US2446349A - Electrodeposition of aluminum - Google Patents

Electrodeposition of aluminum Download PDF

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Publication number
US2446349A
US2446349A US524486A US52448644A US2446349A US 2446349 A US2446349 A US 2446349A US 524486 A US524486 A US 524486A US 52448644 A US52448644 A US 52448644A US 2446349 A US2446349 A US 2446349A
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aluminum
mixture
bath
electrodeposition
chloride
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US524486A
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Jr Thomas P Wier
Frank H Hurley
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William Marsh Rice University
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William Marsh Rice University
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    • 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

Description

Patented Aug. 3, 1948 ELECTRODEPOSITION OF ALUMINUM Thomas P. Wier, Jr., Berkeley, Calif., and Frank H. Hurley, Portland, Orega, assignors to The William Marsh Rice Institute for the Advancement of Literature, Science and Art, 9, corporation of Texas No Drawing. Application February29, 1944,

Serial N 0. 524,486

2 Claims. 1

This invention relates to the electrodeposition of aluminum from a liquid mixture of a nitrogensubstituted alkyl pyridinium chloride or bromide and aluminum chloride.

In a co-pending application, Serial No. 522,375, filed February 14, 1944, Hurley has disclosed a process for the electrodeposition of aluminum on dissimilar metal cathodes from a liquid mixture of aluminum chloride or bromide and an N-alkyl pyridinium chloride or bromide or an N-alkylene dipyridinium chloride or bromide. Hurley points out the temperature of the bath must be suiiiciently elevated to avoid spongy aluminum deposits and that one should generally work at a temperature above 100 C.

It is obvious that if one can successfully plate aluminum at a lower temperature, preferably about room temperature, the operation is materially simplified, the operation can be conducted more economically, and various articles which cannot be handled readily at the more elevated temperatures can be plated at the lower temperature.

It is in general the broad object of the present invention to provide a process for the electrodeposition of aluminum on dissimilar metals at room temperature.

Another object of the present invention is to provide a novel electrolyte for the electrodeposition of aluminum on dissimilar metals. We have discovered that by the addition of certain aromatic compounds to liquid mixtures of aluminum chloride or bromide and the N-alkyl mono-pyridinium mono-chlorides or mono-bromides in which the alkyl radical is unsubstituted, an improved bath is obtained, one which permits successful plating at room temperature.

In addition, by utilization of the aromatic compounds, it is possible to materially lower the cost of the plating solution.

Further, the plate which is secured is materially improved in appearance when compared to a plate on the same material which is efiected at an elevated temperature without the use of the additional compound. Y

In addition to these advantages, there is less loss of the plating solution upon removal of the plated object from the bath. Further, it is possible to use higher current densities.

In making up the bath, we employ a liquid compound selected from the group consisting of liquid aromatic hydrocarbons such as benzene, toluene, xylene and the like, and their liquid chloro-substituted derivatives such as chlorobenzene. Mixtures of these liquids can also be used. 7

One proceeds to make up the desired mixture of aluminum chlorideand the desired nitrogensubstituted alkyl 'mono-pyridinium mono-chloride or mono-bromide. One then adds the aromatic substance, such as benzene, preferably until an excess of the added compound floats on the top of the aluminum chloride-pyridinium compound layer. The lower layer is the plating solution. When the plating mixture is saturated with the aromatic compound in this way, the volume of electrolytev solution is approximately doubled, except in the case of chloro-benzene which appears to be miscible with the aluminum chloride-pyridinium compound mixture in all proportions. The upper layer, which consists principally of the added aromatic compound, is very useful for protecting the bath from atmospheric moisture. However, it is not necessary that completely saturated solutions be employed for the successful operation of the bath, and one need only add a. small amount of the aromatic substance to the aluminum chloride-pyridinium compound mixture to secure some of the advantages of this invention.

Good plates of aluminum can be obtained when the nitrogen-substituted alkyl halide is the ethylited upon the cathode.

In removing the cathode from the bath a thin film of the plating solution remains on the cathode. This should be removed immediately by rinsing with water.

As a container forthe bath, a cell of glass, porcelain or other inert material may be used; or the container may be made of aluminum and can then serve as the anode. If the cell is made of other metals, any moisture which is present may result in corrosion of the metal by moist hydrogen halide. This can carry the metal halide into solution and may result in the formation of a plate consisting of an aluminum 81107.

Under certain conditions these alloy plates may not be disadvantageous and accordingly the term aluminum as used here and in the claims is to be considered as including such alloys in which aluminum forms the major constituent.

To obtain the proper conditions of current density and voltage, a suitably designed cell must be employed. In general, the anode should be as large as or larger than, the cathode object, and the electrodes should beso arranged in the cell that the resistance of the cell is not too high and the cathode current distribution is uniform.

