US3671291A - Electroless process for forming thin metal films - Google Patents

Electroless process for forming thin metal films Download PDF

Info

Publication number
US3671291A
US3671291A US3671291DA US3671291A US 3671291 A US3671291 A US 3671291A US 3671291D A US3671291D A US 3671291DA US 3671291 A US3671291 A US 3671291A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
solution
metal
nickel
films
cobalt
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
Inventor
Richard G Miller
Roy L Cavitt
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.)
PPG Industries Inc
Original Assignee
PPG Industries Inc
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
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C03C17/10Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the liquid phase
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/52Chemical 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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50

Abstract

THE INVENTION DESCRIBED HEREIN RELATES TO AN ELECTROLESS PROCESS FOR FORMING THIN METAL FILMS, PARTICULARLY TRANSPARENT FILMS, ON A REACTIVE SUBSTRATE. IT PARTICULARLY RELATES TO A METHOD OF SPRAYING TWO SOLUTIONS, ONE, AN ACIDIC SOLUTION CONTAINING A METAL SALT AND THE OTHER, AN ALKALINE SOLUTION CONTAINING A BORON REDUCING AGENT, ONTO A REACTIVE SUBSTRATE TO FORM A METAL FILM BY REDUCTION OF THE METAL SALT. MORE PARTICULARLY, THE INVENTION RELATES TO AN ELECTROLESS PROCESS FOR FORMING METAL FILMS OF METALS CONTAINED IN GROUP IB AND GROUP VIII OF THE PERIODIC TABLE, ESPECIALLY IRON, COBALT, AND NICKEL, BY FORMING A SOLUTION OF SOLUBLE SALTS OF SAID METALS IN AN ACIDIC, AQUEOUS MEDIA, PREFERABLY INCLUDING BORIC ACID AND SPRAYING SAID SOLUTION ON A REACTIVE SUBSTRATE AT SUBSTANTIALLY THE SAME TIME THAT AN ALKALINE SOLUTION OF A BORON-CONTAINING REDUCING AGENT, ESPECIALLY ALKALI METAL BOROHYDRIDES, IS SPRAYED ON THE SUBSTRATE. THE INVENTION HAS BEEN FOUND TO BE PARTICULARLY USEFUL FOR FORMING TRANSPARENT FILMS OF COBALT, NICKEL, IRON, AND THE LIKE ON SENSITIZED TRANSPARENT SUBSTRATES SUCH AS GLASS AND PLASTIC.

Description

United States Patent fire 3,671,291 Patented June 20, 1972 3,671,291 ELECTROLESS PROCESS FOR FORMING THIN METAL FILMS Richard G. Miller, Pittsburgh, and Roy L. Cavltt, New Kensington, Pa., assignors to PPG Industries, Inc., Pittsburgh, Pa. No Drawing. Filed June 2, 1969, Ser. No. 829,705 Int. Cl. B44d 1/20, 1/092; C23c 3/02 US. Cl. 117-54 8 Clanns ABSTRACT OF THE DISCLOSURE The invention described herein relates to an electroless process for forming thin metal films, particularly transparent films, on a reactive substrate. It particularly relates to a method of spraying two solutions, one, an acidic solution containing a metal salt and the other, an alkaline solution containing a boron reducing agent, onto a reactive substrate to form a metal film by reduction of the metal salt. More particularly, the invention relates to an electroless process for forming metal films of metals contained in Group Ib and Group VIII of the Periodic Table,

especially iron, cobalt, and nickel, by forming a solution.

of soluble salts of said metals in an acidic, aqueous media, preferably including boric acid and spraying said solution on a reactive substrate at substantially the same time that an alkaline solution of a boron-containing reducing agent, especially alkali metal borohydrides, is sprayed on the substrate. The invention has been found to be particularly useful for forming transparent films of cobalt, nickel, iron, and the like on sensitized transparent substrates such as glass and plastic.

BACKGROUND Techniques of electroless plating of metal films on various types of substrates are well known in the art. Electroless plating of metals such as nickel, cobalt, iron, and the like on metallic substrates or on sensitized non-metallic substrates is an important process in the electro-chemieal industry. An electroless process generally involves an aqueous media having dissolved therein a metal salt and an appropriate reducing agent. A metallic article or a sensitized non-metallic article is immersed in an electroless plating bath whereupon a metal film is deposited upon the article by an autocatalytic mechanism.

