US3418216A - Organometallic electrolyte for galvanic deposition of zinc, aluminum, gallium and indium - Google Patents

Organometallic electrolyte for galvanic deposition of zinc, aluminum, gallium and indium Download PDF

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Publication number
US3418216A
US3418216A US515804A US51580465A US3418216A US 3418216 A US3418216 A US 3418216A US 515804 A US515804 A US 515804A US 51580465 A US51580465 A US 51580465A US 3418216 A US3418216 A US 3418216A
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aluminum
electrolyte
complex
zinc
indium
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US515804A
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Dotzer Richard
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Siemens AG
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Siemens AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • 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
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • 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
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50

Definitions

  • Organometallic electrolytes for galvanic deposition of aluminum are already known. These are complex compounds of aluminum alkyls and alkali halogenides as well as homogeneous liquid phase aluminum alkyls and their complex combinations with quaternary ammonia compounds.
  • the invention concerns an organometallic electrolyte for galvanic depositing of one of the elements zinc, aluminum, gallium or indium, consisting of a complex compound between a metal compound of the formula MeX R and a quaternary onium salt of the formula [R R R R Y]X whereby:
  • Me is an atom of zinc, aluminum, gallium or indium
  • R is an alkyl radical with C to C Y is a nitrogen, phosphorus, arsenic or tellurium atom,
  • R R R R means hydrocarbon radicals and m are values 0, 1 or 2,
  • n are values 1, 2 or 3 and m-l-n is equal to the capacity of the element to combine with hydrogen.
  • the electrolyte is characterized by the fact that at least one of the hydrotarbor radicals R to R is a benzyl, phenyl, cyclohexyl or a strongly branched hydrocarbon radical with C to C while the remaining radicals of the onium salt are alkyl radicals with C to C
  • the molar ratio between onium salt and the metal alkyl in the complex compound amounts, in the electrolyte according to the invention, is 1:1 or preferably, 1:2.
  • the effective organic groups i.e. the benzyl, phenyl, cyclohexyl or branched hydrocarbon radicals are inserted into the onium ion and not into the metal alkyl molecule of the electrolyte.
  • the variably large organic groups are tightly bound to the central atom of the onium ions, i.e. to the nitrogen, phosphorus, arsenic or tellurium atom and do not undergo any exchange or disproportioning process, the mixed organometals of zinc, aluminum, gallium and indium are not stable, but disproportionate into the pure orgauometals.
  • the self-ignition danger and hydrolysis tendency is especially sharply reduced in electrolytes according to the invention, which consist of a complex compound of a mole of an onium salt and one or two moles of a metal alkyl, and whose onium salt contains the benzyl group C H CH
  • electrolytes consist of a complex compound of a mole of an onium salt and one or two moles of a metal alkyl, and whose onium salt contains the benzyl group C H CH
  • trimethylbenzylammoniumhexethylfluorodialanate 3) 3 e s z z s) 3 2 a] respectively s) 3( e 5 2) 2 5) s is reduced so much that the compound which is liquid at room temperature does not even emit smoke when contacting air and no longer burns the skin.
  • a dangerfree handling of this electrolyte for the purpose of galvanic depositing, is therefore quite possible.
  • the zinc alkyls which are even more inflammable by air than the aluminum alkyls, become, in complexes with onium salts containing benzyl groups, readily manageable electrolyte liquids, which may be used for depositing zinc.
  • the 1:1 complex compound and the corresponding 1:2 complex compound are also liquid and not self-igniting at room temperature. They emit only a slight smoke in the air and their reaction with water has only slight vehemence. They are good organometallic electrolytes for depositing zinc, having specific conductances of 2.4 resp. 2.1- ohm -cm. at 100 C.
  • the phenyl and cyclohexyl groups reduce the melting point of the complex compound to a lesser degree, however they are also liquid at room temperature.
  • a phenyl containing electrolyte is the complex compound trimethylphenylammonium-tricthylchloroalanate,
  • the melting range of this compound is 2022 C.
  • the compound has an electric conductance of 149-10 ohm cm.-
  • the 1:2 complex correspond thereto has a melting scope of 97 to --l00 C. and a specific conductance of 1.81-10 ohm cm.- and is therefore a very suitable electrolyte for depositing aluminum.
  • Both compounds may be very favorably produced according to the method disclosed in application Ser. No. 355,222 by reaction of readily produced components dimethylaniline, chloromethane and aluminumtriethyl.
  • the quaternary phosphonium salt complex compound may be obtained This electrolyte complex first solidifies below 33 C., and at 100 C. has a specific conductance capacity of 2410* ohmcm. In this compound, a hydrogen atom of the ethyl radical in the phosphonium ion is substituted by a chlorine atom, which reduces flammability even further.
  • organic groups which also reduce the autooxidation and the hydrolysis rate of the complex compounds, are the strongly branched, and therefore space filling, hydrocarbon radicals with C to C for example, the tertiarybutyl radical-C(CH and the isopropyl radi- Cai'CH(cH3)2.
  • solubility of the complexes containing an inserted radical is increased in aromatic hydrocarbons. This is very important for the washing processes which, for galvanotechnical reasons, follow electroplating of objects.
