EP0770710A1 - Procédé de dépÔt électrolytique de nickel lisse - Google Patents

Procédé de dépÔt électrolytique de nickel lisse Download PDF

Info

Publication number: EP0770710A1
Authority: EP; European Patent Office
Prior art keywords: electrolyte; adducts; operated; nickel; glare
Prior art date: 1995-10-27
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.): Granted

Application number

EP96116639A

Other languages

German (de)

English (en)

Other versions

EP0770710B1 (fr

EP0770710B2 (fr

Inventor

Carmen Elligsen

Gerd Schöngen

Detlef Kowczyk

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.)

LPW Chemie GmbH

Original Assignee

LPW Chemie 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.)

1995-10-27

Filing date

1996-10-17

Publication date

1997-05-02

Family has litigation

First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7775920&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0770710(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.

1996-10-17 Application filed by LPW Chemie GmbH filed Critical LPW Chemie GmbH

1997-05-02 Publication of EP0770710A1 publication Critical patent/EP0770710A1/fr

1999-01-07 Publication of EP0770710B1 publication Critical patent/EP0770710B1/fr

2002-08-14 Application granted granted Critical

2002-08-14 Publication of EP0770710B2 publication Critical patent/EP0770710B2/fr

2016-10-17 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 45
229910052759 nickel Inorganic materials 0.000 title claims abstract description 23
238000000034 method Methods 0.000 title claims abstract description 18
238000009713 electroplating Methods 0.000 title abstract 2
239000003792 electrolyte Substances 0.000 claims abstract description 48
239000000203 mixture Substances 0.000 claims abstract description 8
IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 6
GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 6
IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims abstract description 3
239000000126 substance Substances 0.000 claims description 14
-1 alkali metal salts Chemical class 0.000 claims description 10
238000000151 deposition Methods 0.000 claims description 10
230000008021 deposition Effects 0.000 claims description 10
239000002244 precipitate Substances 0.000 claims description 9
239000003795 chemical substances by application Substances 0.000 claims description 5
229910052783 alkali metal Inorganic materials 0.000 claims description 4
RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical class C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 3
239000002253 acid Substances 0.000 claims description 3
238000004070 electrodeposition Methods 0.000 claims description 3
229940124530 sulfonamide Drugs 0.000 claims description 3
150000003456 sulfonamides Chemical class 0.000 claims description 3
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
150000007513 acids Chemical class 0.000 claims description 2
239000002932 luster Substances 0.000 claims description 2
GPUMPJNVOBTUFM-UHFFFAOYSA-N naphthalene-1,2,3-trisulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC2=C1 GPUMPJNVOBTUFM-UHFFFAOYSA-N 0.000 claims description 2
BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
239000002585 base Substances 0.000 claims 2
238000007689 inspection Methods 0.000 claims 1
CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims 1
230000000694 effects Effects 0.000 abstract description 8
238000000576 coating method Methods 0.000 abstract description 2
JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 abstract 1
239000002184 metal Substances 0.000 abstract 1
229910052751 metal Inorganic materials 0.000 abstract 1
238000011179 visual inspection Methods 0.000 abstract 1
NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
239000000839 emulsion Substances 0.000 description 6
230000004313 glare Effects 0.000 description 5
239000002736 nonionic surfactant Substances 0.000 description 3
239000005711 Benzoic acid Substances 0.000 description 2
WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
229910001369 Brass Inorganic materials 0.000 description 2
229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
241000080590 Niso Species 0.000 description 2
238000005054 agglomeration Methods 0.000 description 2
230000002776 aggregation Effects 0.000 description 2
150000001447 alkali salts Chemical class 0.000 description 2
235000010233 benzoic acid Nutrition 0.000 description 2
230000015572 biosynthetic process Effects 0.000 description 2
KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
239000010951 brass Substances 0.000 description 2
QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
150000003455 sulfinic acids Chemical class 0.000 description 2
150000003460 sulfonic acids Chemical class 0.000 description 2
XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
101100453960 Drosophila melanogaster klar gene Proteins 0.000 description 1
229910000990 Ni alloy Inorganic materials 0.000 description 1
239000002202 Polyethylene glycol Substances 0.000 description 1
125000000217 alkyl group Chemical group 0.000 description 1
SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
229940092714 benzenesulfonic acid Drugs 0.000 description 1
239000011248 coating agent Substances 0.000 description 1
150000001875 compounds Chemical class 0.000 description 1
238000010276 construction Methods 0.000 description 1
238000001816 cooling Methods 0.000 description 1
230000007812 deficiency Effects 0.000 description 1
238000004519 manufacturing process Methods 0.000 description 1
150000002815 nickel Chemical class 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
150000002891 organic anions Chemical class 0.000 description 1
229920001223 polyethylene glycol Polymers 0.000 description 1
229920000642 polymer Polymers 0.000 description 1
239000011148 porous material Substances 0.000 description 1
238000001556 precipitation Methods 0.000 description 1
150000003839 salts Chemical class 0.000 description 1
DIKJULDDNQFCJG-UHFFFAOYSA-M sodium;prop-2-ene-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC=C DIKJULDDNQFCJG-UHFFFAOYSA-M 0.000 description 1
239000004094 surface-active agent Substances 0.000 description 1
239000000080 wetting agent Substances 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt

Definitions

the invention relates to a method for the galvanic deposition of glare-free nickel deposits on a metallic surface.
nickel deposits also includes nickel alloy deposits.
metallic surface also includes metallized surfaces of non-metallic objects.
a concentration of the adducts in the range from 5 to 100 mg / l is used.
the deposition is operated so that the electrolyte has a temperature in the range of 40 to 75 ° C.
the adducts are selected so that the adducts form a finely dispersed emulsion in the working electrolyte, which manifests itself as turbidity.
the droplets of the emulsion are considered to be the reason for the formation of a glare-free surface. Glare-free is in need of improvement.
the substances added for the purpose of producing the satin-like, shiny nickel deposits as part of the known measures are nonionic surfactants. These fail at a higher electrolyte temperature. They form an organic foreign substance in the electrolyte, in the form of an emulsion.
organic foreign substances are generated in the electrolyte by reacting at least one cation-active or amphoteric substance with organic anions of at least one compound.
anion-providing substances include alkyl or aryl sulfates, sulfonic acids and sulfinic acids such as sulfonamides and sulfonimides.
the electrolyte should additionally contain known primary and / or secondary gloss agents.
these organic foreign substances result in a decorative glare control in the form of a matt effect. After this period, however, the foreign substances must be filtered out due to agglomeration phenomena. It is expensive. In addition, the organic foreign substances have to be formed again for the next working cycle, which is also complex.
the invention is based on the technical problem of leading the method of the construction described above and the intended use described at the outset in such a way that a significantly improved defined glare-free quality is reproducibly achieved.
the usual basic gloss agents used are "sulfonic acids such as benzenesulfonic acid, naphthalene trisulfonic acid, alkanesulfonic acids or also sulfonamides or sulfonimides or the corresponding alkali salts" or mixtures thereof, in an amount of 0.5 to 10 g / l.
a substance from the group "the unsaturated aliphatic sulfonic acids or their alkali metal salts" or mixtures thereof are used for the purpose of producing the glare-free nickel deposits.
the concentration of the adducts added is expediently chosen in the range from 0.5 to 10 g / l.
the electrolyte is preferably operated in a temperature range of 50 to 65 ° C during the electrolytic deposition. Wetting agents and organic sulfinic acids or their alkali salts can also be added to the electrolyte.
the invention is based on the knowledge that even without the formation of a visible, cloudy emulsion and corresponding organic foreign bodies in the electrolyte, high-quality glare control is achieved if the teaching of the invention is followed.
the nickel layer applied according to the invention has a completely different structure than that produced by the known method described at the outset. This is explained below in connection with exemplary embodiments. It remains to be seen whether drop-shaped precipitates still occur according to the invention.
droplet-like precipitates are precipitates which are stabilized as droplets mainly via the surface tension. In any case, the effects that are necessary for the high-quality reproducible glare-free effect occur - and surprisingly, disruptive conglomerates that disturb the glare-free effect and have to be filtered off are not observed.
the current densities can largely be adapted to the operating conditions. It has proven useful to operate the electrolyte with a current density of 0.1 to 10 A / dm 2 .
the electrolyte is preferably operated with a current density of approximately 4 A / dm 2 .
the treatment time for the nickel deposition is largely arbitrary and can be adapted to the operating conditions, in particular also the layer thickness. Within the scope of the invention, the treatment time for the nickel deposition is preferably from 1 to 120 minutes, preferably about 10 min. is.
the electrolyte can always be operated without secondary circulation. Secondary circuit free means that a secondary circuit with filter devices or cooling devices is not required.
Figure 1 shows a precipitate in the form of a droplet structure, which can be assigned a droplet diameter of 1 to 7 ⁇ m.
Precipitation can be seen in the form of a drop structure, to which a droplet diameter of 5 to 20 ⁇ m can be assigned.
Example 2 The lack of glare of the coating according to Example 1 is significantly improved compared to the embodiment according to Example 2.

