US2446331A - Electrodeposition of aluminum - Google Patents

Electrodeposition of aluminum Download PDF

Info

Publication number
US2446331A
US2446331A US522375A US52237544A US2446331A US 2446331 A US2446331 A US 2446331A US 522375 A US522375 A US 522375A US 52237544 A US52237544 A US 52237544A US 2446331 A US2446331 A US 2446331A
Authority
US
United States
Prior art keywords
aluminum
bath
chloride
pyridinium
electrodeposition
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.)
Expired - Lifetime
Application number
US522375A
Inventor
Frank H Hurley
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.)
William Marsh Rice University
Original Assignee
William Marsh Rice University
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 William Marsh Rice University filed Critical William Marsh Rice University
Priority to US522375A priority Critical patent/US2446331A/en
Application granted granted Critical
Publication of US2446331A publication Critical patent/US2446331A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

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

Description

Patented Au g. 3, 1948 2,446,331 ELECTRODEPOSITION OF ALUMINUM Frank H. Hurley, Portland, reg., assignor to The William Marsh Rice Institute for the Advancement of Literature, .Science and Art, a corporation of Texas No Drawing. Application February 14, 1944, Serial No. 522,375

1 2 Claims.

This invention relates to the electrodeposition of aluminum, and particularly to a process involving the deposition of aluminum on a suitable cathode from an electrolyte comprising a fused or liquid mixture of a suitable aluminum salt with an N-alkyl pyridinium halide.

It has long been recognized that aluminum possesses many unique properties particularly with respect to corrosion resistance. However, the low tensile strength and especially the low elastic limit of pure aluminum render it rather unsatisfactory as a structuralmaterial for many purposes. Therefore the possibility of electroplating aluminum on steel and on other common metals promises a wider range of mechanical substances, particularly in chemical construction work. The appearance of many articles would also be improved if they could be plated with aluminum.

It is in general the broad object of the present invention to provide a process enabling aluminum to be electroplated on various dissimilar common metals.

A further object of the present invention is to provide a novel electroplating bath which can be successfully employed for electrodeposition of aluminum.

A still further object of the present invention is to provide a bath for the electrodeposition of aluminum which has a relatively high electrical conductivity, a low voltage requirement, and in which high electrode efflciencies are obtained.

In my process for the electroplating with aluminum of dissimilar metals such as iron. copper, brass, bronze, lead and tin, I employ a bath composed essentially of a fused or liquid mixture of an N-alkyl pyridinium halide and an anhydrous aluminum halide, preferably aluminum chloride. I have successfully employed solutions of anhydrous aluminum chloride in various anhydrous fused pyridinium compounds, particularly ethyl pyridinium bromide, ethyl pyridinium chloride, ethylene dipyridinium dlbromide, and ethylene dipyridinium dichloride.

The bath is prepared by mixing the aluminum salt and the pyridinium compound together, melting the mixture by heating, if desired. The addition of the aluminum chloride causes a conslderabie amount of heat to be generated, and in some instances no additional heating is necessary. Generally the bath composition should be such that the pyridinium cation is not reduced at the cathode. The aluminum salt concentration must be sumciently high, having regard to the actual conditions of electrolysis in each instance,

that this does not occur. I have found that one should employ a bath containing approximately two mols of aluminum chloride (taken as AlCl: herein and in the claims) to one moi of halide or nitrogen (taken as N) in the pyridinium salt. With ethyl pyridinium bromide this approximate value represents an eutectic composition corresponding to a 2 to 1 mol ratio of aluminum chloride to ethyl pyridinium bromide. The ethyl pyridinium bromide content can, however, vary between about 46 mol per cent and 30 mol per cent. In any case, if the aluminum chloride concentration is too low, the aforementioned reduction of the pyridinium cation occurs at the cathode, while if the aluminum chloride concentration is too high, the plate will contain what appears to be occluded aluminum chloride.

