EP0084816A2 - Electrolyte pour dépôt électrolytique de l'aluminium - Google Patents

Electrolyte pour dépôt électrolytique de l'aluminium Download PDF

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Publication number
EP0084816A2
EP0084816A2 EP83100245A EP83100245A EP0084816A2 EP 0084816 A2 EP0084816 A2 EP 0084816A2 EP 83100245 A EP83100245 A EP 83100245A EP 83100245 A EP83100245 A EP 83100245A EP 0084816 A2 EP0084816 A2 EP 0084816A2
Authority
EP
European Patent Office
Prior art keywords
electrolyte
organometallic
aluminum
electroplating
mol
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.)
Granted
Application number
EP83100245A
Other languages
German (de)
English (en)
Other versions
EP0084816B2 (fr
EP0084816A3 (en
EP0084816B1 (fr
Inventor
Siegfried Dr. Birkle
Klaus Stöger
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.)
AlumiPlate Inc
Original Assignee
Siemens 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.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6153853&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0084816(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Siemens AG filed Critical Siemens AG
Priority to AT83100245T priority Critical patent/ATE20252T1/de
Publication of EP0084816A2 publication Critical patent/EP0084816A2/fr
Publication of EP0084816A3 publication Critical patent/EP0084816A3/de
Application granted granted Critical
Publication of EP0084816B1 publication Critical patent/EP0084816B1/fr
Publication of EP0084816B2 publication Critical patent/EP0084816B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/42Electroplating: Baths therefor from solutions of light metals
    • C25D3/44Aluminium

Definitions

  • the invention relates to an organometallic electrolyte for the electrodeposition of aluminum and the use of this electrolyte.
  • Organometallic electrolytes ie organo-aluminum complex compounds (DE-PS 1 047 450), can be used for the galvanic deposition of aluminum.
  • organo-aluminum complex compounds DE-PS 1 047 450
  • a large number of compounds have been described which can be used for galvanic aluminizing, for example onium and alkali complex compounds.
  • the complex salt NaF described as optimal has been used.
  • 2 Al (C 2 H 5 ) 3 used ("Journal for inorganic and general chemistry", Vol. 283, 1956, pp. 414 to 424).
  • the object of the invention is to provide an organometallic electrolyte for the electrodeposition of aluminum, which has a high scatterability but also a high conductivity and good solubility and is easily accessible commercially.
  • the organoaluminum electrolyte according to formula (1) according to the invention proves to be extremely progressive in terms of electroplating, i.e. it fulfills the demands placed on electrolytes for a technically widely applicable and economical aluminizing process to a far greater extent than was previously possible.
  • the electrolyte according to the invention namely has a high scattering capacity and, at the same time, electrical conductivity and solubility required for economical aluminizing, as well as good commercial accessibility. For the first time, it combines the electrotechnical properties relevant to electroplating. Another advantage is also that this electrolyte compared to NaF. 2 Al (C2H5) 3 has a significantly lower sensitivity to oxygen and moisture.
  • the electrolyte according to the invention is based on knowledge which has been obtained on the one hand with regard to the relationships between the composition of organo-aluminum complex compounds and the electroplating requirements, such as scatterability, conductivity and solubility (in low-viscosity aromatic hydrocarbons which are liquid at room temperature and have low water absorption). These relationships were previously unknown.
  • the metal ion is decisive for the scatterability, whereas the conductivity is influenced both by the metal ion and by the halogen ion and by the length of the alkyl radicals.
  • the alkyl residues and the metal ion turn out to be particularly relevant for solubility.
  • the electrolyte according to the invention is comparable to cadmium electrolytes in terms of scatterability in the field of electro-technical interest. For the first time there is the possibility to aluminize the same product range as for cadming. This creates the electro-technical prerequisite for replacing cadmium with aluminum as a corrosion protection coating.
  • the electrolyte according to the invention is preferably used in the form of a solution.
  • Aromatic hydrocarbons which are liquid at room temperature, such as toluene, are advantageously used as solvents, advantageously in the following composition: 1 mol of electrolyte salt per 1 to 10 mol, preferably 1 to 5 mol, of solvent.
  • the same method can also be used to produce electrolytes with a different composition.
  • the solvent-free electrolytes can also be produced in this way. To do this, however, it is necessary to carry out the reaction above the melting temperature of the respective electrolyte.
  • the good scatterability of the electrolyte according to the invention is to be demonstrated on the basis of electroplating tests.
  • a galvanizing cell in the form of a rectangular glass vessel (20 cm x 8 cm x 20 cm) was used to carry out the electroplating tests, and an Al anode plate was attached to each end. Since the aluminum electrolytes are sensitive to air and moisture, the electroplating cell was provided with a special cover that has several openings: for a thermometer, for a conductivity cell, for a gas transfer tube (for flooding the cell with nitrogen), for two stirrers (diagonally opposite in the corners of the cell in front of the anodes) and for charging the test specimens to be aluminized. Served as test specimens. Rectangular angle plates made of steel of a certain size. To determine the scatterability, the thickness of the aluminum layer deposited on the angle plates was determined by means of a layer thickness measuring device.
  • test specimens were pretreated, as is customary in electroplating, ie pickled and degreased.
  • the one on a Ka The test specimen attached to the test rod was first degreased using an organic solvent and pickled by immersion in dilute hydrochloric acid. Subsequently, the specimen was cathodically degreased and provided for improving adhesion with an approximately 1 / um thick nickel layer.
  • the toluene-moist test specimen was introduced into the electroplating cell, ie into the electrolyte, and - as a cathode - arranged between the two anodes (cathode area: 2 dm 2 ; distance between anode and cathode: each about 10 cm).
  • the electroplating was carried out at an electrolyte temperature of 100 ° C by means of a so-called pulse current (deposition voltage: + 10 V).
  • the test specimens were alternately poled cathodically and anodically, the cathodic deposition time in each case 80 ms and the anodic deposition time in each case 20 ms.
  • the known electrolyte NaF was examined. 2 Al (C2H5) 3 and, each in a commercially available form, a cadmium electrolyte (cyanidic), a zinc electrolyte (weakly cyanidic) and a nickel electrolyte (weakly acidic), with the last three electrolytes being galvanized using direct current.

