EP3455392A1 - Couches de conversion pour surfaces métalliques - Google Patents

Couches de conversion pour surfaces métalliques

Info

Publication number
EP3455392A1
EP3455392A1 EP17737207.5A EP17737207A EP3455392A1 EP 3455392 A1 EP3455392 A1 EP 3455392A1 EP 17737207 A EP17737207 A EP 17737207A EP 3455392 A1 EP3455392 A1 EP 3455392A1
Authority
EP
European Patent Office
Prior art keywords
treatment solution
ions
zinc
conversion layer
solution according
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.)
Pending
Application number
EP17737207.5A
Other languages
German (de)
English (en)
Inventor
Peter Volk
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.)
Carl Freudenberg KG
Original Assignee
Surtec International GmbH
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 Surtec International GmbH filed Critical Surtec International GmbH
Publication of EP3455392A1 publication Critical patent/EP3455392A1/fr
Pending 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
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the invention further relates to a concentrate for the preparation of the treatment solution and conversion layers, with the
  • Treatment solution according to the invention can be provided while maintaining the decorative and functional properties of the surfaces or improved metallic materials having a, high degree of corrosion protection.
  • the invention relates to the corrosion protection of metallic materials, in particular of zinc-containing surfaces. Background of the invention
  • the corrosion products of the coating metal in the case of zinc so-called white rust, namely have a disturbing effect on the appearance of a component.
  • Treatment solution conversion coatings on metallic surfaces In particular, zinc or zinc alloy surfaces can be produced which offer high corrosion protection and at the same time can be free of cobalt and chromium (VI) compounds.
  • VI cobalt and chromium
  • Conversion layers with a high layer thickness of more than 100 nm to produce This is also possible without the use of solutions with high concentration or high treatment temperatures. Also, treatment solutions according to the invention can be poor at or in the
  • the treatment solution according to the invention makes it possible to use harmful substances Metal ions, in particular of cobalt and chromium (VI) compounds, to dispense and yet conversion coatings on zinc or
  • Zinc alloys may contain foreign metals such as aluminum, iron, nickel up to 30%.
  • the passivation solution contains Cr (III) ions in an amount between 0.1 g / l and 8.0 g / l.
  • the proportion of Cr (III) ions, measured as chromium, can be determined by means of ICP.
  • the passivation solution further contains zirconium and / or titanium ions in an amount between 0.1 g / l and 15 g / l.
  • the proportion of zirconium and / or titanium ions, measured as zirconium and / or titanium, can be determined by means of ICP.
  • the treatment solution according to the invention contains organosilane-modified silica nanoparticles.
  • the silicon oxide is preferably present in the form of a nanoscale agglomerate.
  • This agglomerate can be regarded as a core whose surface is silane-modified, ie on the surface of which organic silane compounds are arranged.
  • organosilane modification is in particular understood that oxygen atoms at least on the surface of the
  • Silica nanoparticles covalently bonded to silicon atoms of an organic silicon compound.
  • the organic silicon compound is preferably an epoxide, amido, ureido, amino, ester, mercapto and / or isocyanate silane.
  • Siliziumoxidnanop be modified with a different number and / or type of organic silicon compounds.
  • the Siliziumoxidnanop may also have different silicon compounds in combination. Due to the production, the stoichiometric composition of the silica nanoparticles can vary.
  • the organosilane-modified silica nanoparticles are present in an amount of from 0.1 g / l to 50 g / l in the treatment solution. These concentration values refer to the respective
  • the organosilane-modified nanoparticles preferably have an average particle size of 5 to 50 nm.
  • the nanoparticles are in the
  • Treatment solution according to the invention advantageously at least partially dispersed before.
  • Such nanoparticles can be prepared, for example, as described in EP 2406328 A1.
  • suitable nanoparticles are commercially available, for example under the brand name Bindzil® from Akzo.
  • Silica nanoparticles are that they have high stability even at acidic pH's. Another advantage is that the silane modification an attack slowed down by the inventively used fluoride ions on the silica nanoparticles.
  • silica nanoparticles enhance the resistivity of the conversion layer.
  • the treatment solution according to the invention contains fluoride in an amount between 0.1 g / l to 15 g / l.
  • Fluoride is understood as meaning both free and complex-bound fluoride.
  • the concentration refers to the total fluoride content.
  • fluoride in conversion baths is advantageous because it is easy to use and analytically controllable, for example by ion selective potentiometry.
  • fluoride is advantageous for dissolving the zirconium and / or titanium components because of the fact that they form
  • the proportion of components contained in the treatment solution may vary depending on the desired performance characteristics. In practical experiments, it has proven to be particularly favorable if the proportion of:
  • Zirconium and / or titanium ions from 0.15 g / l to 10 g / l, more preferably from 0.2 g / l to 8 g / l and / or to
