EP1881090B1 - Elektrolytzusammensetzung und Verfahren zur Abscheidung einer Zink-Nickel-Legierungsschicht auf einem Gusseisen- oder Stahlsubstrat - Google Patents

Elektrolytzusammensetzung und Verfahren zur Abscheidung einer Zink-Nickel-Legierungsschicht auf einem Gusseisen- oder Stahlsubstrat Download PDF

Info

Publication number: EP1881090B1
Authority: EP; European Patent Office
Prior art keywords: electrolyte composition; zinc; substrate; nickel; deposition
Prior art date: 2006-07-13
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.): Active

Application number

EP06014519.0A

Other languages

German (de)

English (en)

French (fr)

Other versions

EP1881090A1 (de

Inventor

Dieter Harald Dr. Gollan

Gerard Patron

Thomas Helden

Andreas Heinz Dr. Kirchhof

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.)

MacDermid Enthone Inc

Original Assignee

Enthone Inc

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.)

2006-07-13

Filing date

2006-07-13

Publication date

2015-09-16

2006-07-13 Application filed by Enthone Inc filed Critical Enthone Inc

2006-07-13 Priority to EP06014519.0A priority Critical patent/EP1881090B1/de

2006-07-13 Priority to ES06014519.0T priority patent/ES2553730T3/es

2006-07-13 Priority to PL06014519T priority patent/PL1881090T3/pl

2006-07-13 Priority to HUE06014519A priority patent/HUE026918T2/en

2006-07-13 Priority to PT60145190T priority patent/PT1881090E/pt

2007-07-13 Priority to US11/778,011 priority patent/US8435398B2/en

2008-01-23 Publication of EP1881090A1 publication Critical patent/EP1881090A1/de

2015-09-16 Application granted granted Critical

2015-09-16 Publication of EP1881090B1 publication Critical patent/EP1881090B1/de

Status Active legal-status Critical Current

2026-07-13 Anticipated expiration legal-status Critical

Links

239000003792 electrolyte Substances 0.000 title claims description 45
239000000203 mixture Substances 0.000 title claims description 30
239000000758 substrate Substances 0.000 title claims description 24
QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims description 22
229910000990 Ni alloy Inorganic materials 0.000 title claims description 19
229910001018 Cast iron Inorganic materials 0.000 title claims description 11
230000008021 deposition Effects 0.000 title claims description 11
238000000034 method Methods 0.000 title claims description 9
239000010959 steel Substances 0.000 title claims description 9
229910001208 Crucible steel Inorganic materials 0.000 title claims description 7
PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
238000000151 deposition Methods 0.000 claims description 20
DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 17
WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 17
229910052759 nickel Inorganic materials 0.000 claims description 10
VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
229960002449 glycine Drugs 0.000 claims description 7
235000013905 glycine and its sodium salt Nutrition 0.000 claims description 7
239000001103 potassium chloride Substances 0.000 claims description 7
235000011164 potassium chloride Nutrition 0.000 claims description 7
KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
239000004327 boric acid Substances 0.000 claims description 6
SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
239000001632 sodium acetate Substances 0.000 claims description 5
235000017281 sodium acetate Nutrition 0.000 claims description 5
229910052725 zinc Inorganic materials 0.000 claims description 5
239000011701 zinc Substances 0.000 claims description 5
QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
235000011056 potassium acetate Nutrition 0.000 claims description 3
-1 potassium halide Chemical class 0.000 claims description 3
USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
239000005695 Ammonium acetate Substances 0.000 claims description 2
235000019257 ammonium acetate Nutrition 0.000 claims description 2