Although the electroless process is an old and established one, improvements are constantly being sought. For example, Brenner and Riddell discovered in 1944 that nickel could be auto-catalytically deposited upon metallic substrates from a nickel salt solution containing sodium hypophosphite. US. Patents 2,532,283 and 2,532,284 were issued to Brenner and Riddell upon their discoveries. The Brenner process, however, proceeds satisfactorily only at elevated temperatures which is disadvantageous for certain substrates such as the thermoplastic organic polymeric materials. Recent improvements in electroless immersion plating involve the use of boron-containing reducing agents which are efiective at room temperature. U.S. Patent 3,140,188 and US. Patent 3,045,334 are representative of improved electroless plating processes of this type.

Although immersion plating of the so-called catalytic metals, that is, iron, platinum, silver, nickel, gold, cobalt, palladium, and copper, on sensitized non-metallic materials, as, for example, materials sensitized in accordance with the method described in U.S. Patent 2,702,253, are quite efiicient for certain purposes, such processes do have disadvantages. An immersion process is not especially adaptable to coating extremely large articles. Also, the composition of the plating bath changes during use, thereby requiring frequent chemical analysis and addition of materials to maintain a constant bath composition. If a constant bath composition is not maintained, the metal films formed therein are non-uniform.

Furthermore, immersion processes are not especially adaptable to forming transparent films inasmuch as the rate of deposition is difficult to control and film non-uniformity results since a heavier coating is deposited upon that portion of the article which is the first to enter and last to leave the plating bath.

Some of the above-mentioned objections can be overcome with a spraying process. One type of spraying process is described in US. Patent 2,956,900 of Carlson et al. wherein two separate solutions are sprayed upon substrates to form nickel coatings. This process uses sodium hydrosulfite and sodium hypophosphite as reducing agents. One disadvantage of the process is the sulphurous fumes which are emitted when hydrosulfite reducing agents are utilized. Another disadvantage is the inability of the process to form uniform, transparent films upon a sensitized glass or plastic substrate.

Although considerable elfort has been expended in the development of an electroless process for deposition of metal coatings, there is no described process which is entirely satisfactory for the formation of uniform, thin films, especially transparent films, upon reactive substrates.

INVENTION It has now been discovered that uniform, thin films can be developed by spraying upon a reactive substrate, an acidic metal salt solution, preferably containing boric acid, and an alkaline reducing solution containing a boroncontaining reducing agent, preferably an alkali metal borohydride. This process has been found to be largely independent of temperature and is effective for coating any of the so-called catalytic metal substrates or non-catalytic substrates sensitized in a manner to promote deposition of continuous, adherent metal films. Catalytic substrates and processes for rendering inert substrates catalytic are well known.

Both opaque and transparent films may be produced by the method of this invention. Best uniformity of transparent films is achieved when the film is deposited to a thickness having light transmission of about 30% or less. The films produced by this invention are continuous and adherent to the substrate.

Sheets of glass filmed with transparent metal films of this invention, especially nickel, cobalt and iron films, are useful as solar control windows, reflecting much of the solar radiation impinging thereon. Opaque metal films can be utilized on metal or other substrates as mirrors or to provide corrosion resistance.

METAL SALT SOLUTION A solution containing a metal of Groups Ib and VIII of the Periodic Table consists generally of a metal salt of an inorganic or organic acid and a small amount of an organic or inorganic acid, preferably boric acid, to maintain a solution pH of less than 7. When an acid other than boric acid is used to adjust solution pH, boric acid is to be included in the solution as well and is to be employed in an amount which is effective to promote film uniformity. The preferred metals are nickel, cobalt, and iron, although copper, lead, antimony, tin, bismuth, and noble metals such as palladium, platinum, osmium, gold, silver, and the like, and alloys of the above, may be utilized according to the practice of this invention.

As mentioned above, various metal salts of inorganic and organic acids soluble in aqueous solutions may be utilized. Metal salts having only slight solubility in aqueous solutions may be utilized inasmuch as active concentrations of metal range from about 0.1% by weight to about 20% by weight of the solution. A preferred concentration is about 0.5% by Weight to about by weight of the metal ion per unit weight of solution. Furthermore, the valence state of the soluble metal ion is unimportant, for example, cobaltous or cobaltic salts are equally effective.

