Classifications

• • 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
  • C23C18/48—Coating with alloys
  • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel

Definitions

• This invention relates to novel metal coatings which exhibit exceptional resistance to corrosion and wear. More particularly this invention relates to metal coatings containing nickel, cobalt, boron and thallium and to the reductive deposition of said coatings on the surfaces of substrate articles from aqueous solutions at high pH.
• cobalt-boron coatings of improved hardness containing controlled amounts of thallium dispersed throughout the coatings. It has now been discovered that coatings containing both nickel and cobalt in combination with boron and thallium exhibit marked advantages over the thallium-containing nickel/boron or cobalt/boron coatings described by Bellis. Metal alloy coatings in accordance with the present invention containing boron, thallium and nickel and cobalt are more wear resistant and remarkably more corrosion resistant than those described in the prior art.
• Electroless coatings containing both nickel and cobalt are described in U.S. Patents 3,378,400 and 3,342,338. However in each of those patents a hypophosphite, and not a boron-containing reducing agent was used to deposit said coatings. Similarly U.S. Patent 3,562,000 exemplifies deposition of a metal coating from a bath containing both cobalt chloride and nickel chloride using sodium hypophosphite. Although it is disclosed in that patent that patent that other suitable reducing agents, including borohydrides, could be used in the numbered examples in place of the preferred hypophosphite, there is provided no description of the improved coatings in accordance with this invention. It is therefore a general object of this invention is to provide improved metal coatings containing both nickel and cobalt, boron and thallium.
• a further object of this invention is to provide an article of manufacture coated on at least a portion of its surface with a hard, ductile, wear and corrosion resistant metal coating comprising nickel and cobalt, boron and thallium.
• Still a further object of this invention is to provide a heterogeneous electroless metal alloy coating containing both nickel and cobalt, boron and thallium having a metal concentration gradient in thickness cross-section.
• Another object of this invention is to provide an electroless metal alloy coating presenting a corrosion and wear resistant surface comprising amorphous nodular deposits of nickel, cobalt, boron and thallium.
• Yet another object of this invention is to provide coating baths from which a hard, ductile, wear and corrosion resistant coating can be deposited on at least a portion of the surface of a metal or activated non-metal substrate.
• a novel metal alloy composition containing both nickel and cobalt, boron and thallium.
• the alloy composition is particularly useful for deposition on a surface of an article of manufacture, which is subject to exposure to corrosive conditions or one subject to -4-
• the metal alloy coating composition of the present invention comprises about 67.5 to about 96.5 weight percent nickel, about 2 to about 15 weight percent cobalt, about 0.5 to about 10 weight percent boron and about 1 to about 8 percent thallium.
• the weight ratio of nickel and cobalt in the bulk coating is about 45:1 to about 4:1, more preferably about 25:1 to about 5:1, respectively. It is remarkably hard, yet ductile, and is highly corrosion and wear resistant.
• the present coating is preferably applied to a substrate electrolessly by contacting the substrate with a coating bath containing nickel ioris, cobalt ions, thallium ions, a metal ion complexing agent, and a borohydride reducing agent at pH about 12 to about 14 and at an elevated temperature of about 180 to about 210°F.
• a coating bath containing nickel ioris, cobalt ions, thallium ions, a metal ion complexing agent, and a borohydride reducing agent at pH about 12 to about 14 and at an elevated temperature of about 180 to about 210°F.
• the same baths used for electroless coating in accordance with a preferred embodiment of this invention can be used at ambient temperature for deposition of the present composition in an electrochemical cell.
• Fig. 1 is an electron photomicrograph of the outer corrosion and wear resistant surface of an electroless coating of this invention.
• Fig. 2 is an electron photomicrograph of the substrate interface side of the coating shown in Fig. 1
• An article of manufacture in accordance with this invention is coated on at least a portion of its surface with a hard, ductile, wear and corrosion resistant metallic coating comprising about 67.5 to about 96.5 weight percent nickel, about 2 to about 15 weight percent cobalt, about 0.5 to about 10 weight percent boron and about 1 to about 8 percent thallium.