  • Organosilane-modified Siliziumoxidnanoparticlen from 0.2 g / l to 40 g / l, more preferably from 0.3 g / l to 30 g / l and / or on
  • Fluoride ions from 0.15 g / l to 15 g / l, more preferably from 0.2 g / l to 10 g / l. It has also proven to be advantageous if the molar ratio between Cr (III) ions on the one hand and zirconium and / or titanium ions on the other hand in the treatment solution is from 0.1 to 2.0, preferably 0.15 to 1.5, especially preferably 0.2 to 1.
  • the source of the chromium (III) ions is preferably water-soluble
  • Chromium (III) salts such as chromium chloride (CrCl 3 ), chromium nitrate (Cr (NO 3 ) 3 ),
  • Chromium sulfate (Cr 2 (SO 4 ) 3 ), chromium fluoride (CrF 3 ), chromium methanesulfonate, MSA (Cr 2 (CH 3 SO 3 ) 3 ).
  • the hexafluoro complexes of zirconium and / or titanium as the acid and / or salts thereof can be used as the source of the fluoride and at the same time zirconium ions and / or titanium ions.
  • complexing agents selected from the group consisting of: carboxylic acids, in particular formic acid,
  • Hydroxypolycarboxylic acids maleic acid, gluconic acid, phthalic acid,
  • Terephthalic acid tartaric acid, citric acid, malic acid, ascorbic acid; and other ligands such as acetylacetone, urea, urea derivatives, and others
  • Complex ligands in which the complexing functional group contains nitrogen, phosphorus or sulfur (-NR2, -PR2, where R is independently
  • each other is an organic, especially Ci to C 5 aliphatic radical and / or H, and / or -SR, wherein R is an organic, in particular Ci to C 5 aliphatic radical or H,); Phosphinates and phosphinate derivatives; as well as their suitable mixtures.
  • the further complexing agents are preferably present in a concentration of between 0.0 g / l and 25 g / l, and / or between 0.1 g / l and 25 g / l. Particularly preferred further complexing agents according to the invention are
  • Chelating ligands for example suitable carboxylic acids, in particular
  • Dicarboxylic acids Dicarboxylic acids, tricarboxylic acids, hydroxycarboxylic acids, and / or
  • the complexing agent is selected such that the Cr (III) ions in the treating solution are at least partially removed from the complexing agent
  • the treatment solution may also comprise further metal or metalloid ions.
  • they contain at least one further metal or metalloid ion selected from the group consisting of Na, Ag, Al, Co, Ni, Fe, Ga, In, lanthanides, Sc, V, cerium, Cr, Mn , Cu, Zn, Y, Nb, Mo, Hf, Ta, W, B, Si, P, Bi, Sb, Se ions, preferably in a concentration between 0.005 and 5 g / l.
  • These metal ions may, for example, act as catalysts and are preferably added to the reaction solution as soluble salts, in particular as nitrates, sulfates or halides.
  • the treatment solution may also contain other anions commonly used in generic treatment solutions.
  • they contain at least one anion selected from the group consisting of halide ions, in particular chloride, iodide; Sulfur-containing ions, in particular sulfate ions, methanesulfonate, hydrogen sulfate; Nitrate ions; Phosphorus-containing ions, in particular phosphate ions and anions of esters of phosphoric acid, diphosphate ions, hydrogen phosphate ions,
  • Dihydrogen phosphate linear and / or cyclic oligophosphate ions, linear and / or cyclic polyphosphations, phosphonic acids, 1-hydroxyethane- (1, 1-diphosphonic acid), aminotrimethylenephosphonic acid,
  • Ethylenediaminetetra (methylenephosphonic acid), 2-phosphonobutane-1, 2,4-tricarboxylic acid, hexafluorophosphate; carboxylate anions; siliceous
  • Anions preferably silicate anions, in particular hexafluorosilicate,
  • Hexafluoroantimonat contains.
  • the further anions, if present, are preferably present in a concentration of between 0.1 g / l and 50 g / l.
  • nitrate ions preferably nitrate ions, sulfate ions, and / or phosphonate ions.
  • the pH of the treatment solution is adjusted to values between about 1, 5 and 5, preferably from 2 to 4 and in particular from 2.5 to 3.5.
  • the desired pH can be adjusted by addition of hydrogen ions, ie by adding an acid or with a base.
  • the aqueous treatment solution contains at least one organic and / or inorganic acid.
  • the organic acid is preferably selected from the group consisting of citric acid, malonic acid, formic acid, tartaric acid,
  • Lactic acid malic acid, gluconic acid, ascorbic acid, oxalic acid,
  • Succinic acid and adipic acid. If an inorganic acid is used, it is preferably selected from the group consisting of
  • Phosphoric acid Phosphoric acid, polyphosphonic acid, nitric acid, hydrochloric acid and
  • Nitric acid is preferred according to the invention.
  • the treatment solution contains weak oxidizing agents, preferably selected from nitrite, amine oxides such as hydroxylamine or hydroxylamine compounds, N-oxides such as m-nitrobenzenesulfonate, nitroguanidine 4-picolines N-oxide, N-methylmorpholine N-oxide and Derivatives thereof.
  • weak oxidizing agents preferably selected from nitrite, amine oxides such as hydroxylamine or hydroxylamine compounds, N-oxides such as m-nitrobenzenesulfonate, nitroguanidine 4-picolines N-oxide, N-methylmorpholine N-oxide and Derivatives thereof.
  • VOC volatile organic compounds
  • alcohol such as methanol or ethanol
  • the content of VOC can be determined, for example, by means of GC or GC / MS.
  • the treatment solution may also include adjuvants, for example selected from the group consisting of polymers, in particular organic polymers, corrosion inhibitors; Silicas, in particular colloidal or
  • dispersed silicas surface-active substances, in particular surfactants; Diols, triols, polyols; organic acids, in particular Monocarboxylic acids; amines; Dispersions of plastics; Dyes, pigments, in particular carbon black, pigment formers, in particular metallic pigment formers; Amino acids, in particular glycine; Dispersants, included.
