US3687824A - Electrodeposition of films of particles on cathodes - Google Patents
Electrodeposition of films of particles on cathodes Download PDFInfo
- Publication number
- US3687824A US3687824A US834901A US3687824DA US3687824A US 3687824 A US3687824 A US 3687824A US 834901 A US834901 A US 834901A US 3687824D A US3687824D A US 3687824DA US 3687824 A US3687824 A US 3687824A
- Authority
- US
- United States
- Prior art keywords
- particles
- films
- nickel
- sulfate
- deposited
- 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
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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
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
- C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
Definitions
- particles such' as barium sulfate, boron and polyvinyl chloride can be deposited on a cathode from solutions of sodium sulfate in which the particles are dispersed.
- These films of particles can be used as such or can then be rinsed and transferred to plating baths and the films of particles can thus be imbedded in a metal matrix.
- Such 2-phase composite plates can be used for engineering purposes such as anti-friction applications, and the like, or with multiple plates to obtain excellent protection against atmospheric corrosion.
- This invention relates to the cathodic electrodeposition of fine bath-insoluble particles dispersed in aqueous electrolytes comprising water-soluble salts of monovalent cations, such as sodium sulfate, potassium sulfate, lithium sulfate and the like, which do not yield, on solid cathodes, electrodeposits of the monovalent cation from aqueous solutions.
- monovalent cations such as sodium sulfate, potassium sulfate, lithium sulfate and the like
- the adherence of the particles to clean steel, brass, copper, nickel, stainless steel or the like, cathodes is surprising.
- the films of deposited particles can be rinsed in fast flowing water without loss of the film of particles.
- the films can be dried at 110 C. for several hours and not lose their adherence.
- the films can, however, be rubbed olf with a brush or a cloth. Nevertheless, the importance of this method to produce films of particles on metal lies in the fact that these films do have suificient adherence that they can be further processed after rinsing or drying of the articles with the electrodeposited films of particles remaining substantially intact.
- duplex foils can be made by plating over a film of deposited particles with, for example, a thin copper plate of about 0.1 mil to 0.5 mil, and then plating on top of the copper with nickel.
- the particles to be cathodically deposited by the methods of this invention are par- .ticles that settle in the bath and sufficient agitation of the solution must be used to maintain the particles in suspension in the bath. This is unlike the electrophoretic deposition of organic resin particles either from monomer form or from colloidal polymer form. In these cases, the organic resin particles deposit on anodes, and in colloidal form do not require agitation to maintain their suspension in the bath.
- the operating baths of the present invention are aqueous solutions containing monovalent cations, such as alkali metal and ammonium cations.
- the alkali metal monovalent cations and the ammonium cation may be used as sulfate salts such as ammonium sulfate, ar carbonate salts such as sodium carbonate, as sulfonates such as sodium methyl or ethyl sulfonates, sodium benzene sulfonate, sodium naphthalene trisulfonate, and the like.
- the preferred operating pH is from about 4 to 10.5, as higher, and especially lower pH values tend to yield thinner films of most of the fine particles suspended in the baths. Mixed salts may be used.
- the lower concentration values of the salts such as 30 to grams/liter are preferred over the higher concentrations to obtain the best deposition rates.
- the temperature of the baths is not critical and deposition rates of the powders are just as good at 60 C. or higher, as at room temperature or lower.
- surfactants such as sodium 2-ethyl hexyl sulfate and sodium n-octyl sulfate may be used in the baths, even non-ionic and cationic or ionically neutral sulfobetaines may be used.
- Buffers such as boric acid decrease the rate of deposition of the particles, and as mentioned, excellent results are obtained from the simple baths consisting of sodium, potassium, lithium, or ammonium, rubidium and cesium sulfates.
- Amine sulfates may also be used but the preferred salts are in general sodium and potassium, lithium and ammonium sulfates or mixtures of these salts.
- Various particles or powders may be incorporated in the baths for plating onto the cathode surfaces.
- a plain air-agitated 100 g./l. sodium sulfate solution there is dispersed 25-150 g./l. of barium sulfate powder of 0.05 to 5 microns particle size, or 5-50 g./l.
- the anodes may be graphite, lead or nickel or other insoluble electrodes in aqueous sulfate solutions and as has been noted the temperature of the bath can be from room or lower to at least 60 C.
- thermoplastic resin particles such as polyvinylidene chloride, PVC, polyethylene, polyamides and polytetrafiuoroethylenes plated out as a film of dense discrete particles can be heated to form a continuous film.
