WO2016044972A1 - Composition de revêtement alcalin à base de cérium pour un pré-traitement de surfaces métalliques - Google Patents

Composition de revêtement alcalin à base de cérium pour un pré-traitement de surfaces métalliques Download PDF

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Publication number
WO2016044972A1
WO2016044972A1 PCT/CN2014/087068 CN2014087068W WO2016044972A1 WO 2016044972 A1 WO2016044972 A1 WO 2016044972A1 CN 2014087068 W CN2014087068 W CN 2014087068W WO 2016044972 A1 WO2016044972 A1 WO 2016044972A1
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WO
WIPO (PCT)
Prior art keywords
cerium
iii
composition according
less
composition
Prior art date
Application number
PCT/CN2014/087068
Other languages
English (en)
Inventor
Huimin Cao
Zongyue WAN
Xiaoshan Wan
Original Assignee
Henkel China Co. Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel China Co. Ltd. filed Critical Henkel China Co. Ltd.
Priority to CN202210192809.3A priority Critical patent/CN114561636A/zh
Priority to EP14902597.5A priority patent/EP3198055A4/fr
Priority to PCT/CN2014/087068 priority patent/WO2016044972A1/fr
Priority to CN201480082091.6A priority patent/CN107002247A/zh
Priority to TW104130755A priority patent/TW201615890A/zh
Publication of WO2016044972A1 publication Critical patent/WO2016044972A1/fr