  • Suitable surfactants are, for example, aliphatic fluorocarbon sulfonates.
  • Another object of the present invention is a concentrate for the preparation of a treatment solution according to the invention.
  • the concentrate may be in solid or liquid form and preferably has an active ingredient concentration which makes it possible to use the present invention
  • Treatment solution by dilution with at least 50 wt.%, Preferably at least 70 wt.%, Water based on the total weight of
  • Treatment solution to produce In practical experiments it has been shown that it is expedient to prepare the treatment solution starting from two concentrates of different composition, since this ensures a longer shelf life of the respective concentrates.
  • Another object of the invention is thus a kit comprising at least two concentrates of different composition, for the preparation of the treatment solution according to the invention.
  • the concentrates preferably have an active ingredient concentration, which in combination
  • passivatable which are provided with a generated by alkaline cyanide, alkaline cyanide or acidic non-cyanide electrolytic zinc plating zinc coating, are coated with zinc layers of thermal diffusion processes, as well as workpieces that are galvanized by a melt, or which are made of zinc or a zinc alloy.
  • Zinc alloys on the workpiece surfaces may be, for example, Zn / Fe, Zn / Ni, Zn / Al and Zn / Co alloys.
  • the reaction solution can also be used to treat workpieces in accordance with the invention in which, in addition to the zinc or zinc alloy surfaces, surfaces which are not zinc or a zinc alloy, for example iron-containing surfaces such as steel surfaces, are also exposed.
  • reaction solution according to the invention for the passivation of aluminum for the passivation of aluminum
  • the present invention relates to a method for producing a conversion layer on metallic surfaces, in particular zinc or zinc alloy layers having workpieces, in which the workpiece to be treated is brought into contact with a treatment solution according to the invention.
  • the contacting is by dipping, i. the workpieces are immersed in the treatment solution contained in a container.
  • the workpieces can either be held on racks and immersed with the racks in the reaction solution or are in a drum or in a centrifuge or on a tray and immerse with the drum or the Horde in the reaction solution.
  • the workpieces are also contacted by spray dipping with the treatment solution.
  • Treatment solution brought into contact In an alternative procedure
  • the work pieces can also be in contact with the surface by flooding
  • Treatment solution to be brought can also be covered with the treatment solution, for example by means of a nozzle, from which a surge of the treatment solution emerges.
  • the method of treatment is to apply the treatment solution to the workpiece surfaces by brushing, rolling or another application technique.
  • the treatment can take place in conventional plants, in which the workpieces are treated batchwise, or in continuous plants, through which the workpieces are continuously passed and treated.
  • Treatment solutions can be performed. Thus, it is possible to resort to the system technology of the prior art.
  • Seconds more preferably between 15 and 600 seconds.
  • Process step can also be omitted, for example, if the workpieces immediately after the electrolytic galvanizing and subsequent rinsing the galvanizing solution with the reaction solution in contact.
  • the workpieces are preferably dried, for example with warm air.
  • the workpieces may also be rinsed before drying to remove excess reaction solution from the surface.
  • the process is in one stage.
  • the treated article is treated before and / or after the application of the conversion layer with a further treatment solution, for example a sealing solution.
  • Another object of the present invention is a
  • the conversion layer made by a method as described above.
  • the conversion layer contains
  • Compounds of the elements Cr, Si, O, F, C, H, as well as Zr and / or Ti more preferably it consists of these compounds, wherein also derived from the metallic surface compounds, for example of iron and / or zinc may be included can.
  • the weight fractions of the elements can be measured by energy dispersive X-ray spectroscopy, EDX.
  • Zinc surface measured by energy dispersive X-ray spectroscopy (EDX) at an excitation voltage of 20 kV, usually in the following ranges: chromium is usually in the range of 0.05 to 2 wt.%, Preferably from 0.1 to 1, 5 wt.%, even more preferably from 0.15 to 1.3
  • EDX energy dispersive X-ray spectroscopy
  • the weight proportion of silicon is usually in the range of 0.05 to 10 wt.%, Preferably 0.1 to 7 wt.%, More preferably 0.2 to 5 wt.%, Especially 0.3 to 3 wt. %, in each case based on the total weight of carbon, oxygen, fluorine, silicon, zirconium, titanium, chromium, iron, zinc.
  • the proportion by weight of oxygen is usually in the range from 1 to 25% by weight, preferably from 1.5 to 22% by weight, more preferably from 2 to 20% by weight, in particular from 3 to 15% by weight, based in each case on the Total weight of carbon, oxygen, fluorine, silicon, zirconium, titanium, chromium, iron, zinc.
  • the proportion by weight of fluorine is usually in the range of 0.05 to 3 wt.%, Preferably from 0.1 to
  • FIG. 1 cross section of a treatment solution according to the invention
  • FIG. 2 shows the cross section of the treatment solution 4 produced

