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EP2419551A2 - Électrolyte et additifs tensio-actifs pour le dépôt galvanique de couches d'aluminium lisses et compactes à partir de liquides ioniques - Google Patents

Électrolyte et additifs tensio-actifs pour le dépôt galvanique de couches d'aluminium lisses et compactes à partir de liquides ioniques

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Publication number
EP2419551A2
EP2419551A2 EP10708571A EP10708571A EP2419551A2 EP 2419551 A2 EP2419551 A2 EP 2419551A2 EP 10708571 A EP10708571 A EP 10708571A EP 10708571 A EP10708571 A EP 10708571A EP 2419551 A2 EP2419551 A2 EP 2419551A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
cycloalkyl
aryl
aralkyl
alkoxyaryl
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Withdrawn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
EP10708571A
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German (de)
English (en)
Inventor
Aurelie Alemany
Itamar Michael Malkowsky
Roland Kalb
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP10708571A priority Critical patent/EP2419551A2/fr
Publication of EP2419551A2 publication Critical patent/EP2419551A2/fr
Withdrawn legal-status Critical Current

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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
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44—Aluminium

Definitions

  • the invention relates to a process for the electrochemical deposition of aluminum and to an electrolyte which can be used in this process.
  • Aluminum is an important material that is used predominantly in vehicle and aircraft construction as well as in mechanical engineering, construction and as packaging material. Both in the production of aluminum and in its purification, electrolysis plays an important role.
  • the conventional method for industrial aluminum production is based on the so-called Hall Heroult process, while aluminum oxide is dissolved in the form of bauxite and cathodically deposited by means of direct current from a melt at temperatures of about 1000 0 C.
  • a process for the electrochemical deposition of aluminum is the so-called SIGAL process, in which a highly reactive, pyrophoric organoaluminum compound is handled in a flammable basic electrolyte.
  • SIGAL process a highly reactive, pyrophoric organoaluminum compound is handled in a flammable basic electrolyte.
  • Such aluminum organyls decompose spontaneously in air by reaction with atmospheric oxygen and moisture, causing flame formation.
  • Such decomposition in the presence of easily combustible toluene or xylene electrolytes can lead to serious industrial accidents up to the destruction of the plant.
  • a disadvantage of the use of electrolytes based on ionic liquids is the poor surface finish which is currently achieved at technically relevant current densities of> 200 A / m 2 .
  • a poor surface finish is understood to mean a rough, dendritic surface which does not cover the electrode or the substrate on which it is deposited flat. For decorative and corrosion protection reasons, even deposition with a gloss or matt finish is desirable.
  • a dense layer is essential for proper corrosion protection.
  • EP 0 084 816 discloses organometallic electrolytes for the electrodeposition of aluminum, which should have a high throwing power coupled with good electrical conductivity.
  • a further object of the present invention is to provide a process for the electrochemical deposition of aluminum from ionic liquids, with the aid of which matt or glossy dense aluminum layers can be obtained.
  • the object is achieved by a method for the electrochemical deposition of aluminum comprising the steps:
  • X 1 and X 2 are independently of one another N or CH, X 3 is NR 1 , O or S, m is an integer from 0 to 4,
  • X 1 , X 2 and X 3 are heteroatoms selected from N, O and S, and
  • R 1 is selected from the group H, alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl and heterocyclyl wherein the groups alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl and heterocyclyl optionally substituted by one or more substituents, and the groups alkyl and cycloalkyl optionally interrupted by 1 to 3 heteroatoms or functional groups, and
  • R 2 independently represents H, alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl and heterocyclyl, wherein the groups alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl and heterocyclyl optionally substituted by one or more substituents, and the groups alkyl and cycloalkyl optionally substituted by 1 to 3 heteroatoms or functional groups are interrupted.
  • the additive according to the general formula (II) is a compound of the general formula (II)
  • R 3 is H, alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl and heterocyclyl, wherein the groups alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl and heterocyclyl optionally substituted with one or more substituents, and the groups alkyl and cycloalkyl optionally substituted by 1 to 3 heteroatoms or functional groups are interrupted, and,
  • B08 / 0552PC R 4 independently of one another are H, alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl and heterocyclyl, where the groups alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl and heterocyclyl optionally substituted by one or more substituents, and the groups alkyl and cycloalkyl optionally are interrupted by 1 to 3 heteroatoms or functional groups, and Hal is selected from the group fluorine, chlorine, bromine and iodine.
  • the additive according to the general formula (III) is a compound of the general formula (III)
  • R 5 is alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl and heterocyclyl, wherein the groups alkyl, cycloalkyl, aralkyl, aryl, alkoxyaryl and heterocyclyl optionally substituted with one or more substituents and the groups alkyl and cycloalkyl optionally substituted by 1 to 3 heteroatoms or are interrupted by functional groups, and M + is Na + or K + .