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  • 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)
  • Conductive Materials (AREA)
  • Primary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
EP83100245A 1982-01-25 1983-01-13 Electrolyte pour dépôt électrolytique de l'aluminium Expired - Lifetime EP0084816B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83100245T ATE20252T1 (de) 1982-01-25 1983-01-13 Elektrolyt zur galvanischen abscheidung von aluminium.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3202265 1982-01-25
DE19823202265 DE3202265A1 (de) 1982-01-25 1982-01-25 Elektrolyt zur galvanischen abscheidung von aluminium

Publications (4)

Publication Number Publication Date
EP0084816A2 true EP0084816A2 (fr) 1983-08-03
EP0084816A3 EP0084816A3 (en) 1984-06-06
EP0084816B1 EP0084816B1 (fr) 1986-06-04
EP0084816B2 EP0084816B2 (fr) 1991-10-30

Family

ID=6153853

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83100245A Expired - Lifetime EP0084816B2 (fr) 1982-01-25 1983-01-13 Electrolyte pour dépôt électrolytique de l'aluminium

Country Status (8)

Country Link
US (1) US4417954A (fr)
EP (1) EP0084816B2 (fr)
JP (1) JPS58171591A (fr)
AT (1) ATE20252T1 (fr)
CA (1) CA1209157A (fr)
DE (2) DE3202265A1 (fr)
DK (1) DK154657C (fr)
ES (1) ES8403490A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998048082A1 (fr) * 1997-04-19 1998-10-29 Aluminal Oberflächentechnik Gmbh Electrolyte pour deposition electrolytique d'aluminium a vitesse elevee sur des produits continus
WO2003102276A1 (fr) * 2002-05-31 2003-12-11 Aluminal Oberflächentechnik Gmbh & Co. Kg Procede de production de complexes organoaluminium et leur utilisation pour produire des solutions electrolytiques servant a deposer electrochimiquement des revetements en alliages aluminium-magnesium
EP1927680A1 (fr) * 2006-11-29 2008-06-04 Aluminal Oberflächentechnik GmbH & Co. KG Electrolyte destiné à la déposition galvanique d'aluminium à partir de solvants aprotiques dans un tambour à galvanisation
WO2010106072A2 (fr) 2009-03-18 2010-09-23 Basf Se Électrolyte et additifs tensio-actifs pour le dépôt galvanique de couches d'aluminium lisses et compactes à partir de liquides ioniques