Typical metal salts useful in this invention include: nickel chloride, nickel bromide, nickel iodide, nickel sulphate, cobalt bromide, cobalt chloride, cobalt fluoride, iron chloride, iron bromide, iron sulphate, and the like. Also useful are the halides, especially chlorides, nitrates, and like salts of copper, lead, antimony, tin, bismuth, and the above-mentioned noble metals.

Typical salts of organic acids useful in this invention include: nickel acetate, nickel propionate, nickel fluorborate, nickel citrate, nickel tartrate, nickel maleate, cobalt acetate, cobalt citrate, cobalt itaconate, and the like. Similar organic salts of a copper, lead, tin, antimony, bismuth, and the above-mentioned noble metals are also useful.

As mentioned hereinabove, the metal containing solution contains sufficient quantity of an acid to maintain a pH of less than 7. Although a pH range of 1 to 7 is effective, a preferred pH range is from about 4 to about 5. Numerous acids, of course, can be utilized to maintain an effective pH range, for example, inorganic acids such as hydrochloric, nitric, sulphuric, boric, and carbonic acids, and the like, may be utilized as well as organic acids such as acetic acid, propionic acid, citric acid, tartaric acid, and the like, may be utilized. Although the above acids are effective in maintaining a proper pH range, it has been found that boric acid is preferred in maintaining a pH range of between 4 and 5. Moreover, boric acid has been found to promote film uniformity and to reduce the tendency of the metal film to peel from the substrate during spraying. These features are especially desirable in the formation of transparent metal films. In order to obtain improved film uniformity boric acid is essential in the metal containing solution even though additional acids may be utilized and to aid in pH control.

The metal-containing solution may contain an appropriate wetting agent. Wetting agents which have been found particularly effective in a spray process for deposition of transparent films of nickel, cobalt, iron, and the like, are non-ionic and cationic wetting agents which are known not to precipitate heavy metals from solution. Wetting agents particularly useful for this purpose include:

Cationic agents such as:

( 1) quaternary ammonium salts, for example tetramethyl ammonium chloride dipropyl dimethyl ammonium chloride (2) alkylene oxide condensation products of organic amines, for example wherein R is a fatty alkyl group preferably having about 12 to 18 carbon atoms and x and y represent whole numbers from 1 to about 20, typical products of this type being ethylene oxide condensation products of coco amines, soybean amines, and the like, having an average molecular Weight of about 200 to about 3000.

Non-ionic agents such as:

( 1) Alkylene oxide condensates of amides, for example hydrogenated tallow amides having a molecular weight of about 200 to about 3-00, and oleyl amides wherein a typical structure is I where R, x and y have the same significance as set forth immediately hereinabove for organic amine condensates;

(2) Alkylene oxide condensates of fatty acids.

Wetting agents of the above types are useful in promoting film uniformity. Of particular utility are the alkylene oxide condensation products of organic amines which have been found to promote substantially mottle-free transparent films of nickel, cobalt, iron and the like formed by the spray process described herein. Coco amine-ethylene oxide condensates having a molecular weight of greater than about 300 have been found especially elfective for this purpose. A typical coco amine is Ethomeen C-15 of Armour and Company, described hereinafter in the examples.

REDUCING SOLUTION The reducing solution comprises an aqueous solution of a boron-containing reducing agent, said solution having a pH of 7 to 14, and preferably of about 8 to 10. The boron-containing reducing agent may be present in solution as about 0.01% by Weight to about 5% by weight of the solution. While boron-containing reducing agents are effective in the aforementioned range, a preferred concentration of 0.05% by weight to about 2% by weight is preferred. Exceptionally useful boron-containing reducing agents are the alkali metal borohydrides such as sodium borohydride, lithium borohydride, and potassium borohydride. Other boron-containing reducing agents, however, are effective although frequently unavailable in commercial quantities. Exemplary boron-containing reducing agents other than borohydrides are the boron-containing compounds listed in U.S. Patent 3,140,188 of Zirngiebl et al., incorporated herein by reference. Amine boranes such as diethylamine borane, trimethylamine borane, triethylamine borane, and pyridine borane may also be used. Other effective boron-containing compounds include substituted borohydrides such as sodium trimethoxy borohydride and the like.