In operation, the electrolyte is maintained at a sufllciently high temperature so that it is in a fused condition, and, more especially, at a temperature at which good plates are obtained. With ethyl pyridinium bromide, temperatures in the range from 40 C. to 150 C. depending on the composition of the bath, have been found useful for plating. The preferred temperature for the aforementioned eutectic mixture is approximately 125 0. Too low a temperature results in low conductivity and produces spongy deposits. At higher temperatures aluminum chloride will distill from the bath and decomposition of the electrolyte can occur. With other pyridinium compounds different temperatures.

are required, generally above C.

As a container for the bath a cell of glass, porcelain, or other inert material may be used; or the containermay 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 alloy. 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.

The anode employed consists, of course, of aluminum; the cathode is the article to be plated. A zinc article should not be employed inasmuch as zinc reacts with the bath.

In=removing the plated object from the bath, care must be taken to remove the adhering liquid before absorption of moisture from the atmosphere can occur. for this will generate hydrogen chloride which will attack the aluminum plate. One method of achieving this is to rinse the plate in a such as benzene, immediately after removal.

It is a feature of the present invention that relatively low voltages can be employed. In fact, relatively low voltages are essential to successful operation, for too high a voltage can produce organic decomposition at the electrodes. In cells in which the anode and cathode were about 1% inches apart, two to three volts was employed; in cells of other design, lower voltages were successfully used.

The optimum cathode current density for baths of this type is approximately 0.5 ampJdmF. Variation in the current density affects the type of plate produced. For example, those obtained at current densities much lower than 0.5 amp./dm. were usually white and dull, whereas at current densities somewhat higher than this value they were usually gray and dull. At the preferred current density bright and shiny plates were usually obtained. If the current density becomes too high, a black deposit appears at the cathode.

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 be so arranged in the cell that the resistance of the cell is not too high and the current distribution on the cathode is uniform.

The following specific operating example is set forth by way of further illustrating the invention and not by way of limitation.

A plating mixture containing 63.0 mol per cent of aluminum chloride (taken as A1013) and 37.0 mol per cent of ethyl pyridinium chloride was prepared by adding the aluminum chloride to the molten pyridinium salt. The mixture was transferred to an-aluminum pot which served both as the container and the anode. This was fitted with a suitably designed top to prevent absorption of moisture by the bath. The cathodes, which could be inserted through the top, consisted of suitably cleaned sheets of steel and other metals. 5 cm. wide and 14 cm. long with a depth of immersion in the plating liquid of 3.5 cm. The temperature of the plating bath was maintained at 125 C. by immersing the aluminum pot in a large oil bath.

solvent miscible with the bath,

Plating tests of several different sorts were made with this bath, using steel cathodes. In one set of tests using voltages ranging from 0.2 to,0.6 volt, the following results were obtained at different current densities, when the total quantity of electricity was held constant:

1. 1.00 amp./dm.=uniform gray plate, somewhat granular 2.0.90 amp./dm. less uniform, granular in spots 3. 0.63 amp./dm. -uniform plate. white in color 4. 0.46 amp/rimfi-shiny, adherent plate 5. 0.30 amp/dmF-partly shiny. partly dull plate consisting essentially of a fused mixture of (1) about 2 mols of aluminum chloride and '(2) 1 mol of ethyl pyridinium chloride.

2. A nonaqueous electrolyte for use in the electro-depositlon of aluminum as a bright, adherent deposit that consists essentially of a fused mixture of (1) about 2 mols of aluminum chloride and (2) 1 mol of ethyl pyridinium chloride.

FRANK H. HURLEY.

REFERENCES CITED The following references are of record in the Chemical Abstracts, vol. 32. No. 18, Sept. 20, 1938, col. 6956.

Elektrochemie Nichtwassriger Losungen, by Paul Walden, pp. 194, 200, 239.

