EP2143828B1 - Elektrolyt und Verfahren zur Ablagerung einer matten Metallschicht - Google Patents

Elektrolyt und Verfahren zur Ablagerung einer matten Metallschicht Download PDF

Info

Publication number
EP2143828B1
EP2143828B1 EP08012262.5A EP08012262A EP2143828B1 EP 2143828 B1 EP2143828 B1 EP 2143828B1 EP 08012262 A EP08012262 A EP 08012262A EP 2143828 B1 EP2143828 B1 EP 2143828B1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
metal
deposited
composition
concentration
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.)
Active
Application number
EP08012262.5A
Other languages
English (en)
French (fr)
Other versions
EP2143828A1 (de
Inventor
Andreas KÖNIGSHOFEN
Danica Elbick
Helmut Starke
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.)
Filing date
Publication date
Priority to EP08012262.5A priority Critical patent/EP2143828B1/de
Application filed by Enthone Inc filed Critical Enthone Inc
Priority to ES08012262.5T priority patent/ES2615337T3/es
Priority to JP2011517566A priority patent/JP5647979B2/ja
Priority to US13/003,398 priority patent/US20110233065A1/en
Priority to KR1020117002872A priority patent/KR101663841B1/ko
Priority to PCT/US2009/049932 priority patent/WO2010006045A1/en
Priority to CN2009801346466A priority patent/CN102144049B/zh
Publication of EP2143828A1 publication Critical patent/EP2143828A1/de
Application granted granted Critical
Publication of EP2143828B1 publication Critical patent/EP2143828B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

Definitions

  • This invention relates to an electrolyte as well as a method for the deposition of a matt metal layer on a substrate surface.
  • the invention relates to an electrolyte which has a low concentration of the deposition metal and a method to deposit a matt metal layer by using such electrolytes.
  • the intention when depositing metal layers on substrate surfaces to gain a plain and glossy metal layer on the substrate surface may have functional properties, which properties can optimise the substrate surface for the later proposal, or decorative effects should be obtained.
  • the substrate sometimes it is preferred to have a non-glossy, matt or so-called pearlbrite metal layer on the substrate surface.
  • this intention can be based on the optical appearance of the deposit, on the other side matt or so-called pearlbrite deposits have specific technical properties, like for example to be non-glare, which properties may be desirable for technical or decorative use.
  • the application area for such a matt or pearlbrite metal layers is, for example, jewellery industry, fitting industry, automotive industry, as well as optical or fine mechanical industry. Especially in these areas non-glare metal layers are desired.
  • the deposition of matt or pearlbrite metal layers of non-allergic or low allergic metals is requested. The same is true for the application of matt or pearlbrite metal layers in the area of kitchen machinery and kitchen implements.
  • the substrate surface can be adapted to the later technical use.
  • the ductility, the hardness, the corrosion resistance, or comparable mechanical properties of the substrate surface can be optimised.
  • the international patent application WO 2007/076898 discloses an electrolyte as well as a method for the deposition of matt metal layers, especially of the metals vanadium, chrome, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tellurium, rhenium, platinum, gold, thallium, bismuth, or alloys of these.
  • an emulsion and/or dispersion is formed in the electrolyte by addition of an emulsion agent and/or dispersion agent, or a wetting agent.
