Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60Q—ARRANGEMENT OF SIGNALLING OR LIGHTING DEVICES, THE MOUNTING OR SUPPORTING THEREOF OR CIRCUITS THEREFOR, FOR VEHICLES IN GENERAL
  • B60Q7/00—Arrangement or adaptation of portable emergency signal devices on vehicles
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1655—Process features
  • C23C18/1664—Process features with additional means during the plating process
  • C23C18/1671—Electric field
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/31—Coating with metals
  • C23C18/38—Coating with copper
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/31—Coating with metals
  • C23C18/38—Coating with copper
  • C23C18/40—Coating with copper using reducing agents
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
  • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
  • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
  • C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
• • 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
  • C25D5/10—Electroplating with more than one layer of the same or of different metals
  • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium

Definitions

• Electroplating involves'the use of a DC. circuit consisting of a source of direct current and an anode and cathode disposed in an electrolytic bath. With this arrangement, the plating metal is used as an anode which is depleted as ions of the plating metal migrate to the cathode where they are reduced to form a coating on the base metal comprising the cathode.
• Immersion plating like electroless plating, does not employ an electric current.
• immersion plating also utilizes a solution of a salt of the plating metal in which the base metal is immersed, in immersion plating the plating metal deposits on the base metal by means of displacement rather than reduction.
• the plating metal must be below hydrogen in the electromotive seriesand the base metal above hydrogen" in order for the substitution of the base metal for the plating metal in solution to occur.
• electroplating is very widely used to provide adherent plated coatings of almost any desired thickness, it is not suitable for use with tiny articles, such as shot, fibers, and granular or other particulate material. This is true principally because it is difficult to utilize such articles or materials as a cathode in'a platingfbath'For this reason, either electroless or immersion plating is preferred where uniform plated coatings aredesired on very tiny articles'or particulate material.
• valve metals such as aluminum, tantalum, titanium and niobium readily form 3,558,349 Patented Jan. 26, 1971 adherent oxide coatings which are electrically resistant. Indeed, this is why the valve metals are anodized and used as electrodes in electrolytic capacitors. Because of this tendency to form oxide coatings in water or water solutions, the valve metals are exceedingly diflicult to plate.
• metals such as beryllium or titanium which readily form oxide coatings that impair the tenacity of a plated coating.
• an object of the present invention to provide an inexpensive, low temperature method of applying adherent coatings on diflicult-to-plate metal substrates such as beryllium, titanium, aluminum, niobium and zirconium.
• my method includes the steps of (1) immersing an article containing one or more of the foregoing metals in a room temperature methanol solution of a halide of the plating metal and (2) removing the article from the solution when the desired plated coating is obtained.
• This method may be carried on at room temperature, or almost any suitable temperature below the boiling point of the solution, thereby eliminating the need for an expense of carrying on a part of the plating process at high temperatures. It also provides a strongly adherent plated coating on base metals such as beryllium, aluminum, titanium, niobium, zirconium, and alloys and solutions of these metals. Even in cases where electroplating is preferred, my methanol solution may be used with a plating current to provide results not readily attainable with the typical plating solutions using water as the solute.
• the halide is the chloride of a metal below hydrogen in the electromotive series.
• EXAMPLE I A piece of titanium was immersed in a solution comprising about 2 gms. of anhydrous copper chloride (CuCI dissolved in 100 cc. of reagent grade absolute methyl alcohol. After a few minutes the titanium was removed from the solution and the surface rinsed under water and wiped dry. A-n adherent copper coating on the titanium was obtained. It should be noted, however, that in this and the following examples, trace amounts of water are actually present in the CuCl and that the presence of minute amounts of water are actually beneficial to the process.
• CuCI anhydrous copper chloride
• Removal of the oxide scale on the base metal prior to plating by my method is not essential for obtaining an adherent deposit.
• an oxide free surface such as might be obtained by mechanical abrasion, is desirable for more rapid and uniform plating.
• Chemical removal of the oxide scale is also suitable as a substitute for mechanical abrasion.
• EXAMPLE III Several strips of aluminum were immersed in 100 ml. of anhydrous methanol containing 3 gms. of CuCl One strip was immersed for 3 minutes, one for 6 minutes and one for 30 minutes.
• the copper thickness on the aluminum was determined by metallographic measurements. That is, the samples were cross sectioned, the edges were polished and the thickness of the plated coating was metallographically measured.
• the sample immersed for 3 minutes had a coating thickness of approximately .1 to .2 mil.
• the sample immersed for 6 minutes had a coating thickness of .3 to .4 mil, and the sample immersed for 30 minutes had a coating thickness of approximately .5 mil.
• ethanol has been found to be completely unsatisfactory as a halide solvent for use in plating beryllium or titanium. It has also been found unsatisfactory as a solvent for 4 plating Lockalloy (Trademark of the Lockheed Aircraft Corporation for a beryllium aluminum alloy).
• salts other than halides as for example nitrates and sulfates of the plating metals, have been tried and under experimental conditions, like those used in the above examples, have also been found to be unsatisfactory.
• an anhydrous methanol solution of nickel chloride may be used to apply an adherent nickel coating on any one of the aforesaid base metals.
• the plating time is significantly reduced when a current is used.
• the methanol solution of nickel chloride is used as the electrolyte in a conventional plating bath.
• the base metal then serves as a cathode and nickel is the anode.
• my method can be used to provide a base coating, such as copper, for subsequent electroplating of metals, such as chromium, which do not readily plate on a variety of substrates.
• a method of electrolessly immersion coating adherent layers of a metal below hydrogen in the electromotive series onto articles comprising at least one of the metals selected from the group consisting of aluminum, beryllium, titanium, niobium and zirconium, said method comprising:

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Electroplating Methods And Accessories (AREA)
• Chemically Coating (AREA)
• Electroplating And Plating Baths Therefor (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=24884186

Family Applications (1)

Country Status (6)

Cited By (2)

• 1968
  • 1968-04-01 US US717950A patent/US3558349A/en not_active Expired - Lifetime
• 1969
  • 1969-04-01 GB GB1257492D patent/GB1257492A/en not_active Expired
  • 1969-04-01 FR FR6909934A patent/FR2005332A1/fr not_active Withdrawn
  • 1969-04-01 DE DE19691916727 patent/DE1916727A1/de active Pending
  • 1969-04-01 JP JP44025162A patent/JPS491699B1/ja active Pending
  • 1969-04-01 SE SE04667/69A patent/SE352905B/xx unknown

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