  • the following table illustrates how the insertion of a phenyl, respectively, a benzyl radical, in place of a methyl radical in the onium ion of an aluminum complex compound efiects a reduction in the melting range and the specific conductance.
  • the aluminum compound whose onium ion contains four methyl groups, autooxidizes and has a strong tendency toward hydrolysis, the two other compounds named in the table, are favorable electrolytes, according to the invention.
  • the loss of conductance capacity may be partially compensated by thinning the complex compound with 2-4 mols of aromatic hydrocarbon, for example, benzene, toluene or xylene, or higher aliphatic or cyclic ethers, for example, di-n-butylether, isopropylether, tetrahydrofuran or dioxane.
  • aromatic hydrocarbon for example, benzene, toluene or xylene, or higher aliphatic or cyclic ethers, for example, di-n-butylether, isopropylether, tetrahydrofuran or dioxane.
  • the electrolyte complex compounds strongly dissociate into onium and metalalkylhalogenide complexes. This increases somewhat the conductance capacity of the electrolyte liquid.
  • electrolytes with little flammability are obtained through a combination of onium ions, which contain benzyl, phenyl, cyclohexyl or strongly branched hydrocarbon radicals, with higher halogen-substituted organometal ions, into a complex compound.
  • the electrolytes which are comprised of a complex compound of an onium salt containing the above mentioned hydrocarbon radicals and a metal alkyl containing one or two halogen substituents, are distinguished by low flammability, poor self-ignition, slight tendency toward autooxidation and hydrolysis, a relatively low melting temperature and a good electrical conductance. These electrolytes are therefore extraordinarily suitable for galvanic depositing of the metals zinc, aluminum, gallium and indium.
  • electrolytes are the complex compounds which are derived from the trimethylbenzylammonium-fluoride-aluminum-triethyl complex by substituting fluorine for one or two ethyl radicals.
  • Table III the melting range and the electric conductivity of these compounds are compared to the triethyl aluminum complex compound.
  • the acid salts of the quaternary onium salts which are used as the starting materials for producing the electrolytes according to the present invention, may be produced according to a process which is closely disclosed in 11.8. patent application Ser. No. 367,578.
  • the acid salt trimethylbenzylammoniuzmhydrogendifluoride is produced by reacting trimethylbenzylammoniumchloride with an excess of hydrogen fluoride.
  • the acid salt resulting from this reaction is then ether extracted whereby trimethylbenzylammoniumtrihydrogentetrafiuoride occurs.
  • This compound is reacted with sodium alcoholate to yield the colorless, crystalline and hygroscopic compound trimethylbenzylammoniumhydrogendifluoride.
  • the equations for the above described process are:
  • the acid salt trimethylbenzylammonium-hydrogendifluoride is reacted with triethyl aluminum.
  • the electrolyte which solidifies at 15 to -17 C., is thermically stable up to C. and shows no development of smoke or heat in the air.
  • the reaction with water is also slow and without danger. Due to the low autooxidation :and rate of hydrolysis there is no danger of self-ignition.
  • the electrolyte is harmless and easy to handle.
  • the acid onium chlorides and onium bromides may be reacted in the same manner as the acid oniumfluorides, with the metal alkylys of zinc, aluminum, gallium or indium.
  • the method, according to the invention, of producing electrolyte complex compounds with higher halogenide substituted metal alkyls of acid onium salts has many advantages.
  • the reactants are easily available.
  • the acid halogenides are even more readily obtainable as solvent free quaternary onium compounds, than the neutral onium salts.
  • Trialkyl-aluminum may be purchased.
  • Trialkylgallium and-indium may be produced according to the methods disclosed in co-assigned applications Ser. Nos. 162,212 and 108,996 now respectively Patent Nos. 3,310,574 and 3,318,931.
  • a method of producing dialkyl zinc is found in the Hiither thesis (Technische Hoch Anlagen Aachen, 1957).
  • the rapid and complete conversion of the solid salts is expedited by the gas development, in the present method, i.e. through the escape of alkanes.
  • the strongly exothermic reactions are preferably performed in ethers, aliphatic or aromatic hydrocarbons, for example, in diethylether, hexane, benzene or toluene.
  • the most favorable reaction mediums were in the aromatic hydrocarbons, since they dissolve the developing complex salts.
  • the solutions of the onium salt complex compound may find use as electrolytes. If the complex compounds are to be obtained per se, then aliphatic ethers or hydrocarbons are recommended as a solvent for removing the considerable heat of reaction.
  • a second combination utilized an electrolyte, thinned with an equimolar amount of toluene.
  • the bath temperature was C.
  • the electrical data was 0.5 a./dm. cathode current density at 1.3 to 1.5 v. cell voltage.
  • An aluminum layer of approximately 80a thickness grew in 16 hours and had a fine crystalline, brightly polished (shining)appearance.
  • R an alkyl radical with C to C Y a nitrogen, phosphorus, arsenic or tellurium atom
  • R R R R represent hydrocarbons and m the values n the values 1, 2 or 3 and m+n is equal to the capacity of the element to combine with hydrogen wherein at least one of the hydrocarbon radicals R to R is selected from the group of benzyl, phenyl, cyclohexyl and strongly branched hydrocarbon radical with C to C and the remaining radicals of the oniurn salt are C to C alkyls.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
US515804A 1964-12-17 1965-12-16 Organometallic electrolyte for galvanic deposition of zinc, aluminum, gallium and indium Expired - Lifetime US3418216A (en)

