EP2175048A1 - Composition de placage métallique pour le dépôt d'alliages d'étain et de zinc sur un substrat - Google Patents

Composition de placage métallique pour le dépôt d'alliages d'étain et de zinc sur un substrat Download PDF

Info

Publication number
EP2175048A1
EP2175048A1 EP08166465A EP08166465A EP2175048A1 EP 2175048 A1 EP2175048 A1 EP 2175048A1 EP 08166465 A EP08166465 A EP 08166465A EP 08166465 A EP08166465 A EP 08166465A EP 2175048 A1 EP2175048 A1 EP 2175048A1
Authority
EP
European Patent Office
Prior art keywords
tin
plating bath
zinc alloy
formula
alloy plating
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.)
Withdrawn
Application number
EP08166465A
Other languages
German (de)
English (en)
Inventor
Nina Dambrowsky
Heiko Brunner
Lukas Bedrnik
Vaclav Kriz
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.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and Co KG
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 Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to EP08166465A priority Critical patent/EP2175048A1/fr
Publication of EP2175048A1 publication Critical patent/EP2175048A1/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys

Definitions

  • the present invention relates to electroplating bath compositions for the deposition of tin-zinc alloys useful for corrosion protection of a metal substrate. Further, the invention relates to a process for the preparation of additives and their use in said metal plating compositions.
  • the electrodeposition of tin-zinc alloys is used for, e.g., corrosion protection of metal substrates, especially steel substrates.
  • the corrosion protection capability by tin-zinc alloy deposits depends on various parameters such as small grain size of the deposit ( Y.-S. Choi, P. Ganesan, S. P. Kumaraguru, B. N. Popov “Development of Sacrificial Zn-Sn Coatings by a Pulse Electrodeposition Process", Journal of Applied Surface Finishing 2 (1), 29-36 (2007 )).
  • the deposits in most cases consist of mixtures of individual tin and zinc grains. Such deposits are referred herein as tin-zinc alloys. Usually, no alloy particles of Sn x Zn y type are formed. Therefore, it is important to generate a deposit with a homogeneous distribution of tin and zinc domains (i.e., grains) within the deposits in order to obtain a good corrosion protection.
  • Polyquaternary amine compounds of different types have been suggested to deposit zinc and zinc alloy coatings possessing a good corrosion protection.
  • Polycondensation products obtained by reacting of di-tertiary amines with a methylene linker are disclosed in EP 1 114 206 B1 .
  • Polycondensation products derived from di-tertiary amines including an amide or thioamide functional group and ether type linkers are disclosed as additives for zinc and zinc-transition metal alloy plating compositions in US 5,405,523 and US 5,435,898 , and for application in tin-zinc alloy plating compositions in EP 1 201 789 B9 .
  • WO 02/08497 discloses polycondensation products derived from di-tertiary amines including an amide or thioamide functional group with a linker bearing an unsaturated moiety and optionally a second di-tertiary amine with or without an unsaturated moiety as additives for zinc and zinc alloy plating compositions. Furthermore, WO 02/08497 describes another type of additive derived by polycondensation of a di-tertiary amine including an amide or thioamide functional group, a di-tertiary amine without an amide or thioamide functional group and a linker.
  • tin-zinc alloy plating compositions are suitable for tin-rich tin-zinc alloy deposits with a tin content > 50 wt.-% but suffer from higher deviations from the targeted composition for tin-zinc alloys deposits with a tin content of 30 to 50 wt.-%.