  • a drawback of the electrolyte as well as the method known from the state of the art is that sometimes it is difficult to gain even deposits on the substrate surface.
  • an electrolyte for the deposition of a matt metal layer of a metal of the group consisting of Co, Ni, Cu, Sn, or an alloy of these metals on a substrate surface, wherein the electrolyte comprises a substituted or unsubstituted polyalkylene oxide or a derivate of a substituted or unsubstituted polyalkylene oxide, or a wetting agent, wherein the wetting agent is fluorated or perfluorated, or is a quaternary ammonium compound substituted with a polyalkalylene oxide, for building an emulsion and/or dispersion in the electrolyte, characterised in that the electrolyte comprises at least one halogenide, sulphate, or sulfonate of an element of the group consisting of sodium, potassium, aluminium, magnesium, or boron. In an embodiment, a methanesulfonate of sodium, potassium, or magnesium is preferred. In another embodiment, aluminium sulphate
  • the cloud point is exceeded, which effect is to be avoided by normal plating electrolytes, but here leads to the desired matt effect of the deposited metal layer.
  • the addition of the mentioned inert compounds which do not comprise any depositable metal cations increases the density so that a matt metal layer is deposited even at a very low concentration of plating metal in the electrolyte.
  • the electrolyte comprises a density increasing compound within a concentration in the range of from 2 0% to 100% by weight of the concentration of the metal to be deposited.
  • the alkali compound or alkaline earth compound is comprised in the inventive electrolyte in a range between 20% to 60% by weight of the concentration of the metal to be deposited.
  • a surface active wetting agent to the inventive electrolyte is possible.
  • the addition of a surface active wetting agent supports the even deposition of metal layers further.
  • the addition of surface active wetting agents was not possible since those surface active wetting agents would influence the formation of an emulsion and/or dispersion in the electrolyte, thereby influencing the matt or pearlbrite effect of the electrolyte. If surface active wetting agents were added to the electrolytes known from the state of the art, the deposited metal layers turned to be glossy instead of being non-glare.
  • the addition of surface active wetting agents is possible without influencing the matt effect of the electrolyte.
  • the surface active wetting agent which can be added to the inventive electrolyte may be a wetting agent of the group consisting of alkyl sulphates, sulfosuccinic acid, and betaines.
  • the surface active wetting agent may be comprised in the inventive electrolyte in a concentration between 0,01 mol/l and 100 mol/l, preferably between 0,1 mol/l and 10 mol/l.
  • the density increasing compound in the inventive electrolyte is sodium sulphate, magnesium sulphate, or aluminium sulphate.
  • the object of the invention is solved by a method for the electrolytic deposition of a matt metal layer on a substrate surface, which matt metal layer is deposited from an electrolyte forming an emulsion and/or dispersion by conducting a current between a cathodic contacted substrate surface and an anode, which method is characterised in that 10 to 50% by weight of the metal to be deposited comprised in the electrolyte is substituted by at least on density increasing halogenide, sulphate, or sulphonate of an element of the group consisting of sodium, potassium, aluminium, magnesium, or boron.
  • Ni-electrolyte comprising:

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)
  • Electroplating Methods And Accessories (AREA)

Claims (3)

  1. Verfahren zum elektrolytischen Abscheiden einer matten Schicht aus einem Metall aus der Gruppe bestehend aus Co, Ni, Cu, Sn oder einer Legierung dieser Metalle auf einer Substratoberfläche von einem Elektrolyt, der eine Emulsion und/oder Dispersion bildet, durch Leiten eines Stroms zwischen einem kathodisch kontaktierten Substrat und einer Anode, wobei das Verfahren die Schritte aufweist:
    a) Auswählen einer ersten Zusammensetzung für einen Elektrolyten, die dazu geeignet ist, eine matte Metallschicht eines Metalls der vorstehend erwähnten Gruppe auf der Substratoberfläche abzuscheiden, wobei die Zusammensetzung eine Konzentration des abzuscheidenden Metalls aufweist, und wobei die Zusammensetzung ein substituiertes oder unsubstituiertes Polyalkylenoxid oder ein Derivat eines substituierten oder unsubstituierten Polyalkylenoxids oder ein Benetzungsmittel aufweist, um eine Emulsion und/oder Dispersion zu bilden, wobei das Benetzungsmittel ein fluoriertes oder perfluoriertes Benetzungsmittel oder eine mit dem Polyalkylenoxid substituierte quaternäre Ammoniumverbindung ist;
    b) Herstellen eines auf der ersten Zusammensetzung basierenden Metallisierungselektrolyts, wobei 10 bis 50 Gew.-% des gemäß der ersten Zusammensetzung abzuscheidenden Metalls durch mindestens ein die Dichte erhöhendes Halogenid, Sulfat oder Sulfonat eines Elements der Gruppe bestehend aus Natrium, Kalium, Aluminium, Magnesium oder Bor ersetzt ist, um die Konzentration des abzuscheidenden Metalls im Vergleich zur ersten Zusammensetzung zu reduzieren, und wobei die Konzentration der die Dichte erhöhenden Verbindung im Bereich zwischen 20 Gew.-% und 100 Gew.-% der Konzentration des abzuscheidenden Metalls beträgt; und
    c) Inkontaktbringen der Substratoberfläche mit dem in Schritt b) erhaltenen Metallisierungselektrolyt und Zuführen des Stroms.
  2. Verfahren nach Anspruch 1, wobei die in Schritt a) ausgewählte Zusammensetzung ein oberflächenaktives Benetzungsmittel in einer Konzentration innerhalb des Bereichs von 0,01 Mol/l und 100 Mol/l aufweist, wobei das oberflächenaktive Benetzungsmittel ausgewählt ist aus der Gruppe bestehend aus Alkylsulfaten, Sulfobernsteinsäure und Betainen.
  3. Verfahren nach Anspruch 1 oder 2, wobei der Elektrolyt gemäß Schritt b) mindestens eine Verbindung der Gruppe bestehend aus Methansulfonat, Kaliummethansulfonat, Magnesiummethansulfonat, Aluminiumsulfat oder Bortetrafluorid aufweist.
EP08012262.5A 2008-07-08 2008-07-08 Elektrolyt und Verfahren zur Ablagerung einer matten Metallschicht Active EP2143828B1 (de)

Priority Applications (7)

Application Number Priority Date Filing Date Title
ES08012262.5T ES2615337T3 (es) 2008-07-08 2008-07-08 Electrolito y método para depositar una capa metálica mate
EP08012262.5A EP2143828B1 (de) 2008-07-08 2008-07-08 Elektrolyt und Verfahren zur Ablagerung einer matten Metallschicht
US13/003,398 US20110233065A1 (en) 2008-07-08 2009-07-08 Electrolyte and method for deposition of matte metal layer
KR1020117002872A KR101663841B1 (ko) 2008-07-08 2009-07-08 무광택 금속 층을 침착시키기 위한 전해질 및 방법
JP2011517566A JP5647979B2 (ja) 2008-07-08 2009-07-08 つや消し金属層の堆積のための電解質および方法
PCT/US2009/049932 WO2010006045A1 (en) 2008-07-08 2009-07-08 Electrolyte and method for deposition of matte metal layer
CN2009801346466A CN102144049B (zh) 2008-07-08 2009-07-08 电解质和无光泽金属层的淀积方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP08012262.5A EP2143828B1 (de) 2008-07-08 2008-07-08 Elektrolyt und Verfahren zur Ablagerung einer matten Metallschicht

Publications (2)

Publication Number Publication Date
EP2143828A1 EP2143828A1 (de) 2010-01-13
EP2143828B1 true EP2143828B1 (de) 2016-12-28

Family

ID=40070778

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08012262.5A Active EP2143828B1 (de) 2008-07-08 2008-07-08 Elektrolyt und Verfahren zur Ablagerung einer matten Metallschicht

Country Status (7)