In electroplating with this type of bath, cathode current densities between 0.5 and 1.0 amp/rim. were found to be most useful. At the lower cathode densities (about 0.5 ampJdmP) white plates of aluminum were obtained, while at the higher current densities (about 1.0 ampJdmF), the plates were very bright and shiny. At still higher current densities brown streaks appeared on the shiny deposits and with excessive current densities, black, non-adherent deposits were obtained. These appeared to contain some occluded aluminum chloride. In some cells we have successfully used cathode current densities as high as 2.0 ampozldm. and obtained bright and shiny plates. The white plates mentioned above may .be polished if desired.

The cathode current eiiiciencies are very high, being about 85% at 0.5 amp./dm. to 92% at 1.0 link/(11113.

In addition, the voltage requirements of this plating solution are very low, of the order of one volt. However. this depends on the cell size and the current density.

To obtain the best results with this bath, it should be used'in a dry atmosphere, free of ongen and other oxidizing gases. The behaviour of the bath in the presence of moist air shows that it is sublcct to oxidation which can lead to deterioration of its plating properties. The oxidation is indicated by the appearance of a red color in the bath. A nitrogen atmosphere or an atmosphere a non-oxidizing gas should be maintained over the bath.

The following example is given as illustrative of a practice within the present invention.

A mixture of ethyl pyridinium bromide and aluminum chloride in the ratio of 66.7 mo1 per cent aluminum chloride (taken as A1013) and 33.3 mol per cent ethyl pyridlnium bromide was Prepared and toluene was added until the mixture was saturated. This mixture was used in a cylindrical glass cell, 5.2 cm. in diameter and filled the cell to a depthof about 5 cm. The mixture was covered with a layer of toluene about 1 cm. deep, which served as a protection against moisture. The anode was a circular aluminum sheet, 5 cm. high and 15 cm. in circumference. Thin sheets of iron or other metal 2.5 to 3.8 cm. wide, wereused as cathode objects and were immersed from 3 to 5 cm. in the plating liquid. These were suitably cleaned before use. The

whole apparatus was fitted with a suitably deherent deposit on a metal from the group consisting of iron, copper, brass, bronze, lead, and nickel and tin from a cell containing a liquid nonaqueous electrolyte consisting essentially of a mixture of (1) about 2 mols of aluminum chloride, (2) about 1 mol of ethyl pyridinium chloride, and (3) a sumcient amount of toluene to saturate the mixture.

2. A nonaqueous electrolyte for use in the electrodeposition of aluminum as a bright, adherent deposit that consists essentially of a mixture of (1) about 2 mols of aluminum chloride, (2) 1 mol of ethyl pyridiniu-m chloride and (3) a suflicient amount of toluene to saturate the mixture.

THOMAS P. WIER. Ja. FRANK H.

REFERENCES crrnn The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,911,122 Keyes et al May 23, 1933 1,939,397 Keyes et a1. Dec. 12, 1933 1,960,334 Ernst et all. May 29, 1934 OTHER REFERENCES 32, No. 18 (Sept. 20,

Society, vol. 19

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2692850A (en) * 1951-11-02 1954-10-26 Battelle Development Corp Aluminum electroforming
US2728718A (en) * 1951-11-02 1955-12-27 Battelle Development Corp Aluminum coating
US2849349A (en) * 1955-06-13 1958-08-26 Ziegler Process for the electrolytic deposition of aluminium
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
US3532609A (en) * 1965-11-09 1970-10-06 Nippon Kokan Kk Process for the preliminary treatment adapted for the electrolytic formation of aluminum coatings on metallic surfaces in molten salt bath
US3775260A (en) * 1971-04-27 1973-11-27 Canadian Patents Dev Electroplating aluminum
US4463072A (en) * 1983-11-30 1984-07-31 Allied Corporation Secondary batteries containing room-temperature molten 1,2,3-trialkylimidazolium halide non-aqueous electrolyte
US4463071A (en) * 1983-11-30 1984-07-31 Allied Corporation Secondary batteries using room-temperature molten non-aqueous electrolytes containing 1,2,3-trialkylimidazolium halides or 1,3-dialkylimidazolium halide
US4747916A (en) * 1987-09-03 1988-05-31 Nisshin Steel Co., Ltd. Plating bath for electrodeposition of aluminum and process for the same
US4904355A (en) * 1988-04-26 1990-02-27 Nisshin Steel Co., Ltd. Plating bath for electrodeposition of aluminum and plating process making use of the bath
US4906342A (en) * 1988-04-26 1990-03-06 Nisshin Steel Co., Ltd. Plating bath for electrodeposition of aluminum and plating process making use of the bath
US4966660A (en) * 1987-07-13 1990-10-30 Nisshin Steel Co., Ltd. Process for electrodeposition of aluminum on metal sheet
US5074973A (en) * 1989-05-23 1991-12-24 Nisshin Steel Co. Ltd. Non-aqueous electrolytic aluminum plating bath composition
US5827602A (en) * 1995-06-30 1998-10-27 Covalent Associates Incorporated Hydrophobic ionic liquids
US20040238352A1 (en) * 2000-10-20 2004-12-02 The University Of Alabama Production, refining and recycling of lightweight and reactive metals in ionic liquids
US20060169590A1 (en) * 2003-03-04 2006-08-03 Hebditch David J Process for separating metals
DE10108893C5 (en) * 2001-02-23 2011-01-13 Rolf Prof. Dr. Hempelmann Process for the production of metals and their alloys
WO2012043129A1 (en) * 2010-09-30 2012-04-05 株式会社日立製作所 Aluminum electroplating solution
US20150144495A1 (en) * 2013-11-22 2015-05-28 Sikorsky Aircraft Corporation Methods and materials for electroplating aluminum in ionic liquids
US9631290B2 (en) 2011-10-07 2017-04-25 The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas Room temperature electrodeposition of actinides from ionic solutions
US10422048B2 (en) 2014-09-30 2019-09-24 The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas Processes for recovering rare earth elements