  • the object of the present invention is to provide a metal plating composition, which can be used to deposit a tin-zinc alloy layer with a composition of 0.1 to 99.9 wt.-% Sn, more preferred 20 to 60 wt.-% Sn and most preferred 30 to 50 wt.-% Sn on a metal substrate.
  • the deposited tin-zinc alloy layer preferably shows the following properties:
  • the tin-zinc alloy plating composition should allow to reach the above mentioned criteria in a wide range of current densities and lead to deposits of high brightness.
  • the present invention relates to an aqueous tin-zinc alloy plating bath composition comprising a novel type of additives for deposition of tin-zinc alloy layers on metal substrates. Furthermore, the inventive plating bath composition allows the deposition of tin-zinc alloys with a tin content of 30 to 50 wt.-% in a wide current density range of 0.01 to 10 A/dm 2 .
  • the aqueous tin-zinc plating bath composition comprises stannous ions in form of at least one water soluble stannous salt, at least one water soluble zinc salt, at least one acid and at least one quaternary ammonium polymer additive which is represented by formula I: wherein a, b, c, d, e and f are identical or different and represent an integer ranging from 1 to 5, n is an integer greater than 1, R1, R2, R3 and R4 are identical or different and represent a substituted or unsubstituted C1 to C6 alkyl or a -CH 2 CH 2 (OCH 2 CH 2 ) y -OH residue, wherein y is ranging from 1 to 6, and X- is a suitable anion.
  • the substituted or unsubstituted C1 to C6 alkyl residues R1, R2, R3 and R4 are more preferred selected independently from the group consisting of methyl, ethyl, propyl and butyl and their hydroxy derivatives
  • Said quaternary ammonium polymers may be prepared by a condensation polymerization of one or more amine monomers of formula III, wherein R1, R2, R3, R4, a and b are defined as in formula I, with one or more hydroxyl functionalized aliphatic dihalogenide compound of formula IV, wherein c, d, e and X are defined as in formula I.
  • the molecular weight of the quaternary ammonium polymer according to formula I may range from about 500 to 100,000 Da, preferred from about 5,000 to 30,000 Da.
  • the amount of the quaternary ammonium polymer according to formula I included in the tin-zinc alloy plating bath composition is added in an amount sufficient to provide desired improvements in the deposited tin-zinc alloy such as reduced burning of high current density deposits, homogeneous composition of tin and zinc domains in the deposit, fine and uniform grain size and improved corrosion resistance.
  • the tin-zinc alloy plating bath composition of the present invention contain from about 0.1 to 10 g/l of the quaternary ammonium polymer according to formula I, more preferred 0.2 to 6 g/l.
  • the inventive additive is characterized by formula II. wherein n is greater than 10 and X- is a halogenide or pseudohalogenide ion.
  • Pseudohalogenide ions are selected from the group comprising -OCN, -NCO, -CNO, -SCN, -NCS, alkylsulfonates, mesitylate and triflate.
  • the tin-zinc alloy plating bath composition of the present invention will contain stannous ions in a concentration of about 1 to 100 g/l, more preferred 5 to 40 g/l.
  • the one or more source of stannous tin ions is preferably selected from the group comprising tin(II) sulfate, tin(II) methanesulfonate, tin(II) chloride, tin(II) fluoride, tin(II) sulfamate, tin(II) acetate and tin(II) oxide.
  • the tin-zinc alloy plating bath composition contains zinc ions in a concentration of about 1 to 100 g/l, more preferred 5 to 50 g/l.
  • the one or more source of zinc ions is preferably selected from the group comprising zinc sulfate, zinc methanesulfonate, zinc sulfamate, zinc chloride, zinc fluoride, zinc acetate and zinc fluoroborate.