• Deposition of the metallic coating on suitable substrates can be accomplished by contacting said substrates with a plating bath comprising an aqueous alkaline (pH about 12 to about 14) solution of nickel, cobalt and thallium salts, a metal ion complexing agent to maintain the metal ions in solution and a borohydride reducing agent.
• Suitable substrates are those with so-called catalytically active surfaces including those composed of nickel, cobalt, iron, steel, aluminum, zinc, palladium, platinum, copper, brass, chromium, tungsten, titanium, tin, silver carbon, graphite and alloys thereof. Those materials function catalytically to -6-
• Non-metallic substrates such as glass, ceramics and plastics are in general, non-catalytic materials; however, such substances can be sensitized to be catalytically active by producing a film of one of the catalytic materials on its surface. This can be accomplished by a variety of techniques known to those skilled in the art. One preferred procedure involves dipping articles of glass, ceramic, or plastic in a solution of stannous chloride and then contacting the treated surface with a solution of palladium chloride. A thin layer of palladium is thereby reduced on the treated surface.
• the article can then be plated or coated with the metallic compositon in accordance with this invention by contact with a coating bath as detailed below. It is to be noted that magnesium, tungsten carbide and some plastics have exibited some resistance to deposition of the present coatings.
• a coating bath for deposition of the present coatings comprises
• nickel ions, cobalt ions, and thallium ions in the amounts indicated, expressed as moles per gallon of coating bath: nickel ions, about 0.4 to about 0.9; cobalt ions, about 0.l to about 0.4; and thallium ions, about 4 x 10 —5 to about 8 x 10 —4; (2) chemical means for adjusting the pH of the bath to between about 12 and about 14; (3) a metal ion complexing agent in an amount sufficient to inhibit precipitation of said ions from the highly alkaline coating bath; and
• the borohydride reducing agent can be selected from among the known borohydrides having a good degree of water solubility and stability in aqueous solutions. Sodium and potassium borohydrides are preferred. In addition, substituted borohydrides in which not more than three of the hydrogen atoms of the borohydride ion have been replaced can be utilized. Sodium trimethoxyborohydride [NaB(OCH 3 ) 3 H] is illustrative of that type of compound. Sodium cyanoborohydride has been found to stabilize electroless coating baths utilizing other borohydride reducing agents (U.S. Patent 3,738,849) .
• the coating bath is prepared to have a pH of about 12 to about 14. Best results have beeh observed when the pH of the bath is maintained during the coating process within that range and more preferably at about pH 13.5. Adjustment of bath pH can be accomplished by addition of any of a wide variety of alkaline salts or solutions thereof.
• Preferred chemical means for establishing and maintaining bath pH are the alkali metal hydroxides, particularly sodium and potassium hydroxide, and ammonium hydroxide. Ammonium hydroxide offers an additional advantage in that the ammonium ion -8-
• a metal ion complexing or sequestering agent is required in the bath to prevent precipitation of the nickel and cobalt hydroxides or other basic salts.
• the metal ion complexing agent functions to lower metal ion reactivity; the complexed or sequestered metal ions have minimal reactity with the borohydride ions in the bulk solution but do react at the catalytic surfaces of substrates in contact with the solution.
• the term catalytic surface refers to the surface any article composed of the aforementioned catalytic materials or to the surface of a non-catalytic material which has been sensitized by application of a film of said catalytic materials on its surface.
• the complexing or sequestering agents suitable for use in this invention include ammonia and organic complex-forming agents containing one or more of the following functional groups: primary amin ⁇ , secondary amino, ' tertiary amino, immino, carboxy and hydroxy.
• Many metal ion complexing agents are known in the art.
• Preferred complexing agents are ethylene diamine, diethylene triamine, triethylene tetramine, the organic acids, oxalic acid, citric acid, tarta ic acid and ethylene diamine tetraacetic acid, and the water soluble salts thereof.