Landscapes

Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Chemical Kinetics & Catalysis (AREA)
Electrochemistry (AREA)
Materials Engineering (AREA)
Metallurgy (AREA)
Organic Chemistry (AREA)
Electroplating And Plating Baths Therefor (AREA)
Preventing Corrosion Or Incrustation Of Metals (AREA)
Physical Vapour Deposition (AREA)
Electrolytic Production Of Metals (AREA)

EP96116639A 1995-10-27 1996-10-17 Procédé de dépôt électrolytique de nickel lisse Expired - Lifetime EP0770710B2 (fr)

Applications Claiming Priority (3)

Application Number	Priority Date	Filing Date	Title
DE19540011		1995-10-27
DE9540011U		1995-10-27
DE19540011A DE19540011C2 (de)	1995-10-27	1995-10-27	Verfahren zur galvanischen Abscheidung von blendfreien Nickel- oder Nickellegierungsniederschlägen

Publications (3)

Publication Number	Publication Date
EP0770710A1 true EP0770710A1 (fr)	1997-05-02
EP0770710B1 EP0770710B1 (fr)	1999-01-07
EP0770710B2 EP0770710B2 (fr)	2002-08-14

Family

ID=7775920

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP96116639A Expired - Lifetime EP0770710B2 (fr)	1995-10-27	1996-10-17	Procédé de dépôt électrolytique de nickel lisse

Country Status (6)

Country	Link
US (1)	US5897763A (fr)
EP (1)	EP0770710B2 (fr)
JP (1)	JPH09202987A (fr)
AT (1)	ATE175453T1 (fr)
DE (2)	DE19540011C2 (fr)
ES (1)	ES2128135T5 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US6251253B1 (en) *	1999-03-19	2001-06-26	Technic, Inc.	Metal alloy sulfate electroplating baths
JP2002540291A (ja) *	1999-03-19	2002-11-26	テクニツク・インコーポレーテツド	電気めっき槽
US6248228B1 (en) *	1999-03-19	2001-06-19	Technic, Inc. And Specialty Chemical System, Inc.	Metal alloy halide electroplating baths
US6797141B1 (en) *	1999-11-25	2004-09-28	Enthone Inc.	Removal of coagulates from a non-glare electroplating bath
US6306275B1 (en) *	2000-03-31	2001-10-23	Lacks Enterprises, Inc.	Method for controlling organic micelle size in nickel-plating solution
DE10025552C1 (de) *	2000-05-19	2001-08-02	Atotech Deutschland Gmbh	Saures galvanisches Nickelbad und Verfahren zum Abscheiden eines satinglänzenden Nickel- oder Nickellegierungsüberzuges
DE10222962A1 (de) *	2002-05-23	2003-12-11	Atotech Deutschland Gmbh	Saurer galvanischer Badelektrolyt und Verfahren zur elektrolytischen Abscheidung satinglänzender Nickelniederschläge
JP4811880B2 (ja) *	2006-01-06	2011-11-09	エントンインコーポレイテッド	艶消し金属層を堆積するための電解液および工程
EP2620529B1 (fr) *	2012-01-25	2014-04-30	Atotech Deutschland GmbH	Procédé de production de dépôts de cuivre mate
JP6760166B2 (ja)	2017-03-23	2020-09-23	トヨタ自動車株式会社	ニッケル皮膜の形成方法及び当該方法に使用するためのニッケル溶液
US11505867B1 (en)	2021-06-14	2022-11-22	Consolidated Nuclear Security, LLC	Methods and systems for electroless plating a first metal onto a second metal in a molten salt bath, and surface pretreatments therefore