Journal of American Chemical Society, vol. 19 (1897), p. 563. 4

US522375A 1944-02-14 1944-02-14 Electrodeposition of aluminum Expired - Lifetime US2446331A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US522375A US2446331A (en) 1944-02-14 1944-02-14 Electrodeposition of aluminum

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US522375A US2446331A (en) 1944-02-14 1944-02-14 Electrodeposition of aluminum

Publications (1)

Publication Number Publication Date
US2446331A true US2446331A (en) 1948-08-03

Family

ID=24080613

Family Applications (1)

Application Number Title Priority Date Filing Date
US522375A Expired - Lifetime US2446331A (en) 1944-02-14 1944-02-14 Electrodeposition of aluminum

Country Status (1)

Country Link
US (1) US2446331A (en)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2568508A (en) * 1949-02-03 1951-09-18 Gerald C Montague Motor block attaching means for motor stands
US2796392A (en) * 1951-08-01 1957-06-18 Milton H Lietzke Process and electrolyte for the electrodeposition of zirconium
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
US5041194A (en) * 1989-05-18 1991-08-20 Mitsubishi Petrochemical Co., Ltd. Aluminum electroplating method
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
US6350721B1 (en) 1998-12-01 2002-02-26 Schlumberger Technology Corporation Fluids and techniques for matrix acidizing
US20040206622A1 (en) * 2001-07-25 2004-10-21 Katsuji Kawakami Apparatus for plating treatment
US20040238352A1 (en) * 2000-10-20 2004-12-02 The University Of Alabama Production, refining and recycling of lightweight and reactive metals in ionic liquids
WO2004106288A2 (en) 2003-06-02 2004-12-09 Merck Patent Gmbh Ionic liquids containing guanidinium cations
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
US20060169590A1 (en) * 2003-03-04 2006-08-03 Hebditch David J Process for separating metals
DE102008014028A1 (en) 2008-03-13 2009-09-17 Doris Dr. Kunz Preparing imidazolium salts, preferably 1,3-disubstiuted imidazolium salts, useful e.g. as precursors of N-heterocyclic carbenes, comprises reducing 1,3-disubstituted-2-alkoxyimidazolium salts with hydrides and/or hydride donors
DE102008031480A1 (en) 2008-07-03 2010-01-07 Merck Patent Gmbh Salts containing a Pyrimidincarbonsäure derivative
US20120189778A1 (en) * 2011-01-26 2012-07-26 Riewe Curtis H Coating method using ionic liquid
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
US9803283B1 (en) 2013-10-18 2017-10-31 Hrl Laboratories, Llc Method of electroless deposition of aluminum or aluminum alloy, an electroless plating composition, and an article including the same
US10208391B2 (en) 2014-10-17 2019-02-19 Ut-Battelle, Llc Aluminum trihalide-neutral ligand ionic liquids and their use in aluminum deposition
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 (4)

* 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
US2170375A (en) * 1937-05-10 1939-08-22 Frank C Mathers Electrodeposition of aluminum

Patent Citations (4)

* 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
US2170375A (en) * 1937-05-10 1939-08-22 Frank C Mathers Electrodeposition of aluminum