The reducing solution is preferably alkaline inasmuch as boron-containing reducing agents oxidize very rapidly in acid and neutral solutions. The alkalinity of the reducing solution should not be so great that the pH of the intermixed metal-containing solution and reducing solution is above 7. It is preferred that the pH of the intermixed solution, that is, the solution formed by the impingement of the two spray solutions at the surface of the object to be coated, be 7 or less.

PROCESS The metal-containing solution and reducing solution are each passed through separate spray nozzles so that the sprays intermix and contact the surface of the article to be coated. Single nozzle guns may also be used where the solutions intermix in the gun or outside the gun. The flow rates of each solution may be approximately equal or may vary greatly. The flow rates of the respective solutions are not critical, however, it is desirable to maintain a weight ratio of reducing agent to metal contained in the metalcontaining solution of about 10:1 to about 1:2000 parts per Weight reducing agent to parts per Weight of metal. The temperature of the article to be coated is not material although the temperature of the article should be uniform in order to promote film uniformity. The process is quite effective at room temperature, although a preferred temperature range is from 40 F. to about 200 F.

The substrate must be receptive to metal deposition. For the deposition of films of nickel, cobalt, iron, and the like, it is preferred to have a reactive metal substrate, for example, in the formation of a transparent article, an appropriate substrate is a transparent glass article coated with a transparent metal film of copper, aluminum, tungsten, cobalt, platinum, silver, boron, thallium, vanadium, titanium nickel, gold, germanium, silicon, chromium, molybdenum, iron, tin, palladium, lead, indium, cadmium, zinc, and the like. These metals are known as catalytic metals for electroless deposition of films of cobalt, nickel, iron, and the like. For example, a transparent copper film could be deposited on a transparent glass or plastic substrate by means of vacuum deposition or sputtering and thereafter sprayed according to the teaching of this invention with a transparent coating of nickel, cobalt, iron, or the like.

A further method of preparing the substrate for electroless deposition according to this invention may be accomplished in accordance with the teaching of US. Patent 2,702,253 or US. Patent 3,011,920, the teachings therein being incorporated herein by reference.

Example I A glass sheet was washed with a commercial detergent until the glass was completely and uniformly wetted by water. The sheet was rinsed with tap water and then rinsed with demineralized water.

The glass surface was then contacted with a dilute solution of stannous chloride (about 0.1 percent by weight of SnCl The glass was thoroughly rinsed with demineralized water and then contacted with a dilute solution of palladium chloride (about 0.025 percent by weight of PdClz). The glass was completely rinsed with demineralized water.

The glass was contacted with two sprays, one of nickel solution, the other of reducing solution, to form a nickel film. The sprays intermingled at the glass surface. Each spray had a fiow rate which ranged from 50 to 500 ml./ min., however, the rates were maintained in a balanced condition.

Nickel solution composition:

NiCl -2H O5.0 grams Boric acid-2.5 grams Water-1 liter Ethomeen C-15--2 drops Ethomeen C-l5 (trademark of Armour and Company) is a cocoamine having an average molecular weight of 422 and the following generalized formula:

wherein R is derived from a cocoamine and x plus y equals 5.

Reducing solution composition:

Sodium borohydride0.5 grams Waterl liter Ethomeen C15-1 drop Adjusted pH to 9-10 with NaOH The nickel coated glass has a light transmission of about 12 percent after being contacted for about 1 min. at a flow rate of about 70 milliliters/min. Film formation occurred in about one to two minues and the film was clear, uniform and substantially mettle-free.

Example II A glass sheet was coated with cobalt in substantially the same manner as in Example I, being cleaned, sensitized, and super-sensitized in the same manner as Example I.

The cobalt solution was indentical to Example I with 5 grams cobaltous chloride replacing the nickel chloride. The reducing solution had the same composition. The spray rates were also the same.

A 12" x 12" glass sample was coated with cobalt metal. The film had a slight brownish tint but was uniformly transparent and had light transmission of percent after spraying for two minutes at a flow rate of about 60-70 milliliters/minute for each solution.

Example III NiCl -2H O-7.5 grams Water-l liter pH4.0-5 .0 (no adjustment necessary) Reducing solution composition:

Sodium borohydride0.5 gram Waterl liter pH adjusted to 9-10 with aqueous NaOH solution of about 0.1 N

A nickel film was formed having a transmission of 14 to 30 percent at a flow rate of 60 to 70 milliliters per minute after one minute. A non-uniform film having good adhesion was formed.