Citations (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3839166A (en) *	1967-05-16	1974-10-01	Henkel & Cie Gmbh	Method for obtaining nickel deposits with satin finish
US3839165A (en) *	1967-08-26	1974-10-01	Henkel & Cie Gmbh	Nickel electroplating method

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US2238861A (en) *	1938-07-06	1941-04-15	Harshaw Chem Corp	Electrodeposition of metals
DE1134258B (de) *	1959-05-06	1962-08-02	Dehydag Gmbh	Saures galvanisches Nickelbad
DE1621085C3 (de) *	1967-05-16	1980-02-14	Henkel Kgaa, 4000 Duesseldorf	Saures galvanisches Bad zur Abscheidung satinglanzender Nickelniederschlage
BE794695A (fr) *	1972-01-29	1973-05-16	W Kampschulte & Cie K G Dr	Bain galvanique de nickel pour la separation de revetements de nickel satines mats
DE2327881B2 (de) *	1973-06-01	1978-06-22	Langbein-Pfanhauser Werke Ag, 4040 Neuss	Verfahren zur galvanischen Abscheidung mattglänzender Nickel- bzw. Nickel/Kobalt-Niederschläge
JPS56152988A (en) *	1980-04-30	1981-11-26	Nobuyuki Koura	Nickel satin finish plating bath of heavy ruggedness
JPS61238993A (ja) *	1985-04-16	1986-10-24	Dai Ichi Kogyo Seiyaku Co Ltd	電気メツキ浴用添加剤
JPS62205041A (ja) *	1986-03-05	1987-09-09	Nisso Yuka Kogyo Kk	１，４−ブチンジオ−ルのヒドロキシアルキルエ−テル化物の製造方法およびこれを用いたニツケルメツキ処理液

1995
- 1995-10-27 DE DE19540011A patent/DE19540011C2/de not_active Expired - Lifetime
1996
- 1996-10-17 AT AT96116639T patent/ATE175453T1/de not_active IP Right Cessation
- 1996-10-17 DE DE59601103T patent/DE59601103D1/de not_active Expired - Lifetime
- 1996-10-17 EP EP96116639A patent/EP0770710B2/fr not_active Expired - Lifetime
- 1996-10-17 ES ES96116639T patent/ES2128135T5/es not_active Expired - Lifetime
- 1996-10-25 JP JP8284052A patent/JPH09202987A/ja active Pending
- 1996-10-25 US US08/736,906 patent/US5897763A/en not_active Expired - Lifetime

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3839166A (en) *	1967-05-16	1974-10-01	Henkel & Cie Gmbh	Method for obtaining nickel deposits with satin finish
US3839165A (en) *	1967-08-26	1974-10-01	Henkel & Cie Gmbh	Nickel electroplating method

Also Published As

Publication number	Publication date
EP0770710B1 (fr)	1999-01-07
ES2128135T3 (es)	1999-05-01
DE59601103D1 (de)	1999-02-18
US5897763A (en)	1999-04-27
ATE175453T1 (de)	1999-01-15
EP0770710B2 (fr)	2002-08-14
JPH09202987A (ja)	1997-08-05
DE19540011A1 (de)	1997-04-30
DE19540011C2 (de)	1998-09-10
ES2128135T5 (es)	2003-03-01

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Publication	Publication Date	Title
DE69127394T2 (de)	1998-01-15	Zinn-Elektroplattierung bei hoher Geschwindigkeit
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EP0770710B2 (fr)	2002-08-14	Procédé de dépôt électrolytique de nickel lisse
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DE3108466C2 (de)	1983-05-26	Verwendung eines Acetylenalkohols in einem Bad zur galvanischen Abscheidung einer Palladium/Nickel-Legierung
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DE1496898C3 (de)	1973-10-25	Verfahren zur galvanischen Ab scheidung von stark glanzenden und eingeebneten Nickelschichten
DE3108467A1 (de)	1982-09-16	Bad zur galvanischen abscheidung einer palladium/nickel-legierung
DE3909811C2 (fr)	1991-05-08