Method for concomitant particulate diamond deposition in electroless plating, and the product thereof

Abstract

This invention is a method for depositing on an article a coating containing at least one member of the group metals and metal alloys plus particulate dispersed diamond comprising contacting the surface of the article with a stable electroless plating bath consisting essentially of an aqueous solution of soluble constituents of the group, electroless reducing agent therefor, a suspension of diamond particles therein and a stabilizer, and maintaining the diamond particles in suspension throughout the bath during the coating of the article for a time sufficient to produce a preselected depth of coating on the article, and the coated article pe se. This is a reissue of a patent which was the subject of a reexamination certificate No. B1 Re. 29,285, dated July 5, 1983, Request No. 90/000,120, Dec. 3, 1981.

What is claimed is: 1. A coated article formed by electroless plating comprising a co-deposited uniform dispersion of .Iadd.polycrystalline .Iaddend.diamond particles secured by substantial nucleation within a metallic matrix comprising one of the group consisting of: (1) an alloy including a metal of the sub-group made up of nickel, cobalt and mixtures thereof with one of the elements phosphorus, boron and mixtures thereof and (2) elemental copper, deposited on a supporting substrate consisting 
     
        of polymer, metal, ceramic or glass. .[..[.2. A method of forming a composite structure on an article by electroless plating comprising immersing said article in a stable electroless plating bath having a composition effecting concurrent deposition of particulate .Iadd.polycrystalline .Iaddend.diamond .Iadd.having a particle size in the range of 0.1μ to 75μ .Iaddend.dispersed in a metallic matrix comprising one of the group consisting of: (1) an alloy including a metal of the sub-group made up of nickel, cobalt and mixtures thereof with one of the elements phosphorus, boron and mixtures thereof and (2) .[.elemental.]. copper, while maintaining agitation of said bath retaining said particulate diamond in suspension, and removing said article carrying said composite structure from said bath .[.when.]. .Iadd.after .Iaddend.said composite structure has been plated out on said article in preselected amount..]..]. 3. A coated article formed by electroless plating consisting of a shaped substrate, a metallic matrix coating deposited on said shaped substrate, and a uniform dispersion of co-deposited .Iadd.polycrystalline .Iaddend.diamond particles secured by nucleation bonding within said metallic matrix, wherein 1. said substrate is one of the group consisting of (a) an organic polymer, including reinforced organic polymers, (b) metals, (c) ceramics, (d) glass,   2. said metallic matrix consists primarily of at least one of the group consisting of (a) nickel, (b) cobalt, (c) copper, together with smaller proportions of other components commonly codeposited from electroless plating baths, and   3. said diamond particles constitute from 1 to 50% by volume of said merallic matrix, with a particle size ranging from about 0.1μ to about 75μ, but predominantly in the size range between 0.5μ to 25μ. 4. A coated article formed by electroless plating consisting of a shaped substrate, a metallic matrix coating deposited on said shaped substrate, and a uniform dispersion of co-deposited diamond particles secured by nucleation bonding within said metallic matrix wherein   1. said substrate is one of the group consisting of (a) an organic polymer, including reinforced organic polymers, (b) metals, (c) ceramics, (d) glass,   2. said metallic matrix consists primarily of at least one of the group consisting of (a) nickel, (b) cobalt, (c) copper, together with smaller proportions of other components commonly codeposited from electroless plating baths, and   3. said diamond particles constitute from 1 to 50% by volume of said metallic matrix, with a particle size ranging from about 0.1μ to 75μ but predominantly in the size range between 0.5μ to 25μ, and said diamond particles individually consist of many individual crystallities tightly bonded to one another in essentially unoriented pattern giving polycrystalline particles having many irregular projections, ledges and   
     
     
        craters. 5. A coated article formed by electroless plating according to claim 3 wherein said article is a fluid jet provided with a discharge orifice. 6. A coated article formed by electroless plating according to claim 4 wherein said article is a fluid jet provided with a discharge orifice. .Iadd.7. A coated article formed by electroless plating comprising a co-deposited uniform dispersion of diamond particles secured by substantial nucleation within a metallic matrix comprising one of the group consisting of: (1) an alloy including a metal of the sub-group made up of nickel, cobalt and mixtures thereof with one of the elements phosphorus, boron and mixtures thereof and (2) elemental copper, deposited on a supporting substrate consisting of polymer, metal, ceramic or glass and an electrolessly deposited strike layer deposited on said substrate beneath said co-deposited uniform dispersion of diamond particles in said metallic matrix, said strike layer being a metallic layer substantially free from solid particulate inclusions. .Iaddend. .Iadd.8. The article of claim 4, wherein said polycrystalline diamond particles, in comparison with other hard particles including natural diamond particles and non-polycrystalline synthetic diamond particles, are characterized by higher resistance to pull-out from said metallic matrix. .Iaddend. .Iadd.9. The article of claim 4, wherein said substrate is a textile machinery component and said coating provides a textile wear surface layer which is characterized by high resistance to surface wear due to contact with textile fibers or yarn. .Iaddend. .Iadd.10. A coated article formed by electroless plating consisting of a shaped substrate, a metallic matrix coating deposited on said shaped substrate, and a uniform dispersion of co-deposited diamond particles secured by nucleation bonding within said metallic matrix, wherein 1. said substrate is one of the group consisting of (a) an organic polymer, including reinforced organic polymers, (b) metals, (c) ceramics, (d) glass,   2. said metallic matrix consists primarily of at least one of the group consisting of (a) nickel, (b) cobalt, (c) copper, together with smaller proportions of other components commonly co-deposited from electroless plating baths, and   3. said diamond particles constitute from 1 to 50% by volume of said metallic matrix, with a particle size ranging from about 0.1μ to 75μ but predominantly in the size range between 0.5μ to 25μ, and said diamond particles individually consist of many individual crystallites tightly bonded to one another in essentially unoriented pattern giving polycrystalline particles having many irregular projections, ledges and craters, and   4. an electrolessly deposited metal strike layer deposited on said substrate prior to the deposition of said metallic matrix containing said diamond particles, said strike layer being substantially free from solid particulate inclusions. .Iaddend. .Iadd.11. The article of claim 10 wherein said polycrystalline diamond particles are characterized by higher resistance to pull-out from said metallic matrix, in comparison with other hard particles including natural diamond particles and non-polycrystalline   
     