- PVC polyvinylidene chloride
- polyethylene polyethylene
- polyamides polytetrafiuoroethylenes plated out as a film of dense discrete particles
- fluorocarbon surfactant to the aqueous bath helps to obtain maximum deposition of dense films of the particles.
- PVC, polyethylene and polyvinylidene chloride are deposited very readily and good continuous films can be formed by heating the films.
- glass and ceramic films formed by heat treatment of articles coated with electrodeposits of fine glass and ceramic particles.
- boron powder or silicon powder on stainless steel or nickel or Monel cathodes.
- the films of boron powder or silicon powder can then act as a flux in the joining of stainless to stainless, or stainless to nickel, or the like, by pressing, for example, boron powder filmed stainless article to another stainless or nickel article and heating to a high temperature in a vacuum.
- Mixed particles such as barium sulfate and PVC, barium sulfate and graphite, and the like may also be used.
- EXAMPE l A film of barium sulfate particles is deposited over the entire cathode. After rinsing, the nickel plated cathode with its film of fine barium sulfate particles is transferred to a chromium plating bath and plated with 0.005 to 0.02 mil of chromium, or similar thicknesses of gold plate from an alkaline or acidic gold plating bath. A beautiful satin appearance is obtained in each case. The corrosion protection for the underlying basis metal of steel or zinc die cast that is copper plated, then nickel plated before electrodepositing the film of fine particles and then the final plating with chromium or gold, or for that matter silver or rhodium, is truly outstanding. Corrodkote and CASS accelerated tests show the extremely excellent corrosion protection obtained compared to the case where there is no film of particles present. The film of particles can be plated with thin nickel prior to the chromium, gold, silver or rhodium final plate.
- EXAMPLE 2 Instead of barium sulfate particles in the same bath as in Example 1, precipitated silica particles or micronized silica hydrogels of ultimate particle size of about 0.01 to 0.03 micron are used in concentrations of 5 to 50 g./l., and when the same plating tests are run, the same excellent results are obtained except that the appearance of the final thin chromium or gold or silver or rhodium plate is as bright or almost as bright as the underneath nickel. That is, when the ultimate particle size of the silica particles is around 0.02 micron, even though agglomerate sizes may be as large as 6 to 10 microns, the particles do not cause appreciable dulling of the subsequent plate.
- EXAMPLE 3 Instead of fine powders of silica, barium sulfate, aluminum silicate and zirconium oxide electrodeposited and processed as described in Example 2, films of fine powders of molybdenum sulfide, graphite, lead powder or mixtures are electrodeposited as films on a metal such as steel, aluminum, copper, nickel, bronze, brass, etc. and subsequently plated with thin plates of copper, nickel, silver, bronze, brass, tin, lead, lead-tin alloy and lead-tincopper alloy. Multiple layers are also plated such as a thin plate of copper followed by a thin film of tin and then heat diffused to obtain a bronze matrix with imbedded particles of lead or graphite or molybdenum sulfide or mixtures. Additionally, a lead-tin plate (-10) can also be plated over the copper or nickel plate. Such surfaces make excellent bearing surfaces of low friction and antiseizing properties and are excellent for cold starting.
- EXAMPLE 4 Following the procedure of the proceeding examples, the powders are electrodeposited on a passive surface such as dry nickel plate or a chromate dipped and rinsed nickel plate, or a stainless steel surface or on a thin film of cadmium plate from an alkaline cyanide bath deposited on steel on which the adhesion is poor. Then after a subsequent deposit of nickel, iron, cobalt or their alloys, or copper, silver, brass or bronze is plated over the particles, foils of these metals are formed which contain the imbedded particles in the metal matrix.
- a passive surface such as dry nickel plate or a chromate dipped and rinsed nickel plate, or a stainless steel surface or on a thin film of cadmium plate from an alkaline cyanide bath deposited on steel on which the adhesion is poor.
- nickel, iron, cobalt or their alloys, or copper, silver, brass or bronze is plated over the particles, foils of these metals are formed which contain the imbedded particles in the metal matrix.
- the particles are polystyrene or a carbonate such as nickel carbonate
- the particles are removed from the foils by, in the case of polystyrene, heating in a vacuum or inert atmosphere, and for nickel carbonate, a hydrogen atmosphere furnace which will reduce the nickel carbonate to nickel.
- a very finely porous foil is formed.
- Fluorocarbon particles are cathodically deposited on a metal or conducting surface with the following bath.
