EP1518946A1 - Electrolyte pour la deposition galvanique d' aluminium - Google Patents

Electrolyte pour la deposition galvanique d' aluminium Download PDF

Info

Publication number
EP1518946A1
EP1518946A1 EP03021876A EP03021876A EP1518946A1 EP 1518946 A1 EP1518946 A1 EP 1518946A1 EP 03021876 A EP03021876 A EP 03021876A EP 03021876 A EP03021876 A EP 03021876A EP 1518946 A1 EP1518946 A1 EP 1518946A1
Authority
EP
European Patent Office
Prior art keywords
naf
electrolyte
electrolyte according
nah
aluminum
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.)
Withdrawn
Application number
EP03021876A
Other languages
German (de)
English (en)
Inventor
Jörg Dr. Heller
Richard Dr. Lisowsky
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.)
Aluminal Oberflachentechnik GmbH
Original Assignee
Aluminal Oberflachentechnik 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.)
Filing date
Publication date
Application filed by Aluminal Oberflachentechnik GmbH filed Critical Aluminal Oberflachentechnik GmbH
Priority to EP03021876A priority Critical patent/EP1518946A1/fr
Priority to PCT/EP2004/052112 priority patent/WO2005059207A1/fr
Priority to EP04820443A priority patent/EP1680533A1/fr
Publication of EP1518946A1 publication Critical patent/EP1518946A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/42—Electroplating: Baths therefor from solutions of light metals
    • C25D3/44—Aluminium
    • 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