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2568508A (en) * 1949-02-03 1951-09-18 Gerald C Montague Motor block attaching means for motor stands
US2796392A (en) * 1951-08-01 1957-06-18 Milton H Lietzke Process and electrolyte for the electrodeposition of zirconium
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
US5041194A (en) * 1989-05-18 1991-08-20 Mitsubishi Petrochemical Co., Ltd. Aluminum electroplating method
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
US6350721B1 (en) 1998-12-01 2002-02-26 Schlumberger Technology Corporation Fluids and techniques for matrix acidizing
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
US20040206622A1 (en) * 2001-07-25 2004-10-21 Katsuji Kawakami Apparatus for plating treatment
US7750166B2 (en) 2002-08-16 2010-07-06 University Of South Alabama Ionic liquids containing a sulfonate anion
US7053232B2 (en) 2002-08-16 2006-05-30 Sachem, Inc. Lewis acid ionic liquids
US20050131118A1 (en) * 2002-08-16 2005-06-16 Roger Moulton Ionic liquids containing a sulfonate anion
US20090200513A1 (en) * 2002-08-16 2009-08-13 University Of South Alabama Ionic Liquids Containing a Sulfonate Anion
US20060169590A1 (en) * 2003-03-04 2006-08-03 Hebditch David J Process for separating metals
WO2004106288A2 (en) 2003-06-02 2004-12-09 Merck Patent Gmbh Ionic liquids containing guanidinium cations
DE102008014028A1 (en) 2008-03-13 2009-09-17 Doris Dr. Kunz Preparing imidazolium salts, preferably 1,3-disubstiuted imidazolium salts, useful e.g. as precursors of N-heterocyclic carbenes, comprises reducing 1,3-disubstituted-2-alkoxyimidazolium salts with hydrides and/or hydride donors
DE102008031480A1 (en) 2008-07-03 2010-01-07 Merck Patent Gmbh Salts containing a Pyrimidincarbonsäure derivative
US20110152292A1 (en) * 2008-07-03 2011-06-23 Merck Patent Gesellschaft Salts comprising a pyrimidinecarboxylic acid derivative for cosmetic use
US20120189778A1 (en) * 2011-01-26 2012-07-26 Riewe Curtis H Coating method using ionic liquid
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
US9803283B1 (en) 2013-10-18 2017-10-31 Hrl Laboratories, Llc Method of electroless deposition of aluminum or aluminum alloy, an electroless plating composition, and an article including the same
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
US10208391B2 (en) 2014-10-17 2019-02-19 Ut-Battelle, Llc Aluminum trihalide-neutral ligand ionic liquids and their use in aluminum deposition

Similar Documents

Publication Publication Date Title
Walsh et al. A review of developments in the electrodeposition of tin-copper alloys
Pitner et al. Electrodeposition of Zinc from the Lewis Acidic Aluminum Chloride‐1‐Methyl‐3‐ethylimidazolium Chloride Room Temperature Molten Salt
Couch et al. A hydride bath for the electrodeposition of aluminum
EP2130949B1 (en) ELECTRIC Al-Zr ALLOY PLATING BATH USING ROOM TEMPERATURE MOLTEN SALT BATH AND PLATING METHOD USING THE SAME
Zhao et al. Electrodeposition of aluminium from nonaqueous organic electrolytic systems and room temperature molten salts
CA1073857A (en) Plated metallic cathode
CA1115654A (en) Bright tin-lead alloy plating
Lin et al. Electrodeposition of zinc from a Lewis acidic zinc chloride-1-ethyl-3-methylimidazolium chloride molten salt
US8586196B2 (en) Aluminum plated film and metallic member
Senna et al. Electrodeposition of copper–zinc alloys in pyrophosphate-based electrolytes
Chen et al. Electrodeposition of Cu‐Zn Alloy from a Lewis Acidic ZnCl2‐EMIC Molten Salt
US6585812B2 (en) High current density zinc sulfate electrogalvanizing process and composition
US3620934A (en) Method of electrolytic tinning sheet steel
Jafarian et al. Electrodeposition of aluminum from molten AlCl 3–NaCl–KCl mixture
Yang et al. Electrodeposition of tin and antimony in 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid
US3663384A (en) Bath for electroplating tin-bismuth alloy
US4668347A (en) Anticorrosive coated rectifier metals and their alloys
US4092226A (en) Process for the treatment of metal surfaces by electro-deposition of metal coatings at high current densities
US3917517A (en) Chromium plating electrolyte and method
US4118289A (en) Tin/lead plating bath and method
JP2008195990A (en) Electric aluminum plating bath and plating method using the same
US2817631A (en) Refining titanium alloys
US3522021A (en) Process for metalliding aluminum surfaces
EP0339536A1 (en) Plating bath for electrodeposition of aluminum and plating process making use of the bath
WO2010044305A1 (en) Electrolytic aluminum plating solution and method for forming aluminum plating film