     
        synthetic diamond particles. .Iaddend. 12. A method of forming a composite structure on an article by electroless plating comprising immersing said article in a stable electroless plating bath having a composition effecting concurrent deposition of particulate diamond having a particle size in the range of 0.1μ to 75μ dispersed in the metallic matrix comprising one of the group consisting of: (1) an alloy including a metal of the sub-group made up of nickel, cobalt and mixtures thereof with one of the elements phosphorus, boron and mixtures thereof and (2) elemental copper, while maintaining agitation of said bath retaining said particulate diamond in suspension, and removing said article carrying said composite structure from said bath after said composite structure has been plated out on said article in preselected amount and prior to immersion of said article in said stable electroless plating bath containing said particulate diamond, electrolessly depositing on said article a preliminary .[..[.strike.]..]. .Badd.barrier .Baddend.layer of metal, said .[..[.strike.]..]. .Badd.barrier .Baddend.layer being substantially free from solid particulate inclusions .Badd.and thereby protecting the article from the abrasive action of the dispersed particles contained in the bath. 
     
     
        .Baddend. .[..[.13.  A method for producing a composite structure on a substrate to impart wear resistant surfaces to said substrate comprising co-depositing by immersion of a substrate in a stable electroless plating bath,   a layer of metallic matrix containing dispersed diamond particles, (a) said substrate being a material selected from the group consisting of an organic polymer, including reinforced organic polymers, metals, ceramics and glass,   (b) said metallic matrix comprising one of the group consisting of: (1) an alloy including a metal of the sub-group made up of nickel, cobalt and mixtures thereof with one of the elements phosphorus, boron, and mixtures thereof, and (2)  elemental copper, while maintaining agitation of said bath retaining said diamond particles in suspension, and   (c) said diamond particles constituting from 1 to 50% by volume of said metallic matrix, with a particle size ranging from about 0.1μ to 75μ put predominantly in the size range between 0.5μ and 25μ, and said diamond particles individually consisting of many individual crystallites tightly bonded to one another in essentially unoriented pattern giving polycrystalline particles having many irregular projections ledges and craters, and removing said plated substrate carrying said composite structure from said bath after said composite structure has been plated out on said article in preselected amount..]..]. .[..[.14. The method of claim 13 further comprising, before co-depositing said layer of metal containing dispersed diamond particles, electrolessly depositing on said     
     
     
        substrate a metallic strike layer..]..]. .Badd.15.  A method of forming a composite structure on an article by electroless plating comprising: electrolessly depositing a preliminary barrier layer of metal on said article, said barrier layer being substantially free from solid particulate inclusions and thereby protecting the article from the abrasive action of dispersed particles in the electroless plating bath employed subsequent to deposition of the barrier layer;   immersing the article carrying the barrier layer in a stable electroless plating bath to which has been added particulate diamond having a particle size in the range of 0.1μ to 75μ in the form of a slurry, said bath having a composition capable of effecting deposition of the composite structure on the article, said composite structure comprising said particulate diamond dispersed in a metallic matrix, said metallic matrix comprising an alloy including a metal of the sub-group made up of nickel, cobalt and mixtures thereof with one of the elements phosphorus, boron and mixtures thereof, for a time sufficient to allow said composite structure to be electrolessly deposited on the article while maintaining agitation of the bath retaining said particulate diamond in suspension; and   removing said article carrying said composite structure from the bath after the composite structure has been plated out on said article in preselected   
     
     
        amount. .Baddend. .Badd.16.  A method of forming a composite structure on an article by electroless plating comprising: electrolessly depositing a preliminary barrier layer of metal on said article, said barrier layer being substantially free from solid particulate inclusions and thereby protecting the article from the abrasive action of dispersed particles in the electroless plating bath employed subsequent to deposition of the barrier layer;   immersing the article carrying the barrier layer in a stable electroless plating bath to which has been added particulate diamond having a particle size in the range of 0.1μ to 75μ, said bath having a composition capable of effecting deposition of the composite structure on the article, said composite structure comprising said particulate diamond dispersed in a metallic nickel matrix, for a time sufficient to allow said composite structure to be electrolessly deposited on the article while maintaining agitation of the bath retaining said particulate diamond in suspension; and   removing said article carrying said composite structure from the bath after the composite structure has been plated out on said article in preselected amount. .Baddend.