Definitions

  • the invention relates to an electrolyte for electrodeposition of aluminum, a process for the preparation of the electrolyte and its Use.
  • electrolytes of the formula NaF ⁇ 2Al (C 2 H 5 ) 3 dissolved in an aromatic hydrocarbon, usually toluene were used.
  • electrolytes of the formula NaF ⁇ 2Al (C 2 H 5 ) 3 dissolved in an aromatic hydrocarbon, usually toluene were used.
  • the aluminum deposits with these systems were of good quality per se, the poor throwing power of the system, which is comparable to aqueous chromium electrolytes, was a major drawback to the industrial breakthrough of this process.
  • KF ⁇ 2Al (C 2 H 5 ) 3 and KF ⁇ 2Al (CH 3 ) 3 are approximately 127-129 ° C and 151-152 ° C, respectively.
  • KF ⁇ 2Al (C 2 H 5 ) 3 ⁇ 4 toluene crystallizes out at 60-65 ° C. This leads to major problems in technical equipment due to clogging and formation of residues in piping, filters and pumps.
  • electrolyte systems which contain several types of aluminum alkyl compounds. It can 2 or 3 different aluminum alkyl components used side by side become.
  • electrolyte systems are described for example in the EP 0 084 816 B2, EP 0 402 761 A1 and DE 1047450. In these systems In addition to aluminum triethyl and aluminum triisobutyl and / or Alumniumtrimethyl used.
  • the object of the invention is therefore to provide an electrolyte for galvanic To provide deposition of aluminum with its Components have good conductivity, high throwing power, high Strom confusebelastiana but also has a good solubility, commercial is easily accessible and can be produced inexpensively.
  • an electrolyte for the electrodeposition of aluminum which contains a mixture of at least two organoaluminium complexes of the formula NaF. 2Al (R 1 ) 3 (I) and NaH. 2AI (R 2 ) 3 (II) R 1 and R 2, independently of one another or different, are a C 1 -C 4 -alkyl group.
  • the electrolyte of the invention proves to be extremely advantageous because it meets all the requirements for an economical and widely applicable method for aluminum deposition.
  • the electrolyte has a high throwing power coupled with good conductivity, excellent solubility and good commercial accessibility.
  • R 1 and R 2 in the general formulas I and II are ethyl.
  • the electrolyte is a mixed complex at 20 ° C liquid, but will preferably used in the form of a solution in an organic solvent.
  • the solvents used at room temperature are liquid, aromatic hydrocarbons such as benzene, xylene and toluene, the ratio to the organoaluminum complexes of the formula I and II 1: 1 to 6: 1, preferably 2: 1 to 4: 1.
  • Another object of the invention is a process for the preparation of the electrolyte.
  • the preparation of the electrolyte can be carried out in a known manner, first by preparation of the corresponding organoaluminium complexes of the formula I and II and subsequent mixing of these complexes.
  • the use of sodium hydride is necessary for the preparation of the organoaluminum complex of formula II.
  • Sodium hydride is a very reactive substance that is self-igniting in moist air and reacts violently with moisture to form NaOH and H 2 . It has therefore proved particularly advantageous in the preparation of the electrolyte of the general formula II, the substance NaH not in pure form but as an industrially available formulation in paraffin oil or other non-reactive with NaH oil, especially white oil use.
  • An inventive method for producing the electrolyte takes place through the following steps:
  • the preparation of the organoaluminum complex II NaH ⁇ 2Al (R 2 ) 3 takes place in situ.
  • the procedure is as follows: first, the organoaluminum complex compound of the formula I NaF ⁇ 2Al (R 1 ) 3 is prepared by reacting NaF with Al (R 1 ) 3 . Thereafter, an addition of Al (R 2 ) 3 to the organoaluminum complex compound of the formula NaF ⁇ 2Al (R 1 ) 3 . This is followed by the addition of NaH, which is present as a commercial product in white oil to the solution of Al (R 2 ) 3 and NaF ⁇ 2Al (R 1 ) 3 This also gives the electrolyte according to the invention.
  • R 1 and R 2 may independently be the same or displace a C 1 -C 4 alkyl group.
  • the reactions are carried out in an organic solvent, more preferably in an aromatic solvent, and most preferably in toluene.
  • the ready-to-use electrolytic solution is prepared in situ by adding NaF and NaH, both in white oil, already in the desired ratio and adding them as a suspension, preferably in toluene. This is followed by the addition of the appropriate amounts of Al (R 2 ) 3 and Al (R 2 ) 3 . After mixing and optionally with the addition of heat, the electrolyte according to the invention is obtained.
  • the electrolyte according to the invention is used for the production of aluminum layers used on electrically conductive materials.
  • electrically conductive Materials within the meaning of the invention become electrically conductive materials as well as layers that are applied to materials and electrically are conductive. These electrically conductive layers can also with Help the electrolyte of the invention are provided with aluminum layers.
  • the materials mentioned can be metals but also conductive plastics be.
  • An electrolyte according to Example 3 was used for coating. Between two anodes of raffinal aluminum, a rotating 8.8 steel screw was electrolyzed as a cathode at 93 to 95 ° C. The cathode current density was successively 1.8, 2.0, 2.2 A / dm 2 in the three experiments. All steel screws could be adequately coated with aluminum. The measured thickness of the aluminum layer were at 1.8 A / dm 2 15 ⁇ / dm 2 at 2.0 A 20 ⁇ and 2.2A / dm 2 10 ⁇ .

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)
EP03021876A 2003-09-27 2003-09-27 Electrolyte pour la deposition galvanique d' aluminium Withdrawn EP1518946A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP03021876A EP1518946A1 (fr) 2003-09-27 2003-09-27 Electrolyte pour la deposition galvanique d' aluminium
PCT/EP2004/052112 WO2005059207A1 (fr) 2003-09-27 2004-09-09 Electrolyte pour le depot galvanique d'aluminium
EP04820443A EP1680533A1 (fr) 2003-09-27 2004-09-09 Electrolyte pour le depot galvanique d'aluminium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP03021876A EP1518946A1 (fr) 2003-09-27 2003-09-27 Electrolyte pour la deposition galvanique d' aluminium

Publications (1)

Publication Number Publication Date
EP1518946A1 true EP1518946A1 (fr) 2005-03-30

Family

ID=34178512

Family Applications (2)

Application Number Title Priority Date Filing Date
EP03021876A Withdrawn EP1518946A1 (fr) 2003-09-27 2003-09-27 Electrolyte pour la deposition galvanique d' aluminium
EP04820443A Withdrawn EP1680533A1 (fr) 2003-09-27 2004-09-09 Electrolyte pour le depot galvanique d'aluminium

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP04820443A Withdrawn EP1680533A1 (fr) 2003-09-27 2004-09-09 Electrolyte pour le depot galvanique d'aluminium

Country Status (2)