Country Link
US (1) US20110233065A1 (de)
EP (1) EP2143828B1 (de)
JP (1) JP5647979B2 (de)
KR (1) KR101663841B1 (de)
CN (1) CN102144049B (de)
ES (1) ES2615337T3 (de)
WO (1) WO2010006045A1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWM404224U (en) * 2010-07-21 2011-05-21 guang-xi Guo Improved structure for silverware
EP2568063A1 (de) * 2011-09-09 2013-03-13 Rohm and Haas Electronic Materials LLC Kupfer-Elektroplattierverfahren mit geringer innerer Spannung
PL2620529T3 (pl) * 2012-01-25 2014-09-30 Atotech Deutschland Gmbh Sposób wytwarzania matowych warstw miedzianych
US10056636B1 (en) * 2013-10-03 2018-08-21 Primus Power Corporation Electrolyte compositions for use in a metal-halogen flow battery
CN104404583A (zh) * 2014-12-22 2015-03-11 常熟市伟达电镀有限责任公司 一种铝镁合金电镀液
JPWO2017077655A1 (ja) * 2015-11-06 2018-08-16 株式会社Ｊｃｕ ニッケルめっき用添加剤およびこれを含有するサテンニッケルめっき浴
CN109680310B (zh) * 2019-01-04 2020-07-07 中国计量大学 一种镍锑电镀液及其制备方法
JP7078185B2 (ja) * 2020-03-03 2022-05-31 日本製鉄株式会社 Ｎｉめっき鋼板、及びその製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005120425A (ja) * 2003-10-16 2005-05-12 Ishihara Chem Co Ltd スズ及びスズ合金メッキ浴

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1621085C3 (de) * 1967-05-16 1980-02-14 Henkel Kgaa, 4000 Duesseldorf Saures galvanisches Bad zur Abscheidung satinglanzender Nickelniederschlage
US3839165A (en) * 1967-08-26 1974-10-01 Henkel & Cie Gmbh Nickel electroplating method
DE1951558C3 (de) * 1969-10-13 1978-06-15 Henkel & Cie Gmbh, 4000 Duesseldorf Saures galvanisches Glanzzinkbad
DE2346942C3 (de) * 1973-09-18 1978-10-26 Dr.-Ing. Max Schloetter Gmbh & Co Kg, 7340 Geislingen Schwach saures Glanzzinkbad
US4119502A (en) * 1977-08-17 1978-10-10 M&T Chemicals Inc. Acid zinc electroplating process and composition
US4617097A (en) * 1983-12-22 1986-10-14 Learonal, Inc. Process and electrolyte for electroplating tin, lead or tin-lead alloys
DE3909811A1 (de) * 1989-03-24 1990-09-27 Lpw Chemie Gmbh Verwendung von zumindest einer organischen sulfinsaeure und/oder von zumindest einem alkalisalz einer organischen sulfinsaeure als mittel ...
DE69929967T2 (de) * 1998-04-21 2007-05-24 Applied Materials, Inc., Santa Clara Elektroplattierungssystem und verfahren zur elektroplattierung auf substraten
US6508927B2 (en) * 1998-11-05 2003-01-21 C. Uyemura & Co., Ltd. Tin-copper alloy electroplating bath
JP3871013B2 (ja) * 1998-11-05 2007-01-24 上村工業株式会社 錫−銅合金電気めっき浴及びそれを使用するめっき方法
US6387229B1 (en) * 1999-05-07 2002-05-14 Enthone, Inc. Alloy plating
US6793793B2 (en) * 2000-08-24 2004-09-21 Hideo Yoshida Electrochemical treating method such as electroplating and electrochemical reaction device therefor
CN1260399C (zh) * 2001-08-31 2006-06-21 罗姆和哈斯电子材料有限责任公司 电解镀锡溶液和用于电镀的方法
DE10222962A1 (de) * 2002-05-23 2003-12-11 Atotech Deutschland Gmbh Saurer galvanischer Badelektrolyt und Verfahren zur elektrolytischen Abscheidung satinglänzender Nickelniederschläge
WO2004101860A1 (en) * 2003-05-12 2004-11-25 Arkema Inc. High purity electrolytic sulfonic acid solutions
JP4603812B2 (ja) * 2003-05-12 2010-12-22 ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． 改良されたスズめっき方法
US20050173255A1 (en) 2004-02-05 2005-08-11 George Bokisa Electroplated quaternary alloys
US20060096868A1 (en) * 2004-11-10 2006-05-11 Siona Bunce Nickel electroplating bath designed to replace monovalent copper strike solutions
US20060283715A1 (en) * 2005-06-20 2006-12-21 Pavco, Inc. Zinc-nickel alloy electroplating system
PL1969160T3 (pl) * 2006-01-06 2011-09-30 Enthone Incorporated Elektrolit i sposób osadzania matowej warstwy metalu
JP2007262430A (ja) * 2006-03-27 2007-10-11 C Uyemura & Co Ltd 電気めっき方法
JP5642928B2 (ja) * 2007-12-12 2014-12-17 ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． 青銅の電気めっき
US8450169B2 (en) * 2010-11-29 2013-05-28 International Business Machines Corporation Replacement metal gate structures providing independent control on work function and gate leakage current