  • the substituents are independently selected from the group fluorine, chlorine, bromine, iodine, optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocyclyl, optionally substituted aralkyl, alkoxy, nitro, carboalkoxy, cyano, alkylmercaptyl, trihaloalkyl, carboxyalkyl, - ( dC 7 ) alkyl, -O- (dC 7 ) -alkyl, -N ((dC 4 ) -alkyl) 2 , -CO-N ((dC 4 ) alkyl) 2 .
  • Alkyl means a saturated aliphatic hydrocarbon group which may be straight chain or branched and may have from 1 to 20 carbon atoms in the chain Preferred alkyl groups may be straight chain or branched and have from 1 to 10 carbon atoms in the chain a lower alkyl group, such as methyl, ethyl or propyl, is attached to a linear alkyl chain, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl 1 -propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2 Methyl 2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl
  • Substituted alkyl means that the alkyl group is substituted with one or more substituents selected from alkyl, optionally substituted aryl, optionally substituted aralkyl, alkoxy, nitro, carboalkoxy, cyano, halo, alkylmercaptyl, trihaloalkyl or carboxyalkyl.
  • Cycloalkyl means an aliphatic ring having from 3 to about 10 carbon atoms in the ring Preferred cycloalkyl groups have from 4 to about 7 carbon atoms in the ring.
  • Aryl means phenyl or naphthyl.
  • Aralkyl means an alkyl group substituted with an aryl group.
  • Substituted aralkyl and “substituted aryl” mean that the aryl group or aryl group of the aralkyl group is substituted with one or more substituents selected from alkyl, alkoxy, nitro, carboalkoxy, cyano, halo, alkylmercaptyl, trihaloalkyl or carboxyalkyl.
  • Alkoxy means an alkyl-O-group in which "alkyl” has the meaning described above. Lower alkoxy groups are preferred. Exemplary groups include methoxy, ethoxy, n-propoxy, i -propoxy and n-butoxy.
  • “Lower alkyl” means an alkyl group having from 1 to about 7 carbon atoms.
  • Alkoxyalkyl means an alkyl group as described above substituted with an alkoxy group as described above.
  • Halogen means chloro, fluoro, bromo or iodo.
  • Heterocyclyl means an approximately 4 to about 10 membered ring structure in which one or more of the ring atoms is other than carbon, for example N, O or S. Heterocyclyl may be aromatic or non-aromatic, ie it may be saturated, partially or completely unsaturated.
  • Substituted heterocyclyl means that the heterocyclyl group is substituted with one or more substituents, which include as substituents: alkoxy, aryl, carbalkoxy, cyano, halo, heterocyclyl, trihalomethyl, alkylmercaptyl or nitro.
  • Carbalkoxy means a carboxyl substituent esterified with an alcohol of the formula C n H 2n + I OH, where n is from 1 to about 6.
  • Alkoxyalkyl means an alkyl group as described above substituted with an alkoxy group as described above.
  • R 1 is selected from methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl and 1-hexyl. According to a particularly preferred embodiment of the invention, the radical R 1 is methyl.
  • R 2 is H and m is 4.
  • the compound according to the general formula (I) is N-methylbenzotriazole.
  • the compound according to the general formula (I) is one or more compounds selected from N-methylbenzodiazole, N-ethylbenzodiazole, benzoxazole, benzisooxazole, benzisothiazole and benzothiazole
  • R 3 is a straight chain, saturated aliphatic hydrocarbon group having from 5 to 20 carbon atoms in the chain, more preferably from 10 to 18 carbon atoms in the chain.
  • R 4 is the same or different and selected from H, methyl, ethyl, 1-propyl and 2-propyl.
  • the compound according to the general formula (II) is one or more compounds selected from hexydecyltrimethylammonium bromide and hexadecyltrimethylammonium chloride.
  • R 5 is a straight-chain, saturated aliphatic hydrocarbon group having 5 to 20 carbon atoms in the chain, more preferably having 10 to 15 carbon atoms in the chain.
  • the compound according to the general formula (III) is sodium lauryl sulfate.
  • the current density at which the method according to the invention is carried out is at least 50 A / m 2 and can vary over wide ranges.
  • the electrical current density is defined as the quotient of current intensity and effective electrode area during electrolysis.
  • the electrical current density is preferably at least 100 A / m 2 , more preferably at least 200 A / m 2 and in particular at least 400 A / m 2
  • Ionic liquids are a suitable electrolyte for the deposition of aluminum.
  • the electrolyte is typically a molten salt with a water content of less than 0.1% by weight, based on the total amount of the electrolyte.
  • the anion of the ionic liquid is tetrachloroaluminate.
  • the cations used are preferably dialkylimidazolium cations in which the two alkyl groups, identical or different, branched or unbranched, may be substituted or unsubstituted by one or more phenyl groups and have from 1 to 6 carbon atoms.