  • the weight ratio of tin and zinc ions in the plating bath composition is ranging from 1 : 5 to 5 : 1, more preferred 2 : 5 to 5 : 2 and is most preferred 2 : 3. Throughout this written description of the invention, the range and ratio limits may be combined.
  • composition of the tin-zinc alloy deposit derived from the metal plating bath contains 0.1 to 99.9 wt.-% of tin, preferred 20 to 60 wt.-% of tin and most preferred 30 to 50 wt.-% of tin.
  • the tin-zinc alloy plating bath composition of the invention also may contain one or more conducting salts such as sodium chloride, sodium fluoride, sodium sulfate, potassium chloride, potassium fluoride, potassium sulfate, ammonium chloride, ammonium fluoride and/or ammonium sulfate in an amount of about 50 to 300 g/l or more.
  • the conductive salt is a chloride
  • the stannous salt is a chloride
  • the zinc salt is a chloride, thus forming an "all chloride" plating composition.
  • the tin-zinc alloy plating bath composition of the present invention also contains at least one acid.
  • Suitable acids are hydroxy polycarboxylic acid and/or hydroxy carboxylic acid with about 3 to 15 carbon atoms per molecule, or a water soluble salt thereof.
  • the hydroxy polycarboxylic acids and/or hydroxy carboxylic acid contains 3 to 7 carbon atoms. Mixtures of hydroxy carboxylic acids can be utilized.
  • Examples of hydroxy carboxylic acids which can be utilized for the tin-zinc plating bath composition of the present invention include monohydroxy and polyhydroxy carboxylic and polycarboxylic acids such as tartaric acid, malic acid, citric acid, gluconic acid and their respective salts, e.
  • Citric acid is a particularly useful hydroxy polycarboxylic acid for the tin-zinc plating bath composition of the present invention. Both stannous and zinc ions form complexes with hydroxy polycarboxylic acids like citric acid. The amount of hydroxy carboxylic acid ranges from about 5 to 200 g/l, more preferred from 10 to 150 g/l.
  • aromatic aldehydes known as brightener additives in tin-zinc alloy plating electrolytes are benzaldehyde, o-chlorbenzaldehyde, m-chlorbenzaldehyde, p-chlorbenzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-aminobenzaldehyde, verataldehyde, 2,4-dichlorbenzaldehyde, 3,4-dichlorbenzaldehyde, 3,5-dichlorbenzaldehyde, 2,6-dichlorbenzaldehyde, tolualdehyde, 3,4-dimethoxybenzaldehyde, cin
  • the tin-zinc alloy plating bath composition contains at least one brightener selected from aromatic carbonyl-containing compounds.
  • the carbonyl compounds are useful for improving the brightness and luster of the deposits produced by the tin-zinc plating compositions of the present invention.
  • the aromatic carbonyl-containing compounds act as a brightener imparting optimum leveling action over a wider plating range.
  • the aromatic carbonyl-containing compounds may be aromatic aldehydes, ketones, or carboxylic acids or the water soluble salts thereof.
  • the amount of aromatic aldehyde or other aromatic carbonyl-containing compounds included in the tin-zinc alloy plating compositions range from about 0.005 to 2 g/l.
  • the aldehyde brighteners are added as a bisulfite addition product.
  • the tin ion sources in metal plating compositions for deposition of tin-zinc alloys are mainly salts of Sn 2+ ions. Therefore, an antioxidant or a mixture of more than one antioxidant is preferably added to such compositions in order to prevent oxidation of Sn 2+ to Sn 4+ and subsequent precipitation of insoluble SnO 2 .
  • An overview of typical compounds used for this purpose is given in the textbook "The Electrodeposition of Tin and its alloys" (M. Jordan, Eugen G. Leuze Publ., 1 st Ed., 1995, p. 80-84) and include hydroquinone and phenol and their respective derivatives.