Country Link
EP (2) EP1518946A1 (fr)
WO (1) WO2005059207A1 (fr)

Citations (4)

* 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
US3234114A (en) * 1961-06-30 1966-02-08 Ziegler Karl Process for the recovery of purified sodium
EP0402761A1 (fr) * 1989-06-10 1990-12-19 Studiengesellschaft Kohle mbH Electrolytes organoaluminiques et procédés de dépôt électrolytique de l'aluminium
WO2002088434A1 (fr) * 2001-04-30 2002-11-07 Alumiplate Incorporated Formulations d'electrodeposition d'aluminium

Patent Citations (4)

* 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
US3234114A (en) * 1961-06-30 1966-02-08 Ziegler Karl Process for the recovery of purified sodium
EP0402761A1 (fr) * 1989-06-10 1990-12-19 Studiengesellschaft Kohle mbH Electrolytes organoaluminiques et procédés de dépôt électrolytique de l'aluminium
WO2002088434A1 (fr) * 2001-04-30 2002-11-07 Alumiplate Incorporated Formulations d'electrodeposition d'aluminium

Also Published As

Publication number Publication date
WO2005059207A1 (fr) 2005-06-30
EP1680533A1 (fr) 2006-07-19

Similar Documents

Publication Publication Date Title
DE3048083C2 (de) Verfahren zur chemischen Entfernung von Oxidschichten von Gegenständen aus Titan oder Titanlegierungen
DE1047450B (de) Elektrolyt zur elektrolytischen Abscheidung von Aluminium
EP1141447B1 (fr) Electrolyte organique d'aluminium et procede de revetement electrolytique avec de l'aluminium ou des alliages aluminium-magnesium
WO2009135505A1 (fr) Bains d'électrolyte au pd et au pd-ni
EP0084816A2 (fr) Electrolyte pour dépôt électrolytique de l'aluminium
DE3875227T2 (de) Verfahren zur herstellung eines bades fuer die elektroplattierung einer binaeren zinn-kobalt-, zinn-nickel- oder zinn-blei- legierung und damit hergestelltes elektroplattierungsbad.
DE69002406T2 (de) Organoaluminium-Elektrolyte und Verfahren zur elektrolytischen Absetzung von Aluminium.
DE3875943T2 (de) Verfahren zur elektroplattierung einer metallschicht mit aluminium.
EP2635724B1 (fr) Procédé de placage de chrome dur à partir d'un électrolyte sans cr(vi)
DE69007341T2 (de) Organoaluminium-Elektrolyte für die elektrolytische Absetzung von hochfeinem Aluminium.
DE3889667T2 (de) Elektroniederschlag von zinn-wismut-legierungen.
EP1664389A1 (fr) Electrolyte servant au depot galvanique d'alliages aluminium-magnesium
EP1518946A1 (fr) Electrolyte pour la deposition galvanique d' aluminium
DE641107C (de) Verfahren zum galvanischen Niederschlagen von Zinn
EP0975823B1 (fr) Electrolyte pour deposition electrolytique d'aluminium a vitesse elevee sur des produits continus
DE1771116B1 (de) Galvanisches Bad zur Abscheidung von Aluminium
DE2806957C2 (de) Bad zur galvanischen Abscheidung von duktilem Aluminium und Verfahren zur Herstellung des Bades
WO2020126817A1 (fr) Électrolyte et procédé pour la préparation de couches de chrome
DE19649000C1 (de) Elektrolyt zur galvanischen Abscheidung von Aluminium und dessen Verwendung
DE1200817B (de) Verfahren zur Darstellung von Oniumsalz-Komplexverbindungen
DE10226360A1 (de) Verfahren zur Herstellung von Alkalitetraalkylaluminaten und deren Verwendung
EP4656775A1 (fr) Revêtement de cr(iii) résistant à la corrosion
EP4656776A1 (fr) Revêtement de cr(iii) résistant à la corrosion
DE102007018489A1 (de) Aluminiumorganischer 4-Komponentenelektrolyt zur Abscheidung von Aluminium
WO2008064954A2 (fr) Électrolyte de dépôt par galvanisation d'aluminium à partir de solvants aprotiques dans un tambour de galvanisation

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

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

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

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 HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

18W Application withdrawn

Effective date: 20050311