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005120425A (ja) * 2003-10-16 2005-05-12 Ishihara Chem Co Ltd スズ及びスズ合金メッキ浴

Also Published As

Publication number Publication date
US20110233065A1 (en) 2011-09-29
KR20110031224A (ko) 2011-03-24
WO2010006045A1 (en) 2010-01-14
JP2011527730A (ja) 2011-11-04
JP5647979B2 (ja) 2015-01-07
KR101663841B1 (ko) 2016-10-07
CN102144049B (zh) 2013-07-31
CN102144049A (zh) 2011-08-03
ES2615337T3 (es) 2017-06-06
EP2143828A1 (de) 2010-01-13

Similar Documents

Publication Publication Date Title
EP2143828B1 (de) Elektrolyt und Verfahren zur Ablagerung einer matten Metallschicht
JP5932214B2 (ja) 減摩コーティング
CN103080381B (zh) 用于滑动元件的分层复合材料,用于生产该复合材料的方法以及其用途
JP4620702B2 (ja) 滑り部材およびその製造方法
EP2096194B1 (de) Schutzbeschichtung für Metalldichtungen
DE102008050135B4 (de) Verfahren zur Abscheidung von Platin-Rhodiumschichten mit verbesserter Helligkeit
EP2116634B1 (de) Modifizierter Kupfer-Zinn-Elektrolyt und Verfahren zur Abscheidung von Bronzeschichten
AT514818B1 (de) Abscheidung von Cu, Sn, Zn-Beschichtungen auf metallischen Substraten
CN106414806A (zh) 用于电镀移动的金属条的方法和由此制造的镀层金属条
Bahramian et al. Cu/Ni/Au multilayers by electrochemistry: A crucial system in electronics-A critical review
JP4817352B2 (ja) 鉄、コバルトまたはニッケルを含む三成分錫亜鉛合金、ガルバーニ溶液およびそれらを生成するガルバーニ法
WO2002052068A1 (en) Zn-co-w alloy electroplated steel sheet with excellent corrosion resistance and welding property, and its electrolyte for it
EP2755819A1 (de) Beschichtete gegenstände, elektrotauchbeschichtungsbäder und zugehörige systeme
CA2908478C (en) Functional chromium layer with improved corrosion resistance
EP0651071B1 (de) Verfahren zur Herstellung von Werkstücken mit verschleissfesten Überzügen
JP5159786B2 (ja) 光吸収性部材およびその製造方法
JPH055911B2 (de)
Petro et al. Development of hybrid electro-electroless deposit (HEED) coatings and applications
JP3817246B2 (ja) 高耐食・高加工性メッキ鋼線およびその製造方法ならびに金網製かご
Chiu et al. Softening of micro Sn electrodeposit by polyethylene glycol (PEG) addition
WO2021199087A1 (en) Galvanic process for the electrodeposition of a protective layer, and associated bath
CN115768927A (zh) 从三价铬电解质电沉积功能性或装饰性铬层的方法
Kunioshi et al. The development of amorphous Fe-Cr-P electrodeposits

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: 20100713

AKX Designation fees paid

Designated state(s): DE ES FR IT

17Q First examination report despatched

Effective date: 20140728

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160928

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KOENIGSHOFEN, ANDREAS

Inventor name: STARKE, HELMUT

Inventor name: ELBICK, DANICA

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR IT

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602008048096

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2615337

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20170606

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008048096

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20170929

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230524

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230620

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20230801

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230724

Year of fee payment: 16

Ref country code: DE

Payment date: 20230620

Year of fee payment: 16