When nickel sulfate was substituted for nickel chloride in the above examples, comparable films are obtained.

When potassium borohydride was substituted in the above examples, comparable results are obtained.

Example IV To determine the elfectiveness of acids other than boric acid, an experiment was conducted where the following nickel containing solution was utilized:

NiSO 25 grams Sodium tartrate25 grams Water-1 liter pH adjusted to 5 with NaOH solution A standard sodium borohydride reducing solution of the type described in Example I was utilized; only a trace of nickel film was formed on the glass.

In another variation of this experiment, 10 grams of sodium hypophosphite was added to the nickel solution but no film was formed.

Example V When citric acid was substituted in the above experiment for sodium tartrate, a trace film was formed.

Example VI Test tube experiments were conducted to determine the effectiveness of the following compounds for reducing nickel ions:

Hydrazine tartrate Hydrazine sulfate Hydroxyl ammonium sulfate Sodium hydrosulfite The only reducing agent which reduced nickel ion to nickel metal was sodium hydrosulfite.

The following solutions were admixed on a glass surface to determine the type of nickel film which might result:

Nickel solution composition:

NiSO 20 grams Citric acid-10 grams Sodium hypophosphite-10 grams NaOH8 grams Water1 liter Reducing solution composition:

10 grams per liter of water of sodium hydrosulfite (sodium dithionite) The above solutions gave no film when simultaneously sprayed upon cleaned, sensitized, supersensitized glass.

The sodium hydrosulfite solutions were found to be unstable; stability was enhanced by addition of zinc sulfate and sodium tetraborate.

Sodium formaldehyde sulfoxalate grams per liter) was found to reduce nickel salts, but did not give a nickel film when used in a spray formulation.

Although specific embodiments of the instant inventions have been set forth hereinabove, the invention is not intended to be limited thereo, but to include all of the modifications and variations falling within the scope of the following claims.

We claim:

1. A process for forming thin metallic films of metals of Group VIII and Group Ib of the Periodic Table on a catalytic sensitized substrate comprising contacting said substrate substantially simultaneously with a spray of a metal salt solution of the selected metal of Groups VIII and Ib having a pH of less than 7 and a spray of a reducing solution having a pH greater than 7:

(a) said metal salt solution comprising water, a metal salt of an organic or inorganic acid, and an effective amount of boric acid to provide an observably uniform metallic film on the substrate; and

'(b) said reducing solution comprising water and a boron-containing reducing agent.

2. The method of claim 1 wherein the metal salt is selected from the class of salts of nickel, cobalt, and iron and mixtures thereof.

3. The method of claim 2 wherein the metal salt is a nickel salt.

4. The method of claim 1 wherein the boron-containing reducing agent is a alkali metal borohydride.

5. The method of claim 1 wherein the metal films and the substrate are transparent.

6. The method of claim 1 wherein the process is carried out at a temperature of about 40 F. to 200 F.

7. A method of forming transparent metal films of nickel, cobalt, and iron on a glass substrate by (a) contacting said substrate with an aqueous stannous chloride sensitizing solution;

(b) contacting said sensitized substrate with an aqueous. super-sensitizing solution of a noble metal selected from the group consisting of salts of palladium and platinum;

(c) contacting said super-sensitized substrate substantially simultaneously with a spray of an aqueous metal salt solution having a pH of less than 7 and a spray of an aqueous reducing solution having a pH greater than 7 said solution intermixing at the glass surface to form a coating solution having a pH of less than 7;

(1) said metal salt solution comprising salt of metals selected from the class consisting of nickel, cobalt, and iron, and mixtures thereof, and an effective amount of boric acid to provide an observably uniform metallic film on the substrate, and

(2) said reducing solution containing an alkali borohydride.

8. The method of claim 7 wherein the metal salt solution contains from about 0.5 to about 10 percent by weight of metal ion based on the weight of the metal salt solution.

References Cited UNITED STATES PATENTS 2,956,900 10/1960 Carlson et al. 11747 A 3,235,473 2/1966 Le Duc 11747 A 3,295,999 l/1967 Klein et al. 117-47 A 3,370,974 2/1968 Hepfer 1061 X ALFRED L. LEAVITT, Primary Examiner I. A. BELL, Assistant Examiner US. Cl. X.R.