  • the ionic liquid has a formula KaCl xn AICI3, where Ka is one of the abovementioned imidazolium cations and n is a value of 1.4 to 2.0, more preferably 1.4 to 1.7, in particular 1.5 having.
  • ionic liquids can also be used.
  • Such ionic liquids are described, for example, in DE-A 10 2005 017 733.
  • ionic liquids which have cations which are selected from the compounds of the formulas (IVa) to (IVw):
  • radical R is hydrogen, a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or
  • radicals R 1 to R 9 are independently hydrogen, a sulfo group or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic, unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups or substituted radical having 1 to 20 carbon atoms, wherein the radicals R 1 to R 9 , which in the abovementioned formulas (IV) are bonded to a carbon atom (and not to a heteroatom), may additionally also stand for halogen or a functional group ; or
  • the radicals R 1 to R 9 are, in the cases in which those in the above formulas (IV) to a carbon atom (and not to a heteroatom) bound also be bound directly via the heteroatom.
  • B08 / 0552PC also functional groups and heteroatoms may be directly adjacent, so that combinations of several adjacent atoms, such as -O- (ether), -S- (thioether), -COO- (ester) or -CONR'- (tertiary Amide), are included, for example, di- (Ci-C 4 alkyl) amino, Ci-C 4 alkyloxycarbonyl or Ci-C 4 alkyloxy.
  • Halogens are fluorine, chlorine, bromine and iodine.
  • the radical R preferably stands for
  • Glycols, butylene glycols and their oligomers having from 1 to 100 units and a hydrogen or a C 1 to C 8 alkyl as end group, such as, for example, R A O- (CHR B -CH 2 -O) n -CHR B -CH 2 - or R 1 - (CH 2 CH 2 CH 2 CH 2 O) n - CH 2 CH 2 CH 2 CH 2 O- where R A and R B are preferably hydrogen, methyl or ethyl and n is preferably 0 to 3, in particular 3-oxabutyl , 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatri- decyl and 3,6,9 , 12-tetraoxatetradecyl;
  • N, N-di-C 1 to C 6 -alkyl-amino such as N, N-dimethylamino and N, N-
  • radical R is unbranched and unsubstituted d-bis
  • Ci ⁇ -alkyl such as, for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, in particular
  • B08 / 0552PC especially for methyl, ethyl, 1-butyl and 1-octyl and for CH 3 O- (CH 2 CH 2 O) n -CH 2 CH 2 - and CH 3 CH 2 O- (CH 2 CH 2 O) n -CH 2 CH 2 - with n equal to 0 to 3.
  • radicals R 1 to R 9 are preferably each independently
  • aryl, alkyl, aryloxy, alkyloxy, halo, heteroatoms and / or heterocycles substituted and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups alkyl;
  • C 2 interrupted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halo, heteroatoms and / or heterocycles and / or interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups cis alkenyl;
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles d- to Ci 8 alkyl is preferably methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl , 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl 1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-
  • B08 / 0552PC substituted imino interrupted C 2 - to C-is alkenyl is preferably vinyl, 2-propenyl, 3-butenyl, cis-2-butenyl, trans-2-butenyl or
  • C 1 -C 12 -alkyl which is optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles, it is preferably phenyl, toIyI, xylene, ⁇ -naphthyl, ⁇ -naphthyl, Diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, / so-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl,
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles is preferably cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl , Diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl, C n F 2 (n- 3 ) - (ib) H 2 3 -b with n ⁇ 30, 0 ⁇ a ⁇
  • An optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted five- to six-membered, oxygen, nitrogen and / or sulfur atoms containing heterocycle is preferably furyl, thiophenyl, pyrryl, Pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxo, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl or difluoropyridyl.
  • B08 / 0552PC Two adjacent radicals together form an unsaturated, saturated or aromatic, optionally substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles and optionally substituted by one or more oxygen and / or sulfur atoms and / or one or more several substituted or unsubstituted imino groups interrupted ring, it is preferably 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propylene, 2-oxa-1, 3-propylene, 1-oxa-1, 3-propenylene, 3-oxa-1, 5-pentylene, 1-aza-1, 3-propenylene, 1-Ci-C 4 -Alkyl-1-aza-1,3-propenylene, 1,4-buta-1,3-dienylene, 1-aza-1, 4-buta-1,3-dienylene or 2-aza-1,
  • radicals contain oxygen and / or sulfur atoms and / or substituted or unsubstituted imino groups
  • the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 in the radical, preferably not more than 4, and very particularly preferably not more than 3.
  • radicals contain heteroatoms, then between two heteroatoms there are generally at least one carbon atom, preferably at least two carbon atoms.