  • Heterocyclic antioxidants, e. g., amino-hydroxy substituted pyridine for tin and tin alloy plating compositions with improved properties are disclosed in the European Patent Application 08075139.9 .
  • the bath is operated at temperatures in the range of about 15 to 60 °C, more preferred at 20 to 30 °C.
  • An average cathode current density of about 0.01 to 10 A/m 2 , preferred 0.5 to 5 A/dm 2 , most preferred 1.5 to 2 A/m 2 is applied.
  • the tin-zinc alloy plating bath composition can be used for barrel and rack plating.
  • N,N'-Bis(dimethylaminopropyl)urea 10 g (0.0434 mol) N,N'-Bis(dimethylaminopropyl)urea are dissolved in 23.6 g DI water. 5.71 g (0.0434 mol) of 1,3-Dichlor-propan-2-ol are added to this solution and held at 90 °C for 5 h.
  • tin-zinc alloy plating solution a tin-zinc alloy plating solution was prepared, the composition is shown below: Sn 2+ salt 12 g/l Sn Zn 2+ salt 18 g/l Zn Sodium-Gluconate 50 g/l Citric acid 20 g/l Inventive additive according to formula II 3.52 g/l Anisaldehyde (brightener) 120 mg/l Ammonium chloride 80 g/l
  • a metal plating solution was prepared, the composition is shown below: Sn 2+ salt 12 g/l Sn Zn 2+ salt 18 g/l Zn Sodium-Gluconate 50 g/l Citric acid 20 g/l Mirapol A-15 ( EP 1 201 789 B1 ; example 1; available from Rhodia) 5.87 g/l Anisaldehyde (brightener) 120 mg/l Ammonium chloride 80 g/l
  • the tin-zinc alloy composition distribution on a substrate was evaluated with EDX for a deposit derived from a tin-zinc alloy plating composition containing an additive according to formula II (example 1 of the present invention) and a deposit derived from a tin-zinc alloy plating composition containing a prior art quaternary ammonium polymer additive disclosed in example 1 of the patent EP 1 201 789 B9 (example 2 of the present invention).
  • the target tin-zinc alloy composition was in both cases 40 wt.-% tin and 60 wt.-% zinc.
  • Table 1 The results of the comparative experiment are summarized in Table 1.
  • the plating bath comprising the inventive additive according to formula II leads to a more homogeneous tin-zinc alloy deposit composition compared to the deposit derived from a prior art plating bath over the entire current density range.
  • Table 1 deviation from the average alloy deposit composition derived from example 1 and comparative example 2. Absolute value of deviation from target average composition of 40 wt.-% tin and 60 wt.-% zinc (values given in %) current density (A/dm 2 ) example 1 (inventive additive) example 2 (prior art additive) >> 3,5 5.47 8.64 3.5 6.56 10.01 2.6 6.88 10.47 1.9 6.56 9.38 1.4 6.41 9.98 1 4.54 6.80 0.7 0.80 2.26 0.4 14.54 11.94
  • a FIB-SEM micrograph ( Figure 1 ) of a tin-zinc alloy deposit obtained according to example 1 shows the reduced grain size of the deposit compared to a deposit derived from a tin-zinc plating composition containing a prior art quaternary ammonium polymer additive ( Figure 2 , example 2). Furthermore, the grain size distribution is narrower for the deposit obtained with an inventive quaternary ammonium polymer according to formula II.
  • a substrate coated from a plating bath according to example 1 was subjected to a salt spray test after deposition of a passivation layer. Formation of white rust was observed after 48 h.
  • a substrate coated form a plating bath according to experiment 2 was subjected to a salt spray test after deposition of a passivation layer. Formation of white rust was observed after 24 h.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
EP08166465A 2008-10-13 2008-10-13 Composition de placage métallique pour le dépôt d'alliages d'étain et de zinc sur un substrat Withdrawn EP2175048A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08166465A EP2175048A1 (fr) 2008-10-13 2008-10-13 Composition de placage métallique pour le dépôt d'alliages d'étain et de zinc sur un substrat