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1911122A (en) * 1929-08-13 1933-05-23 Ellis Foster Co Process for the electrodeposition of aluminum from its compounds
US1939397A (en) * 1929-04-12 1933-12-12 Ellis Foster Co Process of electrodeposition of aluminum
US1960334A (en) * 1934-05-29 Process of preparing n-methyl com

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1960334A (en) * 1934-05-29 Process of preparing n-methyl com
US1939397A (en) * 1929-04-12 1933-12-12 Ellis Foster Co Process of electrodeposition of aluminum
US1911122A (en) * 1929-08-13 1933-05-23 Ellis Foster Co Process for the electrodeposition of aluminum from its compounds

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2692850A (en) * 1951-11-02 1954-10-26 Battelle Development Corp Aluminum electroforming
US2728718A (en) * 1951-11-02 1955-12-27 Battelle Development Corp Aluminum coating
US2849349A (en) * 1955-06-13 1958-08-26 Ziegler Process for the electrolytic deposition of aluminium
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
US3532609A (en) * 1965-11-09 1970-10-06 Nippon Kokan Kk Process for the preliminary treatment adapted for the electrolytic formation of aluminum coatings on metallic surfaces in molten salt bath
US3775260A (en) * 1971-04-27 1973-11-27 Canadian Patents Dev Electroplating aluminum
US4463072A (en) * 1983-11-30 1984-07-31 Allied Corporation Secondary batteries containing room-temperature molten 1,2,3-trialkylimidazolium halide non-aqueous electrolyte
US4463071A (en) * 1983-11-30 1984-07-31 Allied Corporation Secondary batteries using room-temperature molten non-aqueous electrolytes containing 1,2,3-trialkylimidazolium halides or 1,3-dialkylimidazolium halide
US4966660A (en) * 1987-07-13 1990-10-30 Nisshin Steel Co., Ltd. Process for electrodeposition of aluminum on metal sheet
US4747916A (en) * 1987-09-03 1988-05-31 Nisshin Steel Co., Ltd. Plating bath for electrodeposition of aluminum and process for the same
US4904355A (en) * 1988-04-26 1990-02-27 Nisshin Steel Co., Ltd. Plating bath for electrodeposition of aluminum and plating process making use of the bath
US4906342A (en) * 1988-04-26 1990-03-06 Nisshin Steel Co., Ltd. Plating bath for electrodeposition of aluminum and plating process making use of the bath
US5074973A (en) * 1989-05-23 1991-12-24 Nisshin Steel Co. Ltd. Non-aqueous electrolytic aluminum plating bath composition
US5827602A (en) * 1995-06-30 1998-10-27 Covalent Associates Incorporated Hydrophobic ionic liquids
US20040238352A1 (en) * 2000-10-20 2004-12-02 The University Of Alabama Production, refining and recycling of lightweight and reactive metals in ionic liquids
US7347920B2 (en) 2000-10-20 2008-03-25 The Board Of Trustees Of The University Of Alabama Production, refining and recycling of lightweight and reactive metals in ionic liquids
DE10108893C5 (en) * 2001-02-23 2011-01-13 Rolf Prof. Dr. Hempelmann Process for the production of metals and their alloys
US20060169590A1 (en) * 2003-03-04 2006-08-03 Hebditch David J Process for separating metals
WO2012043129A1 (en) * 2010-09-30 2012-04-05 株式会社日立製作所 Aluminum electroplating solution
US9631290B2 (en) 2011-10-07 2017-04-25 The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas Room temperature electrodeposition of actinides from ionic solutions
US20150144495A1 (en) * 2013-11-22 2015-05-28 Sikorsky Aircraft Corporation Methods and materials for electroplating aluminum in ionic liquids
US9903034B2 (en) * 2013-11-22 2018-02-27 Sikorsky Aircraft Corporation Methods and materials for electroplating aluminum in ionic liquids
US10422048B2 (en) 2014-09-30 2019-09-24 The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas Processes for recovering rare earth elements

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