  • radicals R 1 to R 9 are each independently
  • N 1 N-di-Cr to C ⁇ -alkyl-amino such as N, N-dimethylamino and N, N-
  • the radicals R 1 to R 9 independently of one another are hydrogen or C 1 - to C 1 -alkyl, such as, for example, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl , for phenyl, for 2-cyanoethyl, for 2- (methoxycarbonyl) ethyl, for 2- (ethoxycarbonyl) ethyl, for 2- (n-butoxycarbonyl) ethyl, for N, N-dimethylamino, for N, N -diethylamino, for Chlorine and for CH 3 O- (CH 2 CH 2 O) n -CH 2 CH 2 - and CH 3 CH 2 O- (CH 2 CH 2 O) n -CH 2 CH 2 - with n is 0 to 3.
  • radicals R 1 to R 5 are methyl, ethyl or chlorine and the remaining radicals R 1 to R 5 are hydrogen;
  • R 3 is dimethylamino and the remaining radicals R 1 , R 2 , R 4 and R 5 are hydrogen;
  • R 2 is carboxy or carboxamide and the remaining radicals R 1 , R 2 , R 4 and R 5 are hydrogen; or
  • R 1 and R 2 or R 2 and R 3 is 1, 4-buta-1, 3-dienylene and the remaining radicals
  • R 1 , R 2 , R 4 and R 5 are hydrogen
  • R 1 to R 5 are hydrogen
  • radicals R 1 to R 5 are methyl or ethyl and the remaining radicals R 1 to R 5 are hydrogen.
  • pyridinium ions (IVa) there may be mentioned 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1 - (1-Hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-dodecyl) pyridinium, 1- (1-tetradecyl) pyridinium, 1- (1-hexadecyl) pyridinium, 1 , 2-Dimethylpyridinium, 1-ethyl-2-methylpyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1 - (1-dodecyl)
  • R 1 to R 4 are hydrogen
  • radicals R 1 to R 4 are methyl or ethyl and the remaining radicals R 1 to R 4 are hydrogen.
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl; or
  • R 1 is hydrogen, methyl or ethyl
  • R 2 and R 4 are methyl and R 3 is hydrogen.
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl;
  • R 1 is hydrogen, methyl or ethyl, R 2 and R 4 are methyl and R 3 is hydrogen;
  • R 1 to R 4 are methyl; or • R 1 to R 4 are methyl.
  • R 1 is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl and R 2 to R 4 are independently
  • imidazolium ions may be mentioned 1, 3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium, 1 (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 1- (1-octyl) -3- methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-dodecyl) -3-ethylimidazolium, 1- (1-dodecyl) -3-butylimi
  • R 1 is hydrogen, methyl or ethyl and R 2 to R 4 are independently hydrogen or methyl.
  • R 1 to R 4 are independently hydrogen or methyl.
  • R 1 to R 6 are hydrogen or methyl.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 6 are independently of one another hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 to R 6 are independently hydrogen or methyl.
  • Imidazoliniumionen are those in which
  • R 1 and R 2 are independently hydrogen, methyl, ethyl, 1-butyl or phenyl, R 3 and R 4 are independently hydrogen, methyl or ethyl, and R 5 and R 6 are independently hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl or ethyl and R 3 to R:> 6 are independently hydrogen or methyl.
  • R 1 to R 3 are independently hydrogen, methyl or ethyl and R 4 to R 6 are independently hydrogen or methyl.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 and R 3 are independently hydrogen or methyl.
  • R 1 and R 2 are independently hydrogen, methyl, ethyl or phenyl and R 3 is hydrogen, methyl or phenyl.
  • R 1 is hydrogen, methyl or ethyl and R 2 and R 3 are independently hydrogen or methyl, or R 2 and R 3 together are 1, 4-buta-1, 3-dienylene.
  • R 1 is hydrogen, methyl, ethyl or phenyl and R 2 to R 9 are independently of one another hydrogen or methyl.
  • R 1 and R 4 are independently hydrogen, methyl, ethyl or phenyl and R 2 and R 3 and R 5 to R 8 are independently hydrogen or methyl.
  • R 1 to R 3 are independently C 1 to C 8 alkyl
  • R 1 and R 2 together are 1, 5-pentylene or 3-oxa-1, 5-pentylene and R 3 is C r Cr alkyl or 2-cyanoethyl.
  • ammonium ions may be mentioned methyl tri (1-butyl) -ammonium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium.