117--47 A, 105, 105.5, 124 C, B, R; l06--1

US3671291A 1969-06-02 1969-06-02 Electroless process for forming thin metal films Expired - Lifetime US3671291A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US82970569 true 1969-06-02 1969-06-02

Publications (1)

Publication Number Publication Date
US3671291A true US3671291A (en) 1972-06-20

Family

ID=25255310

Family Applications (1)

Application Number Title Priority Date Filing Date
US3671291A Expired - Lifetime US3671291A (en) 1969-06-02 1969-06-02 Electroless process for forming thin metal films

Country Status (1)

Country Link
US (1) US3671291A (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3967010A (en) * 1973-11-30 1976-06-29 Kuraray Co., Ltd. Process for the production of metal-plated staple fibers
US3993491A (en) * 1973-12-07 1976-11-23 Surface Technology, Inc. Electroless plating
US4021314A (en) * 1976-03-25 1977-05-03 Western Electric Company, Inc. Method of depositing a metal on a surface
US4082898A (en) * 1975-06-23 1978-04-04 Ppg Industries, Inc. Electroless deposition of electrically nonconductive copper-boron coatings on nonmetallic substrates
FR2413194A1 (en) * 1977-12-28 1979-07-27 Cbs Sony Records Inc Process for manufacturing record disks having an engraving
US4170461A (en) * 1976-12-29 1979-10-09 Ppg Industries, Inc. Heat treatment of electrolessly deposited cuprous oxide coating
US4308319A (en) * 1978-07-03 1981-12-29 Ppg Industries, Inc. Pyrolytic deposition of a cobalt/tin oxide spinel film
US4315055A (en) * 1976-12-29 1982-02-09 Ppg Industries, Inc. Direct electroless deposition of cuprous oxide films
US4400436A (en) * 1980-06-30 1983-08-23 Ppg Industries, Inc. Direct electroless deposition of cuprous oxide films
US4419390A (en) * 1977-06-06 1983-12-06 Nathan Feldstein Method for rendering non-platable semiconductor substrates platable
US4439465A (en) * 1982-02-19 1984-03-27 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Method of making a light weight battery plaque
US4481249A (en) * 1981-02-21 1984-11-06 Bayer Aktiengesellschaft Metallized carbon fibres and composite materials containing these fibres
US4485153A (en) * 1982-12-15 1984-11-27 Uop Inc. Conductive pigment-coated surfaces
US4574094A (en) * 1983-06-09 1986-03-04 Kollmorgen Technologies Corporation Metallization of ceramics
US4666744A (en) * 1984-05-10 1987-05-19 Kollmorgen Technologies Corporation Process for avoiding blister formation in electroless metallization of ceramic substrates
US4701352A (en) * 1984-05-10 1987-10-20 Kollmorgen Corporation Surface preparation of ceramic substrates for metallization
US4830668A (en) * 1986-11-24 1989-05-16 W. C. Heraeus Gmbh Acidic bath for electroless deposition of gold films
US4983428A (en) * 1988-06-09 1991-01-08 United Technologies Corporation Ethylenethiourea wear resistant electroless nickel-boron coating compositions
US6168825B1 (en) 1998-11-02 2001-01-02 O'brien Dudley Process for producing thin transparent gold coatings
US6251482B1 (en) * 1994-05-12 2001-06-26 Glaverbel Forming a silver coating on a vitreous substrate
US6749307B2 (en) 1994-05-12 2004-06-15 Glaverbel Silver coated mirror