229940043376 ammonium acetate Drugs 0.000 claims description 2
229910052700 potassium Inorganic materials 0.000 claims description 2
239000011591 potassium Substances 0.000 claims description 2
VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 1
239000003513 alkali Substances 0.000 claims 1
238000005282 brightening Methods 0.000 claims 1
150000004820 halides Chemical class 0.000 claims 1
229910001453 nickel ion Inorganic materials 0.000 claims 1
NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 9
BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 8
BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 7
235000019270 ammonium chloride Nutrition 0.000 description 7
238000005260 corrosion Methods 0.000 description 7
230000007797 corrosion Effects 0.000 description 7
QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 7
KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 6
XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 6
DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
238000000576 coating method Methods 0.000 description 4
239000002351 wastewater Substances 0.000 description 4
KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
229910052751 metal Inorganic materials 0.000 description 3
239000002184 metal Substances 0.000 description 3
CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 3
150000003839 salts Chemical class 0.000 description 3
229910052708 sodium Inorganic materials 0.000 description 3
239000011734 sodium Substances 0.000 description 3
238000004065 wastewater treatment Methods 0.000 description 3
239000011592 zinc chloride Substances 0.000 description 3
235000005074 zinc chloride Nutrition 0.000 description 3
FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 2
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
229910000831 Steel Inorganic materials 0.000 description 2
230000002378 acidificating effect Effects 0.000 description 2
229910045601 alloy Inorganic materials 0.000 description 2
239000000956 alloy Substances 0.000 description 2
238000009826 distribution Methods 0.000 description 2
238000010348 incorporation Methods 0.000 description 2
KZVLNAGYSAKYMG-UHFFFAOYSA-N pyridine-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=N1 KZVLNAGYSAKYMG-UHFFFAOYSA-N 0.000 description 2
230000001105 regulatory effect Effects 0.000 description 2
229940081974 saccharin Drugs 0.000 description 2
235000019204 saccharin Nutrition 0.000 description 2
239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 2
YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
239000002253 acid Substances 0.000 description 1
230000004913 activation Effects 0.000 description 1
229910001508 alkali metal halide Inorganic materials 0.000 description 1
150000008045 alkali metal halides Chemical class 0.000 description 1
229910052793 cadmium Inorganic materials 0.000 description 1
BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
239000011248 coating agent Substances 0.000 description 1
230000000536 complexating effect Effects 0.000 description 1
239000008139 complexing agent Substances 0.000 description 1
239000004035 construction material Substances 0.000 description 1
238000011161 development Methods 0.000 description 1
230000018109 developmental process Effects 0.000 description 1
238000009713 electroplating Methods 0.000 description 1
229910052742 iron Inorganic materials 0.000 description 1
239000000463 material Substances 0.000 description 1
LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
229960003512 nicotinic acid Drugs 0.000 description 1
235000001968 nicotinic acid Nutrition 0.000 description 1
239000011664 nicotinic acid Substances 0.000 description 1
FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
238000007747 plating Methods 0.000 description 1
229960004889 salicylic acid Drugs 0.000 description 1
239000000126 substance Substances 0.000 description 1
238000011144 upstream manufacturing Methods 0.000 description 1

