EP0761844A1 - Procédé de dépÔt électrolytique de chrome - Google Patents

Procédé de dépÔt électrolytique de chrome Download PDF

Info

Publication number: EP0761844A1
Authority: EP; European Patent Office
Prior art keywords: chrome; black; galvanic; pearl; hard
Prior art date: 1995-08-12
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

EP96107054A

Other languages

German (de)

English (en)

Other versions

EP0761844B1 (fr

Inventor

Marco Santini

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.)

Aalberts Process Technologies Haerkingen AG

Original Assignee

Duralloy AG

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.)

1995-08-12

Filing date

1996-05-04

Publication date

1997-03-12

1996-05-04 Application filed by Duralloy AG filed Critical Duralloy AG

1997-03-12 Publication of EP0761844A1 publication Critical patent/EP0761844A1/fr

1999-09-29 Application granted granted Critical

1999-09-29 Publication of EP0761844B1 publication Critical patent/EP0761844B1/fr

2016-05-04 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 61
238000000034 method Methods 0.000 title claims description 13
238000007747 plating Methods 0.000 title claims description 11
238000000576 coating method Methods 0.000 claims abstract description 18
239000011248 coating agent Substances 0.000 claims abstract description 12
239000011651 chromium Substances 0.000 claims abstract description 8
229910052804 chromium Inorganic materials 0.000 claims abstract description 7
WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
239000000463 material Substances 0.000 claims description 4
229910000423 chromium oxide Inorganic materials 0.000 claims description 3
239000000839 emulsion Substances 0.000 claims description 2
230000008021 deposition Effects 0.000 claims 1
238000004070 electrodeposition Methods 0.000 abstract description 2
239000000758 substrate Substances 0.000 abstract 1
239000000314 lubricant Substances 0.000 description 3
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
AZRWZYCGBPLOMN-UHFFFAOYSA-N [Cu].[Cu].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn] Chemical compound [Cu].[Cu].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn] AZRWZYCGBPLOMN-UHFFFAOYSA-N 0.000 description 2
238000005299 abrasion Methods 0.000 description 2
239000003792 electrolyte Substances 0.000 description 2
JHJNPOSPVGRIAN-SFHVURJKSA-N n-[3-[(1s)-1-[[6-(3,4-dimethoxyphenyl)pyrazin-2-yl]amino]ethyl]phenyl]-5-methylpyridine-3-carboxamide Chemical compound C1=C(OC)C(OC)=CC=C1C1=CN=CC(N[C@@H](C)C=2C=C(NC(=O)C=3C=C(C)C=NC=3)C=CC=2)=N1 JHJNPOSPVGRIAN-SFHVURJKSA-N 0.000 description 2
239000004810 polytetrafluoroethylene Substances 0.000 description 2
229920001343 polytetrafluoroethylene Polymers 0.000 description 2
KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
239000002253 acid Substances 0.000 description 1
230000002378 acidificating effect Effects 0.000 description 1
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
229940117975 chromium trioxide Drugs 0.000 description 1
GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
238000005260 corrosion Methods 0.000 description 1
230000007797 corrosion Effects 0.000 description 1
238000009713 electroplating Methods 0.000 description 1
230000002349 favourable effect Effects 0.000 description 1
AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
238000010438 heat treatment Methods 0.000 description 1
239000007788 liquid Substances 0.000 description 1
238000005461 lubrication Methods 0.000 description 1
229910052760 oxygen Inorganic materials 0.000 description 1
239000001301 oxygen Substances 0.000 description 1
235000021110 pickles Nutrition 0.000 description 1
238000005498 polishing Methods 0.000 description 1
239000011148 porous material Substances 0.000 description 1
229910052700 potassium Inorganic materials 0.000 description 1
239000011591 potassium Substances 0.000 description 1
150000003839 salts Chemical class 0.000 description 1
239000007921 spray Substances 0.000 description 1

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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
- 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
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers

