-04-29 2021-09-21 Chemetall Gmbh Composition for reducing the removal of material by pickling in the pickling of metal surfaces that contain galvanized and/or ungalvanized steel
US11434573B2 (en) 2017-12-12 2022-09-06 Chemetall Gmbh Boric acid-free composition for removing deposits containing cryolite
US11643731B2 (en) 2017-08-31 2023-05-09 Chemetall Gmbh Method for nickel-free phosphating metal surfaces
RU2815091C2 (ru) * 2019-04-04 2024-03-11 Хеметалл Гмбх Бесфосфатное чистящее средство для металлических поверхностей, обеспечивающее пониженную эрозию при травлении

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108517517B (zh) * 2018-04-16 2019-09-20 江苏科技大学 一种在钛表面制备磷酸钛锌化学转化膜的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4572743A (en) * 1983-04-26 1986-02-25 Huels Aktiengesellschaft Method for pickling metallic surfaces
US5415702A (en) * 1993-09-02 1995-05-16 Mcgean-Rohco, Inc. Black chromium-containing conversion coatings on zinc-nickel and zinc-iron alloys
WO1999032687A1 (fr) * 1997-12-19 1999-07-01 Henkel Kommanditgesellschaft Auf Aktien Procede de phosphatation de feuillard d'acier galvanise d'un seul cote

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4572743A (en) * 1983-04-26 1986-02-25 Huels Aktiengesellschaft Method for pickling metallic surfaces
US5415702A (en) * 1993-09-02 1995-05-16 Mcgean-Rohco, Inc. Black chromium-containing conversion coatings on zinc-nickel and zinc-iron alloys
WO1999032687A1 (fr) * 1997-12-19 1999-07-01 Henkel Kommanditgesellschaft Auf Aktien Procede de phosphatation de feuillard d'acier galvanise d'un seul cote

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11124884B2 (en) 2016-04-29 2021-09-21 Chemetall Gmbh Composition for reducing the removal of material by pickling in the pickling of metal surfaces that contain galvanized and/or ungalvanized steel
US11643731B2 (en) 2017-08-31 2023-05-09 Chemetall Gmbh Method for nickel-free phosphating metal surfaces
US11434573B2 (en) 2017-12-12 2022-09-06 Chemetall Gmbh Boric acid-free composition for removing deposits containing cryolite
WO2020200838A1 (fr) * 2019-04-04 2020-10-08 Chemetall Gmbh Agent de nettoyage sans phosphate pour surfaces métalliques à enlèvement par décapage réduit
CN113646467A (zh) * 2019-04-04 2021-11-12 凯密特尔有限责任公司 具有降低酸洗侵蚀的用于金属表面的无磷酸盐清洗剂
RU2815091C2 (ru) * 2019-04-04 2024-03-11 Хеметалл Гмбх Бесфосфатное чистящее средство для металлических поверхностей, обеспечивающее пониженную эрозию при травлении

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