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP08166465A EP2175048A1 (fr) 2008-10-13 2008-10-13 Composition de placage métallique pour le dépôt d'alliages d'étain et de zinc sur un substrat

Publications (1)

Publication Number Publication Date
EP2175048A1 true EP2175048A1 (fr) 2010-04-14

Family

ID=40386045

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08166465A Withdrawn EP2175048A1 (fr) 2008-10-13 2008-10-13 Composition de placage métallique pour le dépôt d'alliages d'étain et de zinc sur un substrat

Country Status (1)

Country Link
EP (1) EP2175048A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104357884A (zh) * 2014-11-14 2015-02-18 无锡伊佩克科技有限公司 一种钢铁材料镀锌锡合金方法
WO2016118400A1 (fr) 2015-01-22 2016-07-28 Baker Hughes Incorporated Utilisation d'hydroxyacide pour réduire le potentiel de corrosion localisée d'inhibiteurs d'hydrate à faible dose
CN107406999A (zh) * 2015-03-26 2017-11-28 三菱综合材料株式会社 使用了铵盐的电镀液

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163700A (en) * 1977-10-21 1979-08-07 Dipsol Chemicals Co., Ltd. Method for stabilizing tin or tin alloy electroplating baths
US5405523A (en) 1993-12-15 1995-04-11 Taskem Inc. Zinc alloy plating with quaternary ammonium polymer
US5435898A (en) 1994-10-25 1995-07-25 Enthone-Omi Inc. Alkaline zinc and zinc alloy electroplating baths and processes
GB2351084A (en) * 1999-06-16 2000-12-20 Macdermid Canning Plc Zinc and zinc alloy electroplating additives and electroplating methods
WO2002008497A1 (fr) 2000-07-20 2002-01-31 Macdermid Plc Additifs d'electrodeposition de zinc et d'alliage de zinc et procede d'electrodeposition
EP1201789A2 (fr) 2000-10-19 2002-05-02 ATOTECH Deutschland GmbH Bain de placage et methode d'électroplacage d'alliages étain-zinc
EP1114206B1 (fr) 1998-09-02 2003-02-26 ATOTECH Deutschland GmbH Bain alcalin aqueux exempt de cyanure s'utilisant pour le depot par galvanisation de revetements en zinc ou en alliage de zinc
WO2005093132A1 (fr) * 2004-03-04 2005-10-06 Taskem, Inc. Agent de brillance polyamine
WO2007045650A2 (fr) * 2005-10-18 2007-04-26 Basf Se Bain aqueux, alcalin et exempt de cyanure pour le dépôt galvanique de revêtements en zinc et en alliages de zinc

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163700A (en) * 1977-10-21 1979-08-07 Dipsol Chemicals Co., Ltd. Method for stabilizing tin or tin alloy electroplating baths
US5405523A (en) 1993-12-15 1995-04-11 Taskem Inc. Zinc alloy plating with quaternary ammonium polymer
US5435898A (en) 1994-10-25 1995-07-25 Enthone-Omi Inc. Alkaline zinc and zinc alloy electroplating baths and processes
EP1114206B1 (fr) 1998-09-02 2003-02-26 ATOTECH Deutschland GmbH Bain alcalin aqueux exempt de cyanure s'utilisant pour le depot par galvanisation de revetements en zinc ou en alliage de zinc
GB2351084A (en) * 1999-06-16 2000-12-20 Macdermid Canning Plc Zinc and zinc alloy electroplating additives and electroplating methods
WO2002008497A1 (fr) 2000-07-20 2002-01-31 Macdermid Plc Additifs d'electrodeposition de zinc et d'alliage de zinc et procede d'electrodeposition
EP1201789A2 (fr) 2000-10-19 2002-05-02 ATOTECH Deutschland GmbH Bain de placage et methode d'électroplacage d'alliages étain-zinc
EP1201789B1 (fr) 2000-10-19 2006-06-07 ATOTECH Deutschland GmbH Bain de placage et methode d'électroplacage d'alliages étain-zinc
EP1201789B9 (fr) 2000-10-19 2006-11-15 ATOTECH Deutschland GmbH Bain de placage et methode d'électroplacage d'alliages étain-zinc
WO2005093132A1 (fr) * 2004-03-04 2005-10-06 Taskem, Inc. Agent de brillance polyamine
WO2007045650A2 (fr) * 2005-10-18 2007-04-26 Basf Se Bain aqueux, alcalin et exempt de cyanure pour le dépôt galvanique de revêtements en zinc et en alliages de zinc

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"The Electrodeposition of Tin and its alloys", 1995, M. JORDAN, EUGEN G. LEUZE PUBL., pages: 80 - 84
Y.-S. CHOI ET AL.: "Development of Sacrificial Zn-Sn Coatings by a Pulse Electrodeposition Process", JOURNAL OF APPLIED SURFACE FINISHING, vol. 2, no. 1, 2007, pages 29 - 36