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
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel

Definitions

the present invention relates to an electrolyte composition for depositing a zinc-nickel alloy layer on a substrate, particularly a cast iron or steel substrate.
ammonium chloride-containing, low-acid baths for the deposition of zinc-nickel alloy layers allow the deposition of corrosion-resistant layers with nickel incorporation rates in the range of 10 to 15 mass%, but have the typical disadvantage of acidic electrolytes, often to produce uneven metal distributions in the layers.
the ammonium ions present in the electrolyte are environmentally relevant and pollute the waste water strongly.
the ammonium concentration in the waste water of electroplating plants are strictly regulated and subject to constant control. In order to comply with the regulatory requirements therefore expensive and expensive wastewater treatment must be made.
Ammonium chloride-containing zinc-nickel electrolytes for depositing corresponding alloy layers are known, for example, from the US patents US 4388160 and US 4765871 known.
ammonium chloride-containing electrolyte based on nickel chloride or nickel sulfate as a nickel metal salt carrier.
the aforementioned electrolytes typically have ammonium chloride in a concentration of up to 300 g / l, which necessitates extensive wastewater treatment.
the zinc-nickel alloy layers deposited from such alkaline zinc-nickel electrolytes typically exhibit incorporation rates of 10 to 15 mass% nickel.
a typical electrolyte of this kind as in the US 4765871 6 to 17 g / l of zinc, 0.8 to 2.3 g / l of nickel and 112 to 186 g / l of sodium or potassium hydroxide.
EP1295967 and SU524866 disclose electrolytes for depositing zinc-nickel alloys on metallic surfaces, the electrolytes including, inter alia, an aminoacetic acid.
the electrolyte compositions according to the invention are based on an alkali metal halide, preferably a potassium halide, more preferably potassium chloride as conductive salt and furthermore have an acetate of the group consisting of sodium acetate, potassium acetate or ammonium acetate or mixtures thereof.
an alkali metal halide preferably a potassium halide, more preferably potassium chloride as conductive salt and furthermore have an acetate of the group consisting of sodium acetate, potassium acetate or ammonium acetate or mixtures thereof.
the electrolyte composition of the present invention has a molar acetate: aminoacetic acid ratio of about 0.35 to about 0.91.
the electrolyte composition according to the invention preferably comprises boric acid and a brightener system consisting of saccharin, benzalacetone, orthochlorobenzaldehyde, octanol ethoxylate and a potassium salt of a sulfopropylated polyalkoxylated naphthol.
a brightener system consisting of saccharin, benzalacetone, orthochlorobenzaldehyde, octanol ethoxylate and a potassium salt of a sulfopropylated polyalkoxylated naphthol.
the brightener system preferably used comprises between 2 to 4 g / l of sodium saccharin, 0.025 to 0.2 g / l of benzalacetone, 0.006 to 0.01 g / l of orthochlorobenzaldehyde, 0.8 to 1.2 g / l of octanol ethoxylate and 2.5 to 3.2 g / l of potassium salt of the sulfopropylated polyalkoxylated naphthol.
the brightener system may have 0.5 to 1.0 g / L pyridine sulfonic acid.
the potassium chloride preferably used as the conductive salt in the electrolyte composition may be contained in the composition at a concentration of about 190 to 220 g / L.
the aminoacetic acid added according to the invention may be present in a concentration of between 10 and 50 g / l, preferably approximately 30 g / l, in the electrolyte composition.
the object is achieved by a method for depositing a zinc-nickel alloy layer on a substrate, in particular a cast iron or steel substrate, in which the substrate to be coated, in particular a cast iron or iron substrate under application of a current with the electrolyte composition according to the invention will be contacted.
the temperature of the electrolyte composition between about 20 ° C and about 60 ° C, preferably between 30 ° C and 40 ° C.
the current density to be set for the deposition of the layer can be adjusted between about 0.5 and about 5 A / dm 2 , preferably between 1.0 and 3.5 A / dm 2 .
the pH of the electrolyte composition described herein is between 5 and 6.
the pH of the electrolyte composition described herein is between 5 and 6.
a current density between 0.5 and 1.0 A / dm 2 was set.
the pH of the electrolyte composition was between 5 and 6.

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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)
Electroplating Methods And Accessories (AREA)

EP06014519.0A 2006-07-13 2006-07-13 Elektrolytzusammensetzung und Verfahren zur Abscheidung einer Zink-Nickel-Legierungsschicht auf einem Gusseisen- oder Stahlsubstrat Active EP1881090B1 (de)

Priority Applications (6)

Application Number	Priority Date	Filing Date	Title
EP06014519.0A EP1881090B1 (de)	2006-07-13	2006-07-13	Elektrolytzusammensetzung und Verfahren zur Abscheidung einer Zink-Nickel-Legierungsschicht auf einem Gusseisen- oder Stahlsubstrat
ES06014519.0T ES2553730T3 (es)	2006-07-13	2006-07-13	Composición de electrolito y procedimiento para la deposición de una capa de aleación de zinc-níquel sobre un sustrato de hierro fundido o de acero fundido
PL06014519T PL1881090T3 (pl)	2006-07-13	2006-07-13	Kompozycja elektrolityczna i sposób osadzania warstwy stopu cynkowo-niklowego na substrat żeliwny lub stalowy
HUE06014519A HUE026918T2 (en)	2006-07-13	2006-07-13	Electrolytic composition and method for separating zinc / nickel alloy layer on cast iron or steel substrate
PT60145190T PT1881090E (pt)	2006-07-13	2006-07-13	Composição electrolítica e processo para a deposição de uma camada de liga de zinco-níquel num substrato de ferro fundido ou de aço
US11/778,011 US8435398B2 (en)	2006-07-13	2007-07-13	Electrolyte composition and method for the deposition of a zinc-nickel alloy layer on a cast iron or steel substrate

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
EP06014519.0A EP1881090B1 (de)	2006-07-13	2006-07-13	Elektrolytzusammensetzung und Verfahren zur Abscheidung einer Zink-Nickel-Legierungsschicht auf einem Gusseisen- oder Stahlsubstrat

Publications (2)

Publication Number	Publication Date
EP1881090A1 EP1881090A1 (de)	2008-01-23
EP1881090B1 true EP1881090B1 (de)	2015-09-16