  • Examples of the tertiary amines from which the quaternary ammonium ions of the general formula (IVu) are derived by quaternization with the abovementioned radicals R are diethyl-n-butylamine, diethyl-tert-butylamine, diethyl-n-pentylamine, diethylhexylamine, Diethyloctylamine, diethyl (2-ethylhexyl) amine, di-n-propylbutylamine, di-n-propyl-n-pentylamine, di-n-propylhexylamine, di-n-propyloctylamine, di-n-propyl (2-ethyl - hexyl) -amine, di-isopropylethylamine, di-iso-propyl-n-propylamine, di-isopropyl-butylamine, di-isopropylpenty
  • B08 / 0552PC Di-n-butylhexylamine, di-n-butyloctylamine, di-n-butyl (2-ethylhexyl) amine, Nn-butylpyrrolidine, N-sec-butylpyrrodidine, N-tert-butylpyrrolidine, Nn-pentylpyrrolidine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-di-n-butylcyclohexylamine, N-n-propylpiperidine, N-isopropylpiperidine, Nn-butylpiperidine, N-sec-butylpiperidine, N-tert-butylpiperidine, Nn-pentylpiperidine, Nn-butylmorpholine, N-sec-butylmorpholine, N-tert-butylmorpholine, Nn-penty
  • Preferred tertiary amines (IVu) are di-iso-propylethylamine, diethyl-tert-butylamine, diisopropyl-propylamine, di-n-butyl-n-pentylamine, N, N-di-n-butylcyclohexylamine and tertiary amines of pentyl isomers.
  • tertiary amines are di-n-butyl-n-pentylamine and tertiary amines of pentyl isomers.
  • Another preferred tertiary amine having three identical residues is triallylamine.
  • R 1 to R 5 are methyl.
  • guanidinium ion may be mentioned N, N, N ', N', N ", N" - hexamethylguanidinium.
  • R 1 and R 2 are independently methyl, ethyl, 1-butyl or 1-octyl and R 3 is hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 ;
  • R 1 is methyl, ethyl, 1-butyl or 1-octyl
  • R 2 is a -CH 2 -CH 2 -OR 4 group and R 3 and R 4 are independently hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 ; or
  • R 1 is a -CH 2 -CH 2 -OR 4 group
  • R 2 is a -CH 2 -CH 2 -OR 5 group
  • R 3 to R 5 are independently hydrogen, methyl, ethyl, acetyl, -SO 2 OH or -PO (OH) 2 are.
  • Particularly preferred cholinium ions are those in which R 3 is selected from hydrogen, methyl, ethyl, acetyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3,6-dioxo-octyl, 1 1-methoxy 3,6,9-trioxa undecyl, 7-methoxy-4-oxa-heptyl, 11-methoxy-4,8-dioxa undecyl, 15-methoxy-4,8,12-trioxa-pentadecyl, 9-methoxy 5-oxa-nonyl, 14-methoxy-5,10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3,6-dioxa-octyl, 11-ethoxy-3,6,9 trioxa undecyl, 7-ethoxy-4-o
  • IIIx Very particularly preferred phosphonium ions (IVx) are those in which
  • R 1 to R 3 are, independently of one another, C 1 -C 8 -alkyl, in particular butyl, isobutyl, 1-hexyl or 1-octyl.
  • the pyridinium ions, pyrazolinium, pyrazolium ions and imidazolinium and imidazolium ions are preferable. Furthermore, ammonium ions are preferred.
  • B08 / 0552PC Trimethylimidazolium, 1, 4-dimethyl-3-ethylimidazolium, 3-butylimidazolium, 1, 4-dimethyl-3-octylimidazolium, 1, 4,5-trimethylimidazolium, 1, 3,4,5-tetramethylimidazolium, 1, 4, 5-trimethyl-3-ethylimidazolium, 1, 4,5-trimethyl-3-butylimidazolium, butylmethylpyrolidinium and 1, 4,5-trimethyl-3-octylimidazolium.
  • the metal cations [M 1 ] + , [M 2 ] + , [M 3 ] + , [M 4 ] 2+ and [M 5 J 3+ mentioned in formulas (IIIa) to (NIj) are generally to metal cations of the 1st, 2nd, 6th, 7th, 8th, 9th, 10th, 11th, 12th and 13th group of the periodic table.
  • Suitable metal cations are, for example, Li + , Na + , K + , Cs + , Mg 2+ , Ca 2+ , Ba 2+ , Cr 3+ , Fe 2+ , Fe 3+ , Co 2+ , Ni 2+ , Cu 2 + , Ag + , Zn 2+ and Al 3+ .
  • anions in principle, all anions can be used, provided that AICI 4 " and / or Al 2 Cl 7 " are predominantly present.
  • the anion [Y] " 'of the ionic liquid is for example selected from
  • R b is -O 2 S ' SO 2 -R C
  • v is a whole positive number from 2 to 10; advantageously S 2 " , [S v ] 2" ,
  • B08 / 0552PC • the group of complex metal ions such as Fe (CN) 6 3 “ , Fe (CN) 6 4" , MnO 4 “ , Fe (CO) 4 “ .
  • R a , R b , R c and R d are each independently hydrogen, C 1 -C 6 -alkyl, optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups 2 -C 8 alkyl, C 6 -C 4 aryl, C 5 -C 2 cycloalkyl or a five- to six-membered, oxygen-, nitrogen- and / or sulfur-comprising heterocycle, where two of them together form an unsaturated, saturated or aromatic, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more unsubstituted or substituted imino groups ring, said radicals each additionally by functional groups, aryl, alkyl, aryloxy, alkoxy, halogen, hetero - Atoms and / or heterocycles may be substituted.
  • aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and / or heterocycles substituted CrCis-alkyl, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, Hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3- Tetramethylbutyl, benzyl, 1-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butyl),
  • optionally interrupted by one or more non-adjacent oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino interrupted C 2 -C 8 alkyl for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6- dioxaoctyl, 1 1-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 1-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy 5-oxa-
  • B08 / 0552PC nonyl 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxo-octyl, 1-methoxy-3,6,9-trioxa-undecyl, 7-methoxy-4 -oxaheptyl, 1-methoxy-4,8-dioxa- undecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy-5,10-oxatetradecyl, 5-ethoxy 3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 1-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4-oxaheptyl, 1-ethoxy-4,8-dioxaundecyl
  • radicals can be taken together, for example, as fused building block 1, 3-propylene, 1,4-butylene, 2-oxa-1,3-propylene, 1-oxa-1,3-propylene, 2-oxa 1, 3-propenylene, 1-aza-1, 3-propenylene, 1-dC 4 -alkyl-1-aza-1, 3-propenylene, 1, 4-buta-1, 3-dienylene, 1-aza 1, 4-buta-1, 3-dienylene or 2-aza-1,4-buta-1,3-dienylene.
  • the number of non-adjacent oxygen and / or sulfur atoms and / or imino groups is basically not limited, or is automatically limited by the size of the remainder or the ring building block. As a rule, it is not more than 5 in the respective radical, preferably not more than 4 or very particularly preferably not more than 3. Furthermore, at least one, preferably at least two, carbon atoms (e) are generally present between two heteroatoms.
  • Substituted and unsubstituted imino groups may be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
  • C 6 -C 4 -aryl substituted by functional groups are, for example, phenyl, ToIyI, XyIyI, ⁇ -naphthyl, ⁇ -naphthyl, 4-diphenylyl, chlorophenyl, Dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chloronap
  • B08 / 0552PC May optionally be substituted by functional groups, aryl, alkyl, aryloxy, halogen, Heteroato- me and / or heterocyclic C 5 -C 2 -cycloalkyl are for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, Butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl.
  • a five- to six-membered, oxygen, nitrogen and / or sulfur-containing heterocycle is, for example, furyl, thiophenyl, pyryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyryl , Methoxifuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • Preferred anions are selected from the group of halides and halogen-containing compounds, the group of carboxylic acids, the group of sulfates, sulfites and sulfonates and the group of phosphates.
  • Preferred anions are chloride, bromide, iodide, SCN “ , OCN “ , CN “ , acetate, C r C 4 alkyl sulfates, R a -COO " , R 3 SO 3 " , R a R b PO 4 " , methanesulfonates, Tosylate, C r C 4 Dialkylphospha- te, hydrogen sulfate or tetrachloroaluminate.
  • dialkylimidazolium cations in which the two alkyl groups, identical or different, branched or unbranched, may be substituted by one or more phenyl groups or may be unsubstituted and have from 1 to 6 carbon atoms.
  • benzylmethylimidazolium hexylmethylimidazolium, butylmethylimidazolium, ethylmethylimidazolium.
  • Particularly preferred anions are tetrachloroaluminate and / or heptachlorodi-aluminate and / or F " and / or Cl " and / or Br " and / or BF 4 " and / or PF 6 " and / or CF 3 SO 3 " and / or (CF 3 SO 3 ) 2 N " and / or SO 4 2" and / or SO 3 2 " and / or PO 4 3"
  • an electrolysis device which has at least one anode and at least one cathode in an electrolysis space.
  • the at least one anode and the at least one cathode are connected by the electrolyte, which is an ionic liquid, electrolytically conductive.
  • B08 / 0552PC It can be used an anode, it can also be used several anodes. These may have the same composition or have different compositions. The same applies to the cathode (s).
  • the anode acts as a so-called sacrificial anode containing primary aluminum.
  • the at least one anode contains aluminum in a proportion by weight of at least 95 wt .-%, preferably 99 wt .-%, more preferably at least 99.5 wt .-% based on the total weight of the at least one anode.
  • composition of the cathode can be selected in a known manner.
  • the at least one cathode arranged in the electrolysis device can be selected from different conductive materials.
  • the at least one cathode comprises one or more materials selected from metals, alloys, graphite, electrically conductive plastics or polymers and steels.
  • the material of the cathode is selected from metals, alloys and steels, in particular selected from steel, Ni, Cu, Zn and Al alloys.
  • a three-dimensional cathode is used.
  • suitable cathode materials are stainless steel, nickel-base alloys, graphite, copper, and particularly preferably aluminum.
  • the electrolyte is moved on the cathode surface, for example by means of stirring, pumping over or moving the entire device.