• Most preferred for use in the present coating bath are ethylene diamine, the water soluble salts of tartaric acid, ammonia and combinations thereof, -9-
• the nickel, cobalt and thallium ions in the coating bath are provided by the addition to the bath of the respective water soluble nickel, cobalt and thallium salts.
• Any salts of those metals having an anion component which is not antagonistic to the subject coating process is suitable.
• salts of oxidizing acid such as chlorate salts are not desirable since they will react with the borohydride reducing agent in the bath.
• Cobalt, nickel, and thallium chlorides, sulfates, formates, acetates, and other salts whose anions are substantially inert with respect to the other ingredients in the alkaline coating bath are satisfactory.
• the coating bath is typically prepared by forming an aqueous solution of the appropriate amounts of nickel and cobalt salts, adding the complexing agent(s), adjusting the pH to about 12 to about 14, heating to about 195°F, filtering and finally, immediately before introducing the substrate into the bath, adding the required amounts of thallium salt and sodium borohydride (typically in aqueous alkaline solution) .
• the article to be coated or plated using a bath in accordance with this invention is prepared by mechanical cleaning, degreasing, anode-alkaline cleaning, and finally pickling in an acid bath in accordance with the standard practice in the metal-plating art.
• the substrate can be masked if necessary to allow deposition of the metal alloy coating only on selected surfaces.
• coating adhesion is critical or where some adhesion problems are experienced, coating-adhesion can often be enhanced by depositing a nickel strike electrochemically on the substrate surface prior to applying the present coating.
• the cleaned or otherwise surface-prepared article is immersed in the hot (about 180. to about 210°F) coating bath to initiate the coating process.
• a preferred concentration range for each of the metal ion components of the present coating bath is as follows: nickel ions, about 0.5 to about 0.8 moles per gallon; cobalt ions, about 0.15 to about 0.3 moles per gallon; and thallium ions, about 8 x 10 ⁇ to about 4 x 10 —5 moles per gallon.
• a range of about 0.3 to about 0.8 moles per gallon of borohydride reducing agent is preferred.
• the ratio of nickel, cobalt, boron and thallium in the present coatings can be adjusted by varying the relative amounts of the metal salt components and borohydride in the coating bath.
• thallium ions and borohydride reducing agent are added to the coating bath hourly in amount equivalent to their usage in preparation of the bath initially.
• the need to replenish the present coating baths with thallium and borohydride depends on the ratio of coating bath volume to the surface area being coated. Thus replenishment of thallium and borohydride to the present coating bath would not be required where but small surface areas are being treated.
• One gallon of bath prepared in accordance with the preferred embodiment of the present invention will coat approximately 700 square inches to a thickness of 1 mil where the bath is replenished in accordance with the above description with thallium and borohydride ion as those components are depleted from solution.
• the pH of the coating bath will tend to drop during the coating process and should be checked periodically to assure that it is within the preferred pH range of about 12 to about 14. It has been found that any problems with pH maintenance throughout the use of a coating bath can be minimized simply by using a highly alkaline (concentrated sodium hydroxide) solution of borohydride to replenish the borohydride content of the bath as required.
• the coating deposition rate from the present electroless coating bath is about 0.1 to about 1 mil per hour and is dependent on bath -12-
• the electroless coating bath of this invention can also be used for electrolytic deposition of coatings comprising about 67.5 to about 96.5 weight percent nickel, about 2 to about 15 percent weight cobalt, about 0.5 to about 10 weight percent boron and about 1 to about 8 percent thallium.
• the bath is prepared as described above and is used at ambient temperatures as the electrolyte in an electrolytic cell using, for example, a nickel anode and the substrate as the cathode.
• the cell is connected to a 12-volt DC power source and current flow through the cell is adjusted to, for example, about 50 amps per square foot, and current flow is maintained until the metal alloy is deposited on the substrate cathode to the desired thickness.
• the preferred electroless metal alloy coatings of the present invention exhibit unprecedented hardness and concomitant wear resistance. They are highly ductile allowing the coating to flex with the substrate while maintaining a strong bond to the coated material.
• the present coatings are nonporous and exhibit remarkably enhanced corrosion resistance over nickel boron coatings previously known in the art.