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)

Abstract

L'invention concerne une solution aqueuse de traitement pour la génération de couches de conversion, sur des surfaces métalliques, en particulier sur des surfaces en zinc ou en alliage de zinc, la solution contenant : des ions Cr(III) en une quantité de 0,1 g/litre à 8,0 g/litre, des ions zircone et/ou titane en une quantité de 0,1 g/litre à 15 g/litre, des nanoparticules d'oxyde de silicium modifiées par un organosilane en une quantité comprise entre 0,1 g/litre à 50 g/litre, du fluorure en une quantité de 0,1 g/litre à 10 g/litre. La solution de traitement selon l'invention permet de doter des matériaux métalliques d'une protection élevée contre la corrosion et en même temps d'obtenir ou d'améliorer les propriétés décoratives et fonctionnelles des surfaces. En plus, il est possible d'éviter les problèmes connus lors de la mise en œuvre d'ions de métaux lourds, en particulier d'ions cobalt et chrome (VI).
EP17737207.5A 2016-05-11 2017-05-05 Couches de conversion pour surfaces métalliques Pending EP3455392A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016005656.8A DE102016005656A1 (de) 2016-05-11 2016-05-11 Konversionsschichten für metallische Oberflächen
PCT/EP2017/000560 WO2017194187A1 (fr) 2016-05-11 2017-05-05 Couches de conversion pour surfaces métalliques

Publications (1)