  • the cathode is a workpiece, such as a body part, on which aluminum is deposited.
  • the inventive method at a temperature in the range of 20 to 200 0 C, preferably at a temperature in the range of 20 to 120 0 C, particularly preferably at a temperature in the range of 60 to 90 0 C, in particular preferably carried out at a temperature of about 90 ° C.
  • the aluminum is generally supplied to the process according to the invention in the form of a metal salt selected from the group AICI 3 , AIBr 3 , AII 3 and AIF 3 .
  • AICI is 3
  • the invention further relates to the use of additives according to the general formulas (I), (II) and (III) in a process for the electrochemical deposition of aluminum.
  • the invention relates to an electrolyte for the electrochemical deposition of aluminum from an ionic liquid containing an ionic liquid containing anions and cations, and one or more metal salts, one or more additives according to the general formulas (I), (II) and ( III), and optionally one or more solvents.
  • the electrolyte according to the invention in combination with one or more additives according to the general formulas (I), (II) and (III) proves to be extremely progressive from a galvanotechnical point of view, i. It fulfills the requirements placed on electrolytes for a technically widely applicable and economical aluminum deposition process to a far greater extent than was previously possible.
  • a further advantage of the electrolyte according to the invention is that, when used in the electrochemical deposition of aluminum, it leads to an eve-like deposition with gloss or matte finish of aluminum on the cathode.
  • the composition of the electrolyte according to the invention may generally vary over wide ranges, so the electrolyte according to the invention contains 0.1 to 10 wt .-% additive and 99.9 to 90 wt .-% of the ionic liquid, and 0 to 50 wt .-%, preferably 10 to 30 wt .-% of one or more organic solvent (s).
  • the organic solvent is generally selected from the group of aromatics and heteroaromatics. According to a preferred embodiment of the invention, the solvent is selected from toluene, chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 3-dichlorobenzene, trichlorobenzene and xylene.
  • the terminal voltage drops from 991 to 801 mV.
  • the electrodes are removed from the electrolyte and washed off successively with 40 ml of acetonitrile, stirred in 100 ml of water for 15 minutes and washed off with isopropanol. Finally, it is dried at 105 ° C. for one hour. Based on the cathodic mass difference, the current efficiency is determined to be 97.3%. The appearance of the cathode coating is dull and dense.
  • Example 2 Aluminum deposition of EMIMCI * 1.5 AICI 3 in the presence of 1% by weight of benzothiazole
  • the clamping voltage drops from 974 to 850 mV.
  • the electrodes are removed from the electrolyte and washed off successively with 40 ml of acetonitrile, stirred in 100 ml of water for 15 minutes and washed off with isopropanol. Finally, it is dried at 105 ° C. for one hour. Based on the cathodic mass difference, the current efficiency is determined to be 95.8%. The appearance of the gray cathode coating is dull and dense.
  • the terminal voltage drops from 1812 mV to 1626 mV.
  • the electrodes are removed from the electrolyte and washed off successively with 40 ml of acetonitrile, stirred in 100 ml of water for 15 minutes and washed off with isopropanol. Finally, it is dried at 105 ° C. for one hour. Based on the cathodic mass difference, the current efficiency is determined to be 91.3%. The appearance of the cathode coating is silvery shiny.
  • Example 4 Aluminum deposition of EMIMCI x 1.5 AICI 3 in the presence of 9% by weight of hexadecyltrimethylammonium chloride
  • EMIMCI x 1.5 AICI 3 are introduced and slowly mixed with 9 g of hexadecyltrimethylammonium chloride. Under an Ar inert gas atmosphere, the reaction mixture is heated to 95 ° C, resulting in a homogeneous solution from the initial suspension.
  • An Al anode and an Al cathode (both degreased) with an electrode distance of 2 cm and an active surface of 5 cm 2 (1 ⁇ 5 cm) are introduced into the electrolysis cell. Over a period of 10 seconds, an anodic pulse with a potential of 1 V is applied to the cathode.
  • the terminal voltage drops from 1296 mV to 805 mV.
  • the electrodes are removed from the electrolyte and washed off successively with 40 ml of acetonitrile, stirred in 100 ml of water for 15 minutes and washed off with isopropanol. Finally, it is dried at 105 ° C. for one hour. Based on the cathodic mass difference, the current efficiency is determined to be 100%. The appearance of the gray cathode coating is dull and dense.
  • Example 6 Aluminum Deposition from 80.9% by Weight of EMIMCI x 1.5 AICI 3 + 9.1% by Weight of Hexadecyltrimethylammonium Chloride + 10% by Weight of Toluene
  • EMIMCI x 1.5 AICI 3 are introduced and added slowly at 8O 0 C with 6.7 g of hexadecyltrimethylammonium chloride and 7.4 g of toluene. Under an Ar inert gas atmosphere, the reaction mixture is heated to 90 0 C, wherein a homogeneous solution is formed.