• the electroless metal alloy coatings of this invention present a wear and corrosion resistant surface comprising hard, amorphous nodular deposits of metal alloy. Hardness of the present coatings can be increased by heat treatment of the coated articles.
• Heat treatment is accomplished at a temperature of about 375 to about 750°F for a period of about one to about 24 hours. Shorter times, about one to two hours, is preferred for the higher temperatures of between about 550-750°F while longer heat treatment times have been shown to be advantageous at the lower temperature ranges of between about 375 to about 450°F.
• X-ray analysis of the metal alloy coatings prepared in accordance with the preferred embodiments show that the hard, amorphous nodular deposits lie in a somewhat softer metal alloy matrix. See Figs. 1 and 2.
• X-ray analysis (using a JEOL scanning electron microscope with a computerized EDAX analyzer) also revealed that the coating is heterogenous in thickness cross-section having a metal concentration gradient with higher cobalt concentrations at the interface of the coating and the surface of the substrate.
• the corrosion and wear resistant surface (the hard nodular deposits) of several coatings prepared in accordance with preferred embodiments of this invention were shown to comprise about 86 to about 92 percent nickel, about one to about five percent weight cobalt, about one to about eight percent boron, and about one to about five percent thallium. Analysis of those same coatings at the interface of the coating and the surface of the substrate was shown to have high cobalt concentrations (as high as about 95 weight percent cobalt) .
• the nodular deposits making up the wear and corrosion resistant surface presented by the present coatings are believed to be amorphous as deposited from the electroless coating bath.
• X-ray data showed crystalline domains of metal borides selected from nickel boride and cobalt boride dispersed in the amorphous metal alloy matrix.
• the formation of hard crystalline domains of metal borides within the nodular structures is believed to be responsible for the high hardness levels which have been measured for the present heat-treated coatings.
• Heat-treated coatings in accordance with the present invention have been found to have a Knoop hardness value of between about 1230 and about 1300.
• the actual bulk weight percent content of any of the four components in any given coating depends to a some extent on coating thickness.
• the surface-presented nodules are high nickel-low cobalt content while the softer alloy matrix for the nodules formed immediately at the surface of the substrate (i.e., the first deposited component of the present coatings) is of high cobalt and low nickel content.
• the thinner deposits of the present coating have a higher overall weight percent cobalt.
• Thicker coatings in accordance with the present invention have a greater percentage of their thickness in the form of the amorphous nodules and, therefore have lower overall bulk weight percent cobalt content.
• the present coatings have a wide range of applications which will be recognized by those skilled in the art. They have particular utility for coating surfaces of articles which under normal use are subjected to highly abrasive, rubbing, or sliding conditions under high temperatures/pressures. Such high wear conditions are found at many points in construction of tools, internal combustion engines including gas turbine engines, transmissions and in a wide variety of heavy equipment construction applications.
• a five (5) gallon batch unit of coating bath was prepared as follows. Nickel chloride (0.9 pounds, 3.15 moles) was combined with sodium tartrate (2.5 pounds, 4.93 moles) in about two gallons of distilled water having a resistance of approximately ten megohms. To that solution was added 0.25 pounds of cobalt chloride (0.85 mole) and 3.0 pounds or reagent grade (99.5% pure) ethylene diamine (17.4 moles), 3.5 pounds of reagent grade sodium hydroxide (39.7 moles) and 1.0 pound of concentrated ammonium hydroxide solution.
• the volume of the resulting mixture (pH about 13.5) was adjusted to five gallons by the addition of distilled water, and the solution was heated to 180°F and filtered into electroless plating tank capable of continuous filtration, heating and agitation of the bath composition. The temperature of the bath was raised to about 185°F. Two strips of steel 15 mil thick by 1/2 inch in width were degreased and prepared for immersion in the coating bath by successive anodic alkaline oxidation followed by acid pickling.
• the third steel strip which did not have its. surface properly prepared for optimum adhesion of the electroless coating was bent and creased so that the coating was purposely fractured, and a small sample separated from the steel substrate surface.