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US (1) US3418216A (de)
AT (2) AT266861B (de)
BE (1) BE673423A (de)
CH (1) CH484195A (de)
DE (1) DE1496993B1 (de)
FR (1) FR1461819A (de)
GB (1) GB1104930A (de)
SE (1) SE344216B (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USB535813I5 (de) * 1974-12-23 1976-01-27
US4032413A (en) * 1974-11-13 1977-06-28 Siemens Aktiengesellschaft Electroplating bath and method for the electrodeposition of bright aluminum coatings
US5104840A (en) * 1990-03-20 1992-04-14 Institut Francais Du Petrole Non-aqueous liquid composition with an ionic character and its use as a solvent
WO2004016571A2 (en) * 2002-08-16 2004-02-26 Sachem, Inc. Lewis acid ionic liquids
US20050131118A1 (en) * 2002-08-16 2005-06-16 Roger Moulton Ionic liquids containing a sulfonate anion
WO2015069871A1 (en) * 2013-11-06 2015-05-14 Research Foundation Of The City University Of New York Ionic liquid comprising alkaline earth metal

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076600A (en) * 1976-12-20 1978-02-28 R. O. Hull & Company, Inc. Leveling agent for acid zinc electroplating baths and method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3268421A (en) * 1961-12-04 1966-08-23 Nat Steel Corp Electrodeposition of metals from a fused bath of aluminum halohydride organic complex and composition therefor
US3308143A (en) * 1962-11-14 1967-03-07 Continental Oil Co Process for decomposing trialkylaluminum complex

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3268421A (en) * 1961-12-04 1966-08-23 Nat Steel Corp Electrodeposition of metals from a fused bath of aluminum halohydride organic complex and composition therefor
US3308143A (en) * 1962-11-14 1967-03-07 Continental Oil Co Process for decomposing trialkylaluminum complex

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4032413A (en) * 1974-11-13 1977-06-28 Siemens Aktiengesellschaft Electroplating bath and method for the electrodeposition of bright aluminum coatings
USB535813I5 (de) * 1974-12-23 1976-01-27
US3981819A (en) * 1974-12-23 1976-09-21 Rca Corporation Luminescent sulfides of monovalent and trivalent cations
US5104840A (en) * 1990-03-20 1992-04-14 Institut Francais Du Petrole Non-aqueous liquid composition with an ionic character and its use as a solvent
WO2004016571A3 (en) * 2002-08-16 2005-02-24 Sachem Inc Lewis acid ionic liquids
US20040122229A1 (en) * 2002-08-16 2004-06-24 Roger Moulton Lewis acid ionic liquids
WO2004016571A2 (en) * 2002-08-16 2004-02-26 Sachem, Inc. Lewis acid ionic liquids
US20050131118A1 (en) * 2002-08-16 2005-06-16 Roger Moulton Ionic liquids containing a sulfonate anion
US7053232B2 (en) * 2002-08-16 2006-05-30 Sachem, Inc. Lewis acid ionic liquids
US20090200513A1 (en) * 2002-08-16 2009-08-13 University Of South Alabama Ionic Liquids Containing a Sulfonate Anion
US7750166B2 (en) 2002-08-16 2010-07-06 University Of South Alabama Ionic liquids containing a sulfonate anion
WO2015069871A1 (en) * 2013-11-06 2015-05-14 Research Foundation Of The City University Of New York Ionic liquid comprising alkaline earth metal
CN106463769A (zh) * 2013-11-06 2017-02-22 纽约城市大学研究基金会 包含碱土金属的离子液体

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GB1104930A (en) 1968-03-06
CH484195A (de) 1970-01-15
DE1496993B1 (de) 1972-05-04
SE344216B (de) 1972-04-04
AT266861B (de) 1968-12-10
BE673423A (de) 1966-04-01
AT264945B (de) 1968-09-25
FR1461819A (fr) 1966-12-09

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