  • an Al anode and a Cu cathode with an electrode distance of 1 cm and an active surface of 10 cm 2 (2 x 5 cm) are introduced.
  • the Cu cathode was previously degreased for 10 minutes in an ultrasonic bath in 5% strength by weight Mucasolates at 6O 0 C, rinsed with acetone, pickled for 5 seconds in concentrated nitric acid and rinsed again with acetone.
  • Mucasolates at 6O 0 C
  • aluminum is deposited on the cathode for more than 1 h, whereby the anode consumes simultaneously in the sense of a sacrificial anode.
  • the clamping voltage drops from 3.0 to 2.0 V.
  • the electrodes are removed from the electrolyte and washed with 50 ml of acetone. The appearance of the cathode coating is shiny and dense.
  • Example 7 Aluminum deposition from 89.1% by weight of EMIMCI ⁇ 1.5 AICI 3 + 0.9% by weight of SDS (sodium lauryl sulfate) + 10% by weight of toluene
  • the Cu cathode was previously degreased for 10 minutes in an ultrasonic bath in 5% Mucasolates at 60 0 C, rinsed with acetone, pickled for 5 seconds in concentrated nitric acid and rinsed again with acetone.
  • a current density of 40 mA / cm 2 is deposited over 1 h of aluminum on the cathode with the anode consumed simultaneously in the sense of a sacrificial anode.
  • the clamping voltage drops from 2.2 to 1.3 V.
  • the electrodes are removed from the electrolyte and washed with 50 ml of acetone. The appearance of the cathode coating is dull and dense.
  • Example 8 Aluminum Deposition from 69.3% by Weight of EMIMCI x 1.5 AICI 3 + 0.7% by Weight of SDS (Sodium Lauryl Sulfate) + 30% by Weight of Toluene
  • EMIMCI x 1.5 AICI 3 are introduced and slowly mixed at 80 0 C with 0.57 g of sodium lauryl sulfate and 24.46 g of toluene. Under an Ar inert gas atmosphere, the reaction mixture is heated to 90 ° C, forming a homogeneous solution.
  • an Al anode and a Cu cathode with an electrode distance of 1 cm and an active surface of 10 cm 2 (2 x 5 cm) are introduced.
  • the Cu cathode was degreased before 10 minutes in an ultrasonic bath in 5% Mucasolates at 60 ° C, rinsed with acetone, pickled for 5 seconds in concentrated nitric acid and rinsed again with acetone.
  • 5% Mucasolates at 60 ° C, rinsed with acetone, pickled for 5 seconds in concentrated nitric acid and rinsed again with acetone.
  • aluminum is deposited on the cathode for more than 1 h, whereby the anode consumes simultaneously in the sense of a sacrificial anode.
  • the clamping voltage drops from 1.5 to 1.0 V.
  • the electrodes are removed from the electrolyte and washed with 50 ml of acetone. The appearance of the cathode coating is dull and dense.
  • Example 9 Aluminum Deposition from 69.3% by Weight of EMIMCI x 1.5 AICI 3 + 0.7% by Weight of SDS (Sodium Lauryl Sulfate) + 30% by Weight of Chlorobenzene
  • Example 10 Aluminum Deposition from 69.3% by Weight of EMIMCI x 1.5 AICI 3 + 0.7% by Weight of SDS (Sodium Lauryl Sulfate) + 30% by Weight of Chlorobenzene
  • Example 11 Aluminum Deposition from 69.3% by Weight of EMIMCI x 1.5 AICI 3 + 0.7% by Weight of SDS (Sodium Lauryl Sulfate) + 30% by Weight of Chlorobenzene
  • the standard steel cathode was firstly degreased by means of the Metex Cleaner System from MacDermid, rinsed with water, pickled for 10 seconds with concentrated hydrochloric acid and rinsed with acetone. At 90 ° C. and a current density of 40 mA / cm 2 , aluminum is deposited on the cathode for more than 15 minutes, whereby the anode is simulated.

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Abstract

L'invention concerne un procédé de dépôt électrochimique d'aluminium, permettant d'obtenir des couches d'aluminium compactes mates ou brillantes. Le procédé comprend les étapes suivantes: (a) fourniture d'un dispositif électrolytique comportant au moins une anode et au moins une cathode dans une chambre électrolytique, (b) dépôt électrochimique de l'aluminium sur la ou les cathodes de ce dispositif à partir d'un liquide ionique contenant des anions et des cations, ainsi que d'un ou plusieurs sels métalliques, et d'un ou plusieurs additifs; une densité de courant d'au moins 50 A/m2 est appliquée à la cathode ou aux cathodes.
EP10708571A 2009-03-18 2010-03-16 Électrolyte et additifs tensio-actifs pour le dépôt galvanique de couches d'aluminium lisses et compactes à partir de liquides ioniques Withdrawn EP2419551A2 (fr)

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