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3967010A (en) * 1973-11-30 1976-06-29 Kuraray Co., Ltd. Process for the production of metal-plated staple fibers
US3993491A (en) * 1973-12-07 1976-11-23 Surface Technology, Inc. Electroless plating
US4082898A (en) * 1975-06-23 1978-04-04 Ppg Industries, Inc. Electroless deposition of electrically nonconductive copper-boron coatings on nonmetallic substrates
US4158716A (en) * 1975-06-23 1979-06-19 Ppg Industries, Inc. Electrically nonconductive copper-boron coatings on nonmetallic substrates
US4021314A (en) * 1976-03-25 1977-05-03 Western Electric Company, Inc. Method of depositing a metal on a surface
US4097286A (en) * 1976-03-25 1978-06-27 Western Electric Company, Inc. Method of depositing a metal on a surface
US4170461A (en) * 1976-12-29 1979-10-09 Ppg Industries, Inc. Heat treatment of electrolessly deposited cuprous oxide coating
US4315055A (en) * 1976-12-29 1982-02-09 Ppg Industries, Inc. Direct electroless deposition of cuprous oxide films
US4419390A (en) * 1977-06-06 1983-12-06 Nathan Feldstein Method for rendering non-platable semiconductor substrates platable
FR2413194A1 (en) * 1977-12-28 1979-07-27 Cbs Sony Records Inc Process for manufacturing record disks having an engraving
US4308319A (en) * 1978-07-03 1981-12-29 Ppg Industries, Inc. Pyrolytic deposition of a cobalt/tin oxide spinel film
US4400436A (en) * 1980-06-30 1983-08-23 Ppg Industries, Inc. Direct electroless deposition of cuprous oxide films
US4481249A (en) * 1981-02-21 1984-11-06 Bayer Aktiengesellschaft Metallized carbon fibres and composite materials containing these fibres
US4439465A (en) * 1982-02-19 1984-03-27 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Method of making a light weight battery plaque
US4485153A (en) * 1982-12-15 1984-11-27 Uop Inc. Conductive pigment-coated surfaces
US4574094A (en) * 1983-06-09 1986-03-04 Kollmorgen Technologies Corporation Metallization of ceramics
US4666744A (en) * 1984-05-10 1987-05-19 Kollmorgen Technologies Corporation Process for avoiding blister formation in electroless metallization of ceramic substrates
US4701352A (en) * 1984-05-10 1987-10-20 Kollmorgen Corporation Surface preparation of ceramic substrates for metallization
US4830668A (en) * 1986-11-24 1989-05-16 W. C. Heraeus Gmbh Acidic bath for electroless deposition of gold films
US4983428A (en) * 1988-06-09 1991-01-08 United Technologies Corporation Ethylenethiourea wear resistant electroless nickel-boron coating compositions
US6251482B1 (en) * 1994-05-12 2001-06-26 Glaverbel Forming a silver coating on a vitreous substrate
US6565217B2 (en) 1994-05-12 2003-05-20 Glaverbel Silver coated mirror
US6749307B2 (en) 1994-05-12 2004-06-15 Glaverbel Silver coated mirror
US20040223238A1 (en) * 1994-05-12 2004-11-11 Pierre Laroche Forming a silver coating on a vitreous substrate
US6942351B2 (en) 1994-05-12 2005-09-13 Glaverbel Forming a silver coating on a vitreous substrate
US6168825B1 (en) 1998-11-02 2001-01-02 O'brien Dudley Process for producing thin transparent gold coatings

Similar Documents

Publication Publication Date Title
US3532518A (en) Colloidal metal activating solutions for use in chemically plating nonconductors,and process of preparing such solutions
US3457138A (en) Transparent copper coated glass articles and improved electroless method for producing said articles
US3589916A (en) Autocatalytic gold plating solutions
US5910340A (en) Electroless nickel plating solution and method
US3873360A (en) Method of depositing a metal on a surface of a substrate
US4804410A (en) Palladium-base electroless plating solution
US4397812A (en) Electroless nickel polyalloys
US5165972A (en) Coated glass
US4232060A (en) Method of preparing substrate surface for electroless plating and products produced thereby
US4869970A (en) Radiation attenuation shielding
US3958048A (en) Aqueous suspensions for surface activation of nonconductors for electroless plating
US5925415A (en) Electroless plating of a metal layer on an activated substrate
US2369620A (en) Method of coating cupreous metal with tin
US3745039A (en) Electroless cobalt plating bath and process
US2983634A (en) Chemical nickel plating of magnesium and its alloys
US4600609A (en) Method and composition for electroless nickel deposition
US4749626A (en) Whisker resistant tin coatings and baths and methods for making such coatings
Yesugade et al. Structural and optical properties of electrodeposited Bi2S3, Sb2S3 and As2S3 thin films
US3295999A (en) Process of chemical metal plating and baths therefor
US4152467A (en) Electroless copper plating process with dissolved oxygen maintained in bath
US6565217B2 (en) Silver coated mirror
US4617205A (en) Formaldehyde-free autocatalytic electroless copper plating
US6395329B2 (en) Printed circuit board manufacture
Krishnan et al. An overall aspect of electroless Ni-P depositions—A review article
US3776740A (en) Electroless silvering composition and method