Publication Number Publication Date
EP3455392A1 true EP3455392A1 (fr) 2019-03-20

Family

ID=59298430

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17737207.5A Pending EP3455392A1 (fr) 2016-05-11 2017-05-05 Couches de conversion pour surfaces métalliques

Country Status (6)

Country Link
US (1) US20190145009A1 (fr)
EP (1) EP3455392A1 (fr)
JP (1) JP6882340B2 (fr)
CN (1) CN109312467A (fr)
DE (1) DE102016005656A1 (fr)
WO (1) WO2017194187A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7385275B2 (ja) 2020-10-02 2023-11-22 日本表面化学株式会社 コバルトフリーの化成皮膜処理液、及び、それを用いた化成皮膜処理方法
DE102021204609A1 (de) * 2021-05-06 2022-11-10 FNT-GmbH Verfahren zur Beschichtung von Zinkdruckgussteilen, mehrlagige Beschichtung zum Schutz von Zinkdruckgussteilen und beschichtetes Zinkdruckgussteil
DE102022105844A1 (de) 2022-03-14 2023-09-14 Carl Freudenberg Kg Passivierungsschicht für metallhaltige Substrate
DE102022126251A1 (de) 2022-10-11 2024-04-11 Liebherr-Aerospace Lindenberg Gmbh Verfahren zur Oberflächenbehandlung
DE102023001507A1 (de) 2023-04-17 2024-04-04 Mercedes-Benz Group AG Verfahren und Vorrichtung zum Reaktivieren einer Konversionsschicht

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DE19615664A1 (de) 1996-04-19 1997-10-23 Surtec Produkte Und Systeme Fu Chrom(VI)freie Chromatschicht sowie Verfahren zu ihrer Herstellung
US6527841B2 (en) * 2000-10-31 2003-03-04 The United States Of America As Represented By The Secretary Of The Navy Post-treatment for metal coated substrates
DE10055215A1 (de) 2000-11-07 2002-05-08 Walter Hillebrand Galvanotechn Passivierungsverfahren
DE102006002224A1 (de) * 2006-01-16 2007-07-19 Schaeffler Kg Anordnung zum Schutz eines Substrates vor Korrosion, Verfahren zu dessen Herstellung sowie Riemenscheibe
DE102007021002A1 (de) * 2007-05-04 2008-11-06 Wacker Chemie Ag Dispergierbare Nanopartikel
US8591670B2 (en) * 2008-05-07 2013-11-26 Bulk Chemicals, Inc. Process and composition for treating metal surfaces using trivalent chromium compounds
EP2151481A1 (fr) * 2008-08-01 2010-02-10 Chemische Werke Kluthe GmbH Solution aqueuse et procédé de revêtement de surfaces métalliques et utilisation d'acide silique modifié ou de composition de concentré pour la préparation d'une solution de revêtement aqueuse
CA2754594C (fr) 2009-03-13 2018-05-15 Akzo Nobel Chemicals International B.V. Dispersion aqueuse de silice silanisee
US8425692B2 (en) * 2010-05-27 2013-04-23 Bulk Chemicals, Inc. Process and composition for treating metal surfaces
KR101176480B1 (ko) * 2010-12-30 2012-08-28 주식회사 흥아포밍 3가 크로메이트 용액과 크로메이트 처리된 금속체 및 그 제조방법
EP2492371A1 (fr) * 2011-02-24 2012-08-29 Dr.Ing. Max Schlötter GmbH & Co. KG Solution de passivation sans cobalt et procédé de séparation de couches de passivation sans cobalt sur des surfaces de zinc et d'alliage de zinc
EP2691555A2 (fr) * 2011-03-30 2014-02-05 Mahindra & Mahindra Ltd. Formulation de passivation anticorrosion et son procédé de préparation
TWI493077B (zh) * 2012-04-27 2015-07-21 China Steel Corp A water-based metal surface treatment agent and a metal surface treatment method using the same
CN105695971A (zh) * 2016-03-16 2016-06-22 帝业化学品（上海）有限公司 一种铝、铝合金的免水洗铬化钝化剂及使用方法

Also Published As

Publication number Publication date
WO2017194187A1 (fr) 2017-11-16
JP2019515143A (ja) 2019-06-06
CN109312467A (zh) 2019-02-05
US20190145009A1 (en) 2019-05-16
JP6882340B2 (ja) 2021-06-02
DE102016005656A1 (de) 2017-11-16

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