- a method of electroplating which comprises electrodepositing at a current density of to 100 amps per sq. ft., in the absence of ions that can be electroplated, a film of fine particles of water-insoluble powders from a dispersion thereof in an agitated aqueous solution of a salt of a monovalent cation selected from the class of alkali metal cations and an ammonium cation, on a cathode surface selected from the group consisting of nickel, brass, and copper, and then electrodepositing on the same cathode a plate of less than about 0.5 mil thickness of a metal selected from a group consisting of nickel, chromium, gold, rhodium, brass, bronze, silver, and an alloy consisting of 65% tin and 35% nickel.
Abstract
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US83490169A | 1969-06-19 | 1969-06-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3687824A true US3687824A (en) | 1972-08-29 |
Family
ID=25268087
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US834901A Expired - Lifetime US3687824A (en) | 1969-06-19 | 1969-06-19 | Electrodeposition of films of particles on cathodes |
Country Status (1)
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US (1) | US3687824A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3787338A (en) * | 1972-02-25 | 1974-01-22 | Gen Electric | Aqueous dispersions of finely divided lubricants in polyamide acid |
US3868311A (en) * | 1971-11-09 | 1975-02-25 | Citroen Sa | Methods for the formation on a wall exposed to frictional forces and belonging to a light alloy element, of a wear-resistant composite coating metallic |
US3922207A (en) * | 1974-05-31 | 1975-11-25 | United Technologies Corp | Method for plating articles with particles in a metal matrix |
US3926761A (en) * | 1973-04-09 | 1975-12-16 | Kansai Paint Co Ltd | Aqueous electrophoretic coating compositions comprised of polycarboxylic acid binder resin and sparingly soluble alkaline earth metal molybdate |
FR2325735A1 (en) * | 1975-09-26 | 1977-04-22 | Siemens Ag | SILVER-BASED ELECTROLYTE CYANIDE FOR THE ELECTROLYTIC DEPOSIT OF SILVER-GRAPHITE DISPERSION COATINGS |
US4160707A (en) * | 1976-04-26 | 1979-07-10 | Akzo N.V. | Process for applying coatings containing both a metal and a synthetic resin |
US4975160A (en) * | 1985-04-13 | 1990-12-04 | Licentia Patent-Verwaltungs-Gmbh | Process for wet chemical metallization of a substrate |
US5580375A (en) * | 1993-06-18 | 1996-12-03 | Surface Technology, Inc. | Prestabilization of particulate matter prior the dispersion |
-
1969
- 1969-06-19 US US834901A patent/US3687824A/en not_active Expired - Lifetime
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3868311A (en) * | 1971-11-09 | 1975-02-25 | Citroen Sa | Methods for the formation on a wall exposed to frictional forces and belonging to a light alloy element, of a wear-resistant composite coating metallic |
US3787338A (en) * | 1972-02-25 | 1974-01-22 | Gen Electric | Aqueous dispersions of finely divided lubricants in polyamide acid |
US3926761A (en) * | 1973-04-09 | 1975-12-16 | Kansai Paint Co Ltd | Aqueous electrophoretic coating compositions comprised of polycarboxylic acid binder resin and sparingly soluble alkaline earth metal molybdate |
US3922207A (en) * | 1974-05-31 | 1975-11-25 | United Technologies Corp | Method for plating articles with particles in a metal matrix |
FR2325735A1 (en) * | 1975-09-26 | 1977-04-22 | Siemens Ag | SILVER-BASED ELECTROLYTE CYANIDE FOR THE ELECTROLYTIC DEPOSIT OF SILVER-GRAPHITE DISPERSION COATINGS |
US4160707A (en) * | 1976-04-26 | 1979-07-10 | Akzo N.V. | Process for applying coatings containing both a metal and a synthetic resin |
US4975160A (en) * | 1985-04-13 | 1990-12-04 | Licentia Patent-Verwaltungs-Gmbh | Process for wet chemical metallization of a substrate |
US5580375A (en) * | 1993-06-18 | 1996-12-03 | Surface Technology, Inc. | Prestabilization of particulate matter prior the dispersion |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: OXY METAL INDUSTRIES CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084 Effective date: 19741220 |
|
AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP. Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885 Effective date: 19801222 |
|
AS | Assignment |
Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |
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AS | Assignment |
Owner name: OMI INTERNATIONAL CORPORATION, 21441 HOOVER ROAD, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004190/0827 Effective date: 19830915 |
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AS | Assignment |
Owner name: MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF NY Free format text: SECURITY INTEREST;ASSIGNOR:INTERNATIONAL CORPORATION, A CORP OF DE;REEL/FRAME:004201/0733 Effective date: 19830930 |