Family

ID=37499374

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP06014519.0A Active EP1881090B1 (de)	2006-07-13	2006-07-13	Elektrolytzusammensetzung und Verfahren zur Abscheidung einer Zink-Nickel-Legierungsschicht auf einem Gusseisen- oder Stahlsubstrat

Country Status (6)

Country	Link
US (1)	US8435398B2 (es)
EP (1)	EP1881090B1 (es)
ES (1)	ES2553730T3 (es)
HU (1)	HUE026918T2 (es)
PL (1)	PL1881090T3 (es)
PT (1)	PT1881090E (es)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE102008007133A1 (de) *	2008-01-31	2009-08-06	Metallveredelung Huber Gmbh	Beschichtung enthaltend einen galvanisch aufgebrachten Korrosionsschutz, insbesondere auf Beschlagteilen, sowie ein Verfahren zur Herstellung einer Beschichtung
FR2956123B1 (fr) *	2010-02-08	2017-10-27	Dalic	Procede de protection d'un substrat metallique contre la corrosion et l'abrasion, et substrat metallique obtenu par ce procede.
PL2784188T5 (pl) *	2013-03-26	2018-10-31	Atotech Deutschland Gmbh	Sposób antykorozyjnego zabezpieczania materiałów zawierających żelazo
CN104651888B (zh) *	2015-03-04	2017-03-22	武汉风帆电化科技股份有限公司	一种弱酸性至中性具有高耐蚀性锌镍合金电镀添加剂及电镀液

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Publication number	Priority date	Publication date	Assignee	Title
US3930965A (en) *	1974-03-18	1976-01-06	Mcgean Chemical Company, Inc.	Zinc-copper alloy electroplating baths
SU524866A1 (ru) *	1975-04-10	1976-08-15	Предприятие П/Я А-7697	Электролит дл осаждени цинк-никелевых сплавов
US4146441A (en) *	1977-10-06	1979-03-27	R. O. Hull & Company, Inc.	Additive compositions, baths, and methods for electrodepositing bright zinc deposits
US4388160A (en)	1980-02-20	1983-06-14	Rynne George B	Zinc-nickel alloy electroplating process
US4765871A (en)	1981-12-28	1988-08-23	The Boeing Company	Zinc-nickel electroplated article and method for producing the same
US4543166A (en)	1984-10-01	1985-09-24	Omi International Corporation	Zinc-alloy electrolyte and process
US4825009A (en) *	1985-12-23	1989-04-25	Shell Oil Company	Preparation of nonionic surfactants
JPH01219188A (ja) *	1988-02-26	1989-09-01	Okuno Seiyaku Kogyo Kk	亜鉛−ニッケル合金めっき浴
US4832802A (en)	1988-06-10	1989-05-23	Mcgean-Rohco, Inc.	Acid zinc-nickel plating baths and methods for electrodepositing bright and ductile zinc-nickel alloys and additive composition therefor
JP2901523B2 (ja) *	1995-08-09	1999-06-07	日本カニゼン株式会社	無電解黒色めっき浴組成と皮膜の形成方法
US6238542B1 (en)	1998-09-15	2001-05-29	Thomas Helden	Water soluble brighteners for zinc and zinc alloy electrolytes
DE10146559A1 (de) *	2001-09-21	2003-04-10	Enthone Omi Deutschland Gmbh	Verfahren zur Abscheidung einer Zink-Nickel-Legierung aus einem Elektrolyten
CN101273157A (zh) *	2005-06-20	2008-09-24	百富可公司	锌镍合金电镀***

2006
- 2006-07-13 ES ES06014519.0T patent/ES2553730T3/es active Active
- 2006-07-13 HU HUE06014519A patent/HUE026918T2/en unknown
- 2006-07-13 PT PT60145190T patent/PT1881090E/pt unknown
- 2006-07-13 PL PL06014519T patent/PL1881090T3/pl unknown
- 2006-07-13 EP EP06014519.0A patent/EP1881090B1/de active Active
2007
- 2007-07-13 US US11/778,011 patent/US8435398B2/en active Active

Also Published As

Publication number	Publication date
PL1881090T3 (pl)	2016-03-31
PT1881090E (pt)	2015-12-01
HUE026918T2 (en)	2016-07-28
ES2553730T3 (es)	2015-12-11
US8435398B2 (en)	2013-05-07
EP1881090A1 (de)	2008-01-23
US20080110762A1 (en)	2008-05-15

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