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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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • 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
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C25D13/16—Wires; Strips; Foils
    • 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
    • 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 present invention relates to an alkaline aqueous composition for the pretreatment of metal substrates wherein the composition is based on a source of cerium cations as well as the presence of an amino-functional organosilane.
  • a process of pre-treating a metal substrate based on such an alkaline aqueous composition and its use for the corrosion pretreatment is as well encompassed.
  • a thin essentially inorganic coating is usually applied that at least temporarily imparts corrosion resistance and in addition acts as an adhesion promoting layer when organic top coatings are to be applied in subsequent process steps of surface finishing.
  • the most widely used pretreatment methods for metal parts or metal coils are either based on thin film passivates such as Cr (VI) containing compositions or conventional phosphatizing. Due to the toxicology of the Cr (VI) system to both health and environment, non-Cr (VI) systems have been developed that are often based on acidic compositions of fluorometallates. In other attempts, the effectiveness of organosilanes to form protective coatings in a wet chemical treatment process has been reported. Among those substitutive methods, few of them could reach comparable performance with the Cr (VI) conversion coating system with respect to corrosion protection.
  • Patent US 5292549 discloses a metallic coated steel sheet having a thin siloxane film for providing temporary corrosion protection and a method thereof by applying a siloxane film which is removable by alkaline rinse. Although such process of pre-treatment provides a non-toxic coating that is impervious to moisture, only temporary corrosion resistance is conferred to the metallic coated steel and needs to be removed prior to any further coating step.
  • Patent CN 101098982A discloses a method of coating a metal surface with an aqueous composition comprising silanes as well as a mixture of compounds of Ti, Zr, Al and B.
  • Such compositions are reported to provide an anti-corrosion performance comparable to the Cr (VI) system, but do rely on certain complex fluorides and often on a certain amount of free fluorine, especially when used to pretreat different metallic materials in the same pretreatment line.
  • fluorine is harmful to environment and health and thereby imposes additional occupational safety measures when operating such a pretreatment bath.
  • Yet another problem consists in the fact that the concentration of fluoride will increase during the operation of a pretreatment bath in turn giving rise to excess fluoride that may lead to defects in the formed conversion coating. Therefore, within a continuously operated pretreatment line there currently exists the need to dose regulating fluoride scavengers, such as aluminium ions, in order to sustain suitable levels of free fluoride.
  • Patent US 2003/0034095A1 a method for treating a metallic substrate is disclosed that comprises the steps of contacting at least a portion of the metal substrate with an alkaline pretreatment composition being substantially free of chromates comprising compounds like stannates, molybdates, vanadates and hydrated cerium compounds; drying the substrate; rinsing the substrate; and again drying the substrate.
  • an adherent coating is applied that is based on silanes or conventional organic binders such as epoxies, silicones, amines, alkyds, urethanes and acrylics.
  • the treatment with a silane based coating composition thus appears after the bare metal surface has been conversion coated with the chromate free alkaline pretreatment composition.
  • an alkaline aqueous composition that comprises
  • component b) at least one silane containing at least one non-hydrolyzable Si-C bond carrying at least one amino-functional group and at least one hydrolyzable Si-O bond; wherein the weight ratio of component a) with respect to the element cerium to component b) with respect to the element Si does not exceed 5.
  • Another object of the present invention consists in a process of pre-treating a metal part, comprising a wet chemical treatment step of bringing the metal part into contact with the alkaline aqueous composition.
  • any amount of a compound that is quantified by means of “wt%” in the context of the present invention shall refer to the amount in percentages by weight with respect to the corresponding total composition unless otherwise stated. Where the amount of a compound is quantified by means of “ppm” , such amount refers to parts per million (10 -6 ) based on a weight portion.
  • the present invention relates to an alkaline aqueous composition
  • an alkaline aqueous composition comprising
  • source of cerium cations shall mean any cerium containing compound that when dissolved in water releases cerium cations or complex ions with cerium as the central atom.
  • any composition of this invention to be alkaline relates to a pH value of above 7 while the pH value is to be understood to be the negative logarithm to the base 10 of the activity of the hydronium ion concentration at 20°C.
  • compositions of this invention are capable of forming a protective coating on metal surfaces upon bringing the respective metal in contact with said composition.
  • the protective coating imparts sufficient temporary corrosion protection to the metal surface.
  • the treated metal parts can be temporarily stored in humid or dry atmosphere while no significant amounts of visible corrosion products do occur. Thereby, the further processing of such treated metal parts, e. g. application of protective and decorative organic coatings, without the need to rework the metal surfaces is possible.
  • Water-soluble salts of cerium (III) and/or cerium (IV) are preferably used as the source of cerium cations in the present invention.
  • the water-soluble salts of cerium (III) and/or cerium (IV) are selected from ammonium cerium (IV) sulfate, ammonium cerium (IV) nitrate, cerium (IV) sulfate, cerium (III) carbonate, cerium (III) nitrate, cerium (III) acetate and cerium (III) sulphide.
  • the source of cerium cations is selected from cerium (III) salts and most preferably selected from cerium (III) carbonate, cerium (III) nitrate and cerium (III) acetate.
  • water-soluble as used herein shall mean that more than 5g/L of cerium salts can be dissolved into deionized water ( ⁇ 1 ⁇ Scm -1 ) at 20°C while still a homogenous solution is attained without visible precipitates over a period of 24 h.
  • the amount of compound a) in an alkaline aqueous composition of the present invention is preferably not less than 0.002 wt%, more preferably not less than 0.02 wt% with respect to the element cerium. If the concentration of said water-soluble salts in a composition ready to be applied to a metal substrate is lower than 0.002wt%, the amount of the active component tends to be too less to form a protective coating when conventional means such as spraying or dip coating are applied. On the other hand, it is preferred that the source of cerium according to compound a) of the alkaline aqueous composition of this invention does not exceed 2 wt% with respect to the element cerium as compositions with a higher amount of cerium tend to aggregate and to form precipitates.
  • the aqueous composition is capable of being directly used by conventional means of application and thus preferably does not comprise more than 0.2 wt%, more preferably not more than 0.12 wt%, even more preferably not more than 0.08 wt%of compound a) with respect to the element cerium to ensure an optimum formation of a thin protective film.
  • the amino-functional silane preferably has the following general structure (I) :