Definitions

the invention relates to a method for the electrodeposition of chrome coatings on an electrically conductive, in particular metallic base material, the base material being first cleaned and activated and then being subjected to a galvanic chromium plating bath in order to form a hard chrome coating with a hardness of at least 600 HV with pearl - or columnar structure-like surface, in particular according to German patent 25 02 284.
a chrome plating bath is described, with which shiny to metal-gray chrome coatings with a pearl-like surface with a hardness of up to approximately 1,500 HV can be achieved.
These chrome coatings with the trade name "DURALLOY” are characterized on the one hand by high wear resistance, on the other hand by favorable sliding properties, since the homogeneous spherical surface favors the wettability and thus the formation of a stable oil film.
the present invention has for its object to improve the known chrome coating to the extent that it has high wear resistance with low coefficients of friction even without lubricants.
the pearl or columnar structure-like surface of the hard chrome coating is filled and smoothed by galvanically applied black chrome.
This black chrome is applied in a layer thickness of at least 1 micron, preferably from about 2 micron to about 6 micron, which ensures that the pearl or column structure of the lower hard chrome layer is completely or largely covered.
the black chrome protrudes above the lower hard chrome layer, it is compacted in a kind of running-in process in a short time depending on the application and load and thus embedded in the homogeneous pearl structure.
the pearl or columnar surface of the hard chrome layer has a center distance between adjacent elevations of approximately 1 ⁇ to approximately 5 ⁇ . This can be reliably controlled by observing the parameters for the chromium plating bath described in German Patent 25 02 284.
the starting point is a metallic workpiece that first degreases thermally at a maximum of 70 ° C and electrolytically and then is converted from the basic to the acidic state by a 5% sulfuric acid pickle in order to activate it for the subsequent galvanic treatment. Then the workpiece is immersed in a chrome plating bath containing 400 to 500 g / l chromium trioxide, 2 to 14 g / l strontium sulfate, 4 to 26 g / l potassium silicofluoride, 2 to 8 g / l potassium dichromate and 4 to 50 g / l technical 2.2 -Dichloromonic acid contains. With regard to the other treatment parameters, reference is made to the already mentioned German patent 25 02 284.
the workpiece 1 (cf. FIGS. 1 and 2) thereby receives a hard chrome coating 2 with a layer thickness of at least 2 ⁇ m, preferably approximately 4-6 ⁇ m or more.
the bath parameters are set so that a more or less regular pearl structure 2a with a roughness depth of at least about 1 .mu.m, preferably about 1.5 .mu.m to about 5 .mu.m is established on the surface of the hard chrome layer.
the black chrome baths sold under the trade names ANKOR 1130 and 1131 are suitable. They contain approximately 420 to 480 g / l chromic acid, approximately 2 to 15 g / l chromium oxide, Cr 2 O 3 and are preferably sulfate-free.
the bath temperature is at room temperature and the current density is between 15 and 30 A / dm 2 . After a treatment time of a few minutes, a black chrome layer of about 2 ⁇ to about 5 ⁇ is obtained.
the layer thickness is chosen approximately so that the pearl structure 2a of the hard chrome layer is at least filled and leveled, expediently also has a certain overlap, as shown in FIG. 1.
This covering is removed due to the low abrasion resistance of the black chrome after a short running-in phase and compacted into the pearl structure, which results in the surface structure shown in FIG. 2. It is characterized by a continuous black chrome phase, which is interspersed with a large number of hard chrome islands. It has no pores or cracks.
the black chrome layer in particular to bind the chromium mixed oxide, it can be sealed with a polishing emulsion.
the service life of a workpiece coated according to the invention was determined to be 400 hours compared to a service life of 24 hours for a normal hard-chromium-plated workpiece and for a service life of 120 hours, one with 2 - 4 ⁇ DURALLOY hard chrome-plated workpiece.
the invention is characterized by a considerably longer service life, lower coefficients of friction and by saving lubricants.

Landscapes

Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Chemical Kinetics & Catalysis (AREA)
Electrochemistry (AREA)
Materials Engineering (AREA)
Metallurgy (AREA)
Organic Chemistry (AREA)
Electroplating Methods And Accessories (AREA)
Electroplating And Plating Baths Therefor (AREA)

EP96107054A 1995-08-12 1996-05-04 Procédé de dépÔt électrolytique de chrome Expired - Lifetime EP0761844B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE19529843		1995-08-12
DE19529843A DE19529843A1 (de)	1995-08-12	1995-08-12	Verfahren zur galvanischen Verchromung

Publications (2)

Publication Number	Publication Date
EP0761844A1 true EP0761844A1 (fr)	1997-03-12
EP0761844B1 EP0761844B1 (fr)	1999-09-29

Family

ID=7769427

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP96107054A Expired - Lifetime EP0761844B1 (fr)	1995-08-12	1996-05-04	Procédé de dépÔt électrolytique de chrome

Country Status (4)

Country	Link
US (1)	US5632880A (fr)
EP (1)	EP0761844B1 (fr)
JP (1)	JPH09104995A (fr)
DE (2)	DE19529843A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE10121593A1 (de) *	2001-05-03	2002-11-07	Duralloy Ag Haerkingen	Verfahren zur Beschichtung von Werkstücken mit einem Lagermetall
EP1918425A1 (fr) *	2006-10-24	2008-05-07	Wolf-Dieter Franz	Surface chromée grisâtre
US9194416B2 (en)	2012-05-10	2015-11-24	Sfs Intec Holding Ag	Self-drilling screw and use thereof

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE19929090A1 (de) *	1999-06-24	2000-12-28	Duralloy Ag Haerkingen	Verfahren zur Beschichtung eines Werkstückes mit einem Schmierstoff
CN1318650C (zh) *	2002-11-19	2007-05-30	深圳富泰宏精密工业有限公司	转轴座加工方法
DE102004006098A1 (de) *	2004-02-06	2005-09-01	Huwil-Werke Gmbh Möbelschloss- Und Beschlagfabriken	Verfahren zum Beschichten eines Bauteils und Bauteil
CN101555614B (zh) *	2008-04-11	2011-03-30	深圳富泰宏精密工业有限公司	塑料表面电镀方法
CN101638801A (zh) *	2008-07-30	2010-02-03	深圳富泰宏精密工业有限公司	壳体的表面处理方法
CN103122469A (zh) *	2011-11-18	2013-05-29	欧忠文	枪管内膛镀铬高效添加剂及其镀液
JP7602786B2 (ja) *	2020-11-14	2024-12-19	睦技研株式会社	メッキ方法
JP7523483B2 (ja) *	2022-02-18	2024-07-26	オテック株式会社	複合化クロムめっき物品
KR102761612B1 (ko) *	2024-03-27	2025-01-31	김영준	무광 블랙 크롬도금 방법