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4517253A (en) * 1984-01-23 1985-05-14 Rose Robert M Cryoelectrodeposition
NL8602856A (nl) * 1986-11-11 1988-06-01 Hga Galvano Aluminium B V Werkwijze en inrichting voor het galvanisch afscheiden van metalen op een substraat.
US4778575A (en) * 1988-01-21 1988-10-18 The United States Of America As Represented By The United States Department Of Energy Electrodeposition of magnesium and magnesium/aluminum alloys
DE3919068A1 (de) * 1989-06-10 1990-12-13 Studiengesellschaft Kohle Mbh Aluminiumorganische elektrolyte zur elektrolytischen abscheidung von hochreinem aluminium
DE3919069A1 (de) * 1989-06-10 1990-12-13 Studiengesellschaft Kohle Mbh Aluminiumorganische elektrolyte und verfahren zur elektrolytischen abscheidung von aluminium
EP0504704A1 (fr) * 1991-03-20 1992-09-23 Siemens Aktiengesellschaft Prétraitement pour matériaux métalliques pour la déposition de métaux par électrolyse
EP0504705A1 (fr) * 1991-03-20 1992-09-23 Siemens Aktiengesellschaft Prétraitement pour matériaux métalliques pour la déposition de métaux par électrolyse
EP0505886A1 (fr) * 1991-03-28 1992-09-30 Siemens Aktiengesellschaft Formation de revêtements décoratifs d'aluminium
DE19649000C1 (de) * 1996-11-27 1998-08-13 Alcotec Beschichtungsanlagen G Elektrolyt zur galvanischen Abscheidung von Aluminium und dessen Verwendung
DE19716493C2 (de) * 1997-04-19 2001-11-29 Aluminal Oberflaechentechnik Verfahren zum elektrolytischen Beschichten von metallischen oder nichtmetallischen Endlosprodukten und Vorrichtung zur Durchführung des Verfahrens
US7250102B2 (en) * 2002-04-30 2007-07-31 Alumiplate Incorporated Aluminium electroplating formulations
WO2002088434A1 (fr) * 2001-04-30 2002-11-07 Alumiplate Incorporated Formulations d'electrodeposition d'aluminium
DE102007018489A1 (de) 2007-04-19 2008-10-23 Tec-Chem Gmbh Aluminiumorganischer 4-Komponentenelektrolyt zur Abscheidung von Aluminium
US10190640B2 (en) 2016-03-23 2019-01-29 Schaeffler Technologies AG & Co. KG Bearing with integrated shunt
US10794427B2 (en) 2016-04-05 2020-10-06 Schaeffler Technologies AG & Co. KG Bearing ring with insulating coating
US10539178B2 (en) 2017-05-18 2020-01-21 Schaeffler Technologies AG & Co. KG Vapor deposition bearing coating
US11142841B2 (en) 2019-09-17 2021-10-12 Consolidated Nuclear Security, LLC Methods for electropolishing and coating aluminum on air and/or moisture sensitive substrates
US11661665B2 (en) 2020-04-30 2023-05-30 The Boeing Company Aluminum and aluminum alloy electroplated coatings

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1047450B (de) * 1955-06-13 1958-12-24 Dr E H Karl Ziegler Dr Elektrolyt zur elektrolytischen Abscheidung von Aluminium
US4101386A (en) * 1971-05-07 1978-07-18 Siemens Aktiengesellschaft Methods of coating and surface finishing articles made of metals and their alloys

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929611A (en) * 1974-07-19 1975-12-30 Ametek Inc Electrodepositing of aluminum
NL8100569A (nl) * 1981-02-06 1982-09-01 Philips Nv Elektrolytvloeistof voor het galvanisch neerslaan van aluminium.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1047450B (de) * 1955-06-13 1958-12-24 Dr E H Karl Ziegler Dr Elektrolyt zur elektrolytischen Abscheidung von Aluminium
US4101386A (en) * 1971-05-07 1978-07-18 Siemens Aktiengesellschaft Methods of coating and surface finishing articles made of metals and their alloys

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998048082A1 (fr) * 1997-04-19 1998-10-29 Aluminal Oberflächentechnik Gmbh Electrolyte pour deposition electrolytique d'aluminium a vitesse elevee sur des produits continus
WO2003102276A1 (fr) * 2002-05-31 2003-12-11 Aluminal Oberflächentechnik Gmbh & Co. Kg Procede de production de complexes organoaluminium et leur utilisation pour produire des solutions electrolytiques servant a deposer electrochimiquement des revetements en alliages aluminium-magnesium
EP1927680A1 (fr) * 2006-11-29 2008-06-04 Aluminal Oberflächentechnik GmbH & Co. KG Electrolyte destiné à la déposition galvanique d'aluminium à partir de solvants aprotiques dans un tambour à galvanisation
WO2008064954A2 (fr) * 2006-11-29 2008-06-05 Aluminal Oberflächentechnik Gmbh & Co. Kg Électrolyte de dépôt par galvanisation d'aluminium à partir de solvants aprotiques dans un tambour de galvanisation
WO2008064954A3 (fr) * 2006-11-29 2009-06-04 Aluminal Oberflaechentechnik Électrolyte de dépôt par galvanisation d'aluminium à partir de solvants aprotiques dans un tambour de galvanisation
WO2010106072A2 (fr) 2009-03-18 2010-09-23 Basf Se Électrolyte et additifs tensio-actifs pour le dépôt galvanique de couches d'aluminium lisses et compactes à partir de liquides ioniques

Also Published As

Publication number Publication date
ES519248A0 (es) 1984-03-16
ATE20252T1 (de) 1986-06-15
EP0084816B2 (fr) 1991-10-30
DK154657C (da) 1989-05-01
US4417954A (en) 1983-11-29
DK25183A (da) 1983-07-26
DE3363841D1 (en) 1986-07-10
JPS58171591A (ja) 1983-10-08
JPS6122038B2 (fr) 1986-05-29
DE3202265A1 (de) 1983-07-28
ES8403490A1 (es) 1984-03-16
DK25183D0 (da) 1983-01-24
DK154657B (da) 1988-12-05
EP0084816A3 (en) 1984-06-06
EP0084816B1 (fr) 1986-06-04
CA1209157A (fr) 1986-08-05

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