  • the hydrolyzable substituents X are independently from each other selected from alkoxy groups with not more than 4, preferably not more than 2 carbon atoms; m and p each independently from another are integer numbers in the range from 1 to 4; n is an integer number in the range from 0 to 8, preferably from 0 to 3; and y is an integer number in the range from 1 to 3, and preferably y equals to 1.
  • the amino-functional silane is selected from:
  • the pH value of the composition plays a key role in the formation process of the conversion coating layer.
  • the conversion coating layer with good anti-corrosion property could only occur under a certain pH regime.
  • the aqueous composition for metal surface pre-treatment in present invention is thus adjusted to be alkaline.
  • the alkaline aqueous composition has a pH value of at least 8, but preferably of not more than 12, more preferably of not more than 10.
  • the pH value adjuster is one or more selected from alkaline materials preferably selected from NaOH, KOH, NH 3 and NH 4 HCO 3 as well as alkanolamines.
  • the ratio of component a) to component b) influences the stability of the alkaline aqueous composition in the present invention.
  • the weight ratio of component a) with respect to the element cerium to component b) with respect to the element silicon is less than 5 and preferably less than 4, more preferably less than 3. If said ratio is higher than 5, the composition is not stable so that precipitates are immediately formed.
  • said weight ratio is at least 0.1 and more preferably at least 0.5. If said ratio is lower than 0.1, the composition tends to yield coatings on metal substrates that perform worse in the salt spray test. Optimum conditions are fulfilled were said weight ratio lies within the range of 0.5 to 3.
  • the present invention characterizes that the coatings formed by way of the alkaline aqueous compositions are capable to sufficiently protect metal substrates from corrosion especially when further organic coatings are applied.
  • the present invention does not rely on the formation of coatings that are essentially constituted of chromates, phosphates or hydroxides/oxides of the elements Zr, Ti and/or Hf. Consequently, within the alkaline aqueous composition of this invention the amount of each of the elements Mn, Zn or Fe is preferably less than 500 ppm, preferably less than 100 ppm.
  • the amount of each of the elements Zr, Ti or Hf in the alkaline aqueous composition is less than 50 ppm, more preferably less than 10 ppm, even more preferably less than 5 ppm.
  • the amount of phosphates is preferably less than 1000 ppm, more preferably less than 100 ppm calculated with respect to the element P.
  • the amount of each of the elements Ni, Co or Cu is less than 100 ppm, preferably less than 10 ppm in order to avoid electroless metallization of the substrate.
  • a process of pre-treating a metal substrate comprises a wet chemical treatment step of bringing the metal substrate into contact with the alkaline aqueous composition of the present invention.
  • the method of application of the alkaline aqueous composition is not limited and might occur through any method conventional in the art, such as immersing, spraying or wet film application by means of squeegees.
  • the metal substrate is brought into contact with the composition by immersing or spraying.
  • the metal substrates are preferably cleaned or degreased prior to the application of the alkaline aqueous composition and preferably shall not carry any conversion coating with a thickness of more than 5 nm.
  • the metal substrate is preferably dried in order to attain a protective coating that confers optimum adhesion to most organic coatings.
  • Such further organic coating is preferably selected from a powder coating or an electro-coating.
  • the wet chemical treatment step of contacting the metal substrate with an alkaline aqueous composition of this invention is directly followed by a rinsing step and a subsequent drying step prior the application of a powder coating.
  • a rinsing step characterizes a process that is solely dedicated to rinse off active components that exist in a wet film adhered to the metal substrate and stem from any one of the preceding wet chemical treatment steps without substituting the formerly adhering active components with other active components.
  • An active component in this respect equals any chemical compound dissolved or dispersed in such an amount in a liquid phase that such amount effects a surface loading of at least 1mg/m 2 on the metallic surface in the due course of the respective wet chemical treatment step.
  • the rinsing is accomplished by making use of a rinse solution, e. g. deionized water.
  • a drying step according to this invention characterizes a process step upon which an adhering wet film is dried upon intentional and purposeful application of heat.
  • the alkaline aqueous composition of the present invention can be applied on metal substrates selected from cold rolled steel, hot rolled steel, galvanized steel, galvannealed steel and aluminum, preferably in such an amount or for a time effective to give rise to an elemental loading of at least 1 mg/m 2 , more preferably at least 5 mg/m 2 , but preferably not more than 100 mg/m 2 with respect to the element cerium on the surfaces of the metal substrate.
  • a multitude of working compositions according to Table 1 was prepared based on a concentrate comprising 0.5 wt%Cerium nitrate Ce (NO 3 ) 3 ⁇ 6H 2 O and an respective amount of an organosilane according to the weight ratios indicated in Table 1.
  • the pH of each working composition was adjusted to the respective value with ammonia or ammonium bicarbonate.
  • “A” denotes JH A110 ( ⁇ -aminopropyltriethoxylsilane) and “B” denotes Z6610 ( ⁇ -aminopropyltrimethoxylsilane) and the column “concentration” denotes: [weight of component a) + weight of component b) ] /total weight of the respective working composition.
  • CRS panels were immersed at room temperature for 5 minutes in a mixture of 3 wt% Ridoline-1022R and 0.3 wt%Ridoline-1020S diluted by deionized water;
  • CRS panels were brought into contact with a treatment composition according to table 1 through immersing for a time period of 4 min;
  • CRS Panels were rinsed with deionized water (k ⁇ 1 ⁇ Scm -1 ) and thereafter dried in oven at temperature at around 120°C;
  • a Powder coating based on a mixture of a polyester and an epoxy resin was electrostatically applied to the CRS panels using a spray gun to yield a coating layer thickness of 60 to 80 ⁇ m.
  • the coated CRS panels were subjected to the Neutral Salt Spray Test (NSST according to ASTM B117-03) .
  • the corrosive delamination of the powder coating is assessed by means of maximum creepage at a scribe after 500 h of exposure in the afore-mentioned test.
  • composition according to this invention could prevent the metal substrates from flush rust in a pretreatment line while sufficiently protecting the coated metal substrate from corrosivedelamination.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition aqueuse alcaline pour le pré-traitement de substrats métalliques, la composition étant à base d'une source de cations de cérium ainsi que de la présence d'un organosilane amino-fonctionnel. L'invention concerne également un procédé de pré-traitement d'un substrat métallique à base d'une telle composition aqueuse alcaline et son utilisation pour le pré-traitement de la corrosion.
PCT/CN2014/087068 2014-09-22 2014-09-22 Composition de revêtement alcalin à base de cérium pour un pré-traitement de surfaces métalliques WO2016044972A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN202210192809.3A CN114561636A (zh) 2014-09-22 2014-09-22 用于金属表面预处理的碱性基于铈的涂层组合物
EP14902597.5A EP3198055A4 (fr) 2014-09-22 2014-09-22 Composition de revêtement alcalin à base de cérium pour un pré-traitement de surfaces métalliques
PCT/CN2014/087068 WO2016044972A1 (fr) 2014-09-22 2014-09-22 Composition de revêtement alcalin à base de cérium pour un pré-traitement de surfaces métalliques
CN201480082091.6A CN107002247A (zh) 2014-09-22 2014-09-22 用于金属表面预处理的碱性基于铈的涂层组合物
TW104130755A TW201615890A (zh) 2014-09-22 2015-09-17 用於金屬表面預處理的鹼性含水工作組合物、預處理金屬基材的方法及其在腐蝕預處理中的用途