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104357884A (zh) * 2014-11-14 2015-02-18 无锡伊佩克科技有限公司 一种钢铁材料镀锌锡合金方法
WO2016118400A1 (fr) 2015-01-22 2016-07-28 Baker Hughes Incorporated Utilisation d'hydroxyacide pour réduire le potentiel de corrosion localisée d'inhibiteurs d'hydrate à faible dose
EP3247761A4 (fr) * 2015-01-22 2018-07-04 Baker Hughes, A Ge Company, Llc Utilisation d'hydroxyacide pour réduire le potentiel de corrosion localisée d'inhibiteurs d'hydrate à faible dose
CN107406999A (zh) * 2015-03-26 2017-11-28 三菱综合材料株式会社 使用了铵盐的电镀液
CN107406999B (zh) * 2015-03-26 2019-08-27 三菱综合材料株式会社 使用了铵盐的电镀液
US10450665B2 (en) 2015-03-26 2019-10-22 Mitsubishi Materials Corporation Plating solution using ammonium salt

Similar Documents

Publication Publication Date Title
US20100236936A1 (en) Aqueous,alkaline,cyanide-free bath for the galvanic deposition of zinc and zinc alloy coatings
KR101502804B1 (ko) Ｐｄ 및 Ｐｄ-Ｎｉ 전해질 욕조
EP2292679A1 (fr) Polymères dotés de groupes terminaux aminés et leur utilisation comme additifs pour bains galvaniques de zinc et d'alliages de zinc
EP2980279B1 (fr) Solution de placage d'alliage zinc-nickel et procédé de placage
US6436269B1 (en) Plating bath and method for electroplating tin-zinc alloys
US20170029971A1 (en) Process to deposit zinc-iron alloy layer material
US4290860A (en) Process for manufacturing electro-galvanized steel sheet excellent in paint adherence
EP2175048A1 (fr) Composition de placage métallique pour le dépôt d'alliages d'étain et de zinc sur un substrat
EP2489762B1 (fr) Additif pour bains de zingage et bains de zingage alcalins sans cyanure
US4439283A (en) Zinc cobalt alloy plating
EP2096193A1 (fr) Processus de préparation de zinc résistant à la corrosion et linéair platiné en zinc-nickel ou pièces formées complexes
KR101998605B1 (ko) 아연니켈합금 전기도금액 및 이를 이용한 전기도금법
EP2698449B1 (fr) Composition de bain de placage pour dépôt par immersion de l'or
EP0566121B1 (fr) Procédé de production d'une feuille d'acier recouverte d'un alliage zinc-chrome d'une excellente adhérence
CN104583457A (zh) 金属表面处理液、金属基材的表面处理方法及由此而得的金属基材
US5273643A (en) Method of producing zinc-chromium alloy plated steel sheet with excellent plating adhesiveness
JP6925985B2 (ja) アルカリ性亜鉛めっきのための添加剤
KR100961364B1 (ko) 표면 외관이 우수한 염화물계 아연-니켈합금 전기도금용액조성물 및 이를 이용한 아연-니켈 전기도금강판 제조방법
EP3889318B1 (fr) Procédé de formation d'une couche de passivation noire sur un alliage de fer-zinc et composition de passivation noire
KR100940669B1 (ko) 도금층의 표면외관, 밀착성 및 저온 치핑성이 우수한아연-니켈 합금 전기도금조성물, 도금강판 제조방법 및이에 따라 제조된 아연-니켈 합금전기 도금강판
JPH03120393A (ja) Ｚｎ―Ｃｒ電気めっき鋼板の製造方法
GB2160223A (en) Zinc cobalt alloy plating
KR100711767B1 (ko) 아연-니켈 합금 전기 도금 조성물, 이를 이용한 전기 도금강판의 제조방법 및 이에 따라 제조된 아연-니켈 합금 전기도금 강판
JPS6140315B2 (fr)
JPH07268679A (ja) 外観品位に優れたＺｎ−Ｃｒ合金電気めっき鋼板の製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

17P Request for examination filed

Effective date: 20101014

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ATOTECH DEUTSCHLAND GMBH

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KRIZ, VACLAV

Inventor name: BRUNNER, HEIKO

Inventor name: BEDRNIK, LUKAS

Inventor name: DAMBROWSKY, NINA

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KRIZ, VACLAV

Inventor name: BRUNNER, HEIKO

Inventor name: DAMBROWSKY, NINA

Inventor name: BEDRNIK, LUKAS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20150501