Citations (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
JPS5896892A (ja) *	1981-12-02	1983-06-09	Suzuki Motor Co Ltd	黒色クロムメツキ法

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US3615741A (en) *	1969-04-09	1971-10-26	Scm Corp	Chromium-containing component for surface coatings, process for making same and surface coating compositions containing same
US4039399A (en) *	1971-03-11	1977-08-02	Dana Corporation	Method of making a bearing surface
GB1492702A (en) *	1974-01-23	1977-11-23	Vintage Curacao Nv	Electroplating process for chrome
JPS5248711A (en) *	1975-10-16	1977-04-19	Mazda Motor Corp	Rotary piston engine
GB1591051A (en) *	1977-01-26	1981-06-10	Ibm	Electroplating chromium and its alloys
JPS61594A (ja) *	1984-06-14	1986-01-06	Seiko Epson Corp	時計用外装部品の製造方法
DE3531410A1 (de) *	1985-09-03	1987-03-05	Goetze Ag	Galvanische hartchromschicht
DE3813617C1 (fr) *	1988-04-22	1989-10-05	Goetze Ag, 5093 Burscheid, De
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DE4011201C1 (en) *	1990-04-06	1991-08-22	Lpw-Chemie Gmbh, 4040 Neuss, De	Coating workpiece with chromium for improved corrosion resistance - comprises using aq. electrolyte soln. contg. chromic acid sulphate ions, and fluoro:complexes to increase deposition
JP3054425B2 (ja) *	1990-06-01	2000-06-19	株式会社共立	摺動面の製作方法
JPH05222575A (ja) *	1992-02-10	1993-08-31	Tsubakimoto Chain Co	金属表面処理方法
JPH07301241A (ja) *	1994-04-28	1995-11-14	Ntn Corp	耐食性軸受

1995
- 1995-08-12 DE DE19529843A patent/DE19529843A1/de not_active Withdrawn
1996
- 1996-05-04 EP EP96107054A patent/EP0761844B1/fr not_active Expired - Lifetime
- 1996-05-04 DE DE59603210T patent/DE59603210D1/de not_active Expired - Lifetime
- 1996-08-09 US US08/694,738 patent/US5632880A/en not_active Expired - Lifetime
- 1996-08-12 JP JP8211815A patent/JPH09104995A/ja active Pending

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
JPS5896892A (ja) *	1981-12-02	1983-06-09	Suzuki Motor Co Ltd	黒色クロムメツキ法

Non-Patent Citations (1)

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Title
PATENT ABSTRACTS OF JAPAN vol. 7, no. 195 (C - 183) 25 August 1983 (1983-08-25) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE10121593A1 (de) *	2001-05-03	2002-11-07	Duralloy Ag Haerkingen	Verfahren zur Beschichtung von Werkstücken mit einem Lagermetall
US6875330B2 (en)	2001-05-03	2005-04-05	Duralloy Ag	Process for coating workpieces with bearing metal
EP1918425A1 (fr) *	2006-10-24	2008-05-07	Wolf-Dieter Franz	Surface chromée grisâtre
US9194416B2 (en)	2012-05-10	2015-11-24	Sfs Intec Holding Ag	Self-drilling screw and use thereof

Also Published As

Publication number	Publication date
DE59603210D1 (de)	1999-11-04
JPH09104995A (ja)	1997-04-22
US5632880A (en)	1997-05-27
EP0761844B1 (fr)	1999-09-29
DE19529843A1 (de)	1997-02-13

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Publication	Publication Date	Title
EP0565070B1 (fr)	1997-07-30	Procédé d'électrodéposition
EP0761844B1 (fr)	1999-09-29	Procédé de dépÔt électrolytique de chrome
DE69706678T2 (de)	2002-06-20	Galvanisiertes aluminiumblech
DE1771323A1 (de)	1972-02-03	Verfahren zum UEberziehen von Mctalloberflaechen mit einem fluorhaltigen Polymer
DE2462450A1 (de)	1977-03-31	Verfahren zum stromlosen plattieren oder galvanisieren von metallen sowie mit diesem verfahren hergestellter gegenstand
DE68926485T2 (de)	1996-12-05	Ein eine Aluminium-Plattierung enthaltendes Bestandteil für die anodische Oxidation
DE2800258A1 (de)	1978-07-20	Verfahren zur erzeugung zinkhaltiger mehrfachueberzuege
DE3606430C2 (fr)	1988-10-20
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