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2014/087068 WO2016044972A1 (fr) 2014-09-22 2014-09-22 Composition de revêtement alcalin à base de cérium pour un pré-traitement de surfaces métalliques

Publications (1)

Publication Number Publication Date
WO2016044972A1 true WO2016044972A1 (fr) 2016-03-31

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PCT/CN2014/087068 WO2016044972A1 (fr) 2014-09-22 2014-09-22 Composition de revêtement alcalin à base de cérium pour un pré-traitement de surfaces métalliques

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Country Link
EP (1) EP3198055A4 (fr)
CN (2) CN114561636A (fr)
TW (1) TW201615890A (fr)
WO (1) WO2016044972A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109722661A (zh) * 2019-02-23 2019-05-07 沈阳帕卡濑精有限总公司 一种用于金属表面处理的碱性硅烷稀土掺杂处理剂及其制备方法和应用

Citations (4)

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WO2004076717A1 (fr) * 2003-02-25 2004-09-10 Chemetall Gmbh Procede de revetement de surfaces metalliques au moyen d'une composition riche en silane
CN101542018A (zh) * 2006-11-21 2009-09-23 日本帕卡濑精株式会社 环保型预涂金属材料用水性表面处理剂、以及表面处理金属材料和环保型预涂金属材料
CN102703893A (zh) * 2012-05-28 2012-10-03 武汉永正科技发展有限公司 镀锌件环保钝化液及其制备方法
CN102943259A (zh) * 2012-09-24 2013-02-27 中国海洋石油总公司 一种用于镀锌系列钢板的水系无铬表面处理液

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WO2009077412A2 (fr) * 2007-12-14 2009-06-25 Akzo Nobel N.V. Boue aqueuse comprenant des matières particulaires inorganiques contenant de l'oxygène
CN101717930B (zh) * 2009-12-25 2012-02-01 华烁科技股份有限公司 可以提高金属表面防腐性能的环保型纳米水性硅烷处理剂
DE102010001686A1 (de) * 2010-02-09 2011-08-11 Henkel AG & Co. KGaA, 40589 Zusammensetzung für die alkalische Passivierung von Zinkoberflächen
JP6072569B2 (ja) * 2012-02-28 2017-02-01 日鉄住金鋼板株式会社 表面被覆アルミニウム含有亜鉛系めっき鋼板

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WO2004076717A1 (fr) * 2003-02-25 2004-09-10 Chemetall Gmbh Procede de revetement de surfaces metalliques au moyen d'une composition riche en silane
CN101542018A (zh) * 2006-11-21 2009-09-23 日本帕卡濑精株式会社 环保型预涂金属材料用水性表面处理剂、以及表面处理金属材料和环保型预涂金属材料
CN102703893A (zh) * 2012-05-28 2012-10-03 武汉永正科技发展有限公司 镀锌件环保钝化液及其制备方法
CN102943259A (zh) * 2012-09-24 2013-02-27 中国海洋石油总公司 一种用于镀锌系列钢板的水系无铬表面处理液

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Title
See also references of EP3198055A4 *

Also Published As

Publication number Publication date
EP3198055A1 (fr) 2017-08-02
CN114561636A (zh) 2022-05-31
EP3198055A4 (fr) 2018-05-02
TW201615890A (zh) 2016-05-01
CN107002247A (zh) 2017-08-01

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