• Analysis of the substrate interface side of the coating deposited on the steel surface revealed that it contained in excess of 95 weight per ent cobalt. (See Fig. 2)
• analysis of apparent holes in the interface side of the coating showed lower cobalt levels and much higher nickel levels.
• x-ray analysis of the "valleys" between the nodules on the outer surface of the coating showed nickel levels lower than those in the upper surfaces of the nodules and higher cobalt levels.
• the coating prepared in accordance with preferred embodiments of the present invention are heterogeneous in thickness cross-section having a higher cobalt concentration at the interface of the coating and the substrate surface.
• the high nickel alloy nodules at the outer surface of the coating are imbedded in a softer high cobalt alloy matrix deposited during the early stages of the electroless coating process.
• a coated steel strip was tested for surface hardness using a Knoop hardness measuring device (KH 100) and found to exhibit a Knoop hardness of 1100 which surpasses that of commercial grade hard chrome.
• KH 100 Knoop hardness measuring device
• Electroless coatings deposited from a bath prepared in accordance with the example have also shown exceptional corrosion resistance under laboratory test conditions: ASTB B117 Salt Spray-1200 hours.
• Example 2 The same procedure was followed as in Example 1 except for variation of the relative amounts of the bath constituents: nickel chloride, 0.9 pounds (3.12 moles); cobalt chloride, 0.3 pounds (1.05 moles); thallium I sulfate, 0.05 gram (1 x 10 mole); sodium borhydride, 0.0275 pounds (0.33 moles); ethylene diamine, 3.0 pounds (17.4 moles); sodium hydroxide, 6.0 pounds (68 moles); concentrated ammonium hydroxide, 0.75 pounds; sodium tartrate, 2.5 pounds (5 moles).
• X-ray analysis of the nodules at the wear and corrosion resistant surface of the coated steel strips showed the nodules to contain -19-
• Example 2 The same procedure was followed as in Example 1 except that the coating bath constituents were utilized in the following amounts: nickel chloride, 1 pound (3.5 moles); cobalt chloride, 0.375 pounds (1.3 moles); thallium I sulfate, 0.25 gram (5 x 10 —4 moles); sodium borohydride, 0.0175 pounds (0.21 moles); ethylene diamine, 2.5 pounds (14.5 moles); sodium hydroxide, 5 pounds (57 moles); ammonium hydroxide, 0.75 pounds; sodium tartrate, 4 pounds (7.9 moles).
• X-ray analysis of the surface nodules presented by the deposited electroless coating showed them to contain about 90 weight percent nickel, about 4 weight percent cobalt, about 1 weight percent boron, and about 5 weight percent thallium.
• An electroless coating bath having a volume of one gallon was prepared as follows: 81 grams of nickel chloride (0.625 mole); 34 grams of c bait chloride (0.26 moles), 227 grams of ethylene diamine (2.9 moles), and 136 grams of sodium tartrate (0.59 moles) were combined in about 3 quarts of distilled/deionized water. The pH of the solution was adjusted to about 13.5 by the addition of 181 grams of sodium hydroxide (4.5 moles) and 68 grams of concentrated ammonium hydroxide solution. The volume of the resulting mixture was adjusted to about one gallon by the addition of distilled water. The coating bath mixture was then heated to approximately 190°F.
• the coated substrates were removed from the coating bath, washed and scanned by x-ray for 5 surface nodule elemental content and found to have about
• the coating exhibits exceptional hardness and corrosion and wear resistance.
• the coating bath of Example 4 is used to apply an electroless metal strike before and after application

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• 1987
  • 1987-05-26 JP JP50348587A patent/JPH01502678A/ja active Pending
  • 1987-05-26 AU AU74885/87A patent/AU7488587A/en not_active Abandoned
  • 1987-05-26 EP EP19870903805 patent/EP0309466A1/en not_active Withdrawn
  • 1987-05-26 CA CA000538036A patent/CA1269286A/en not_active Expired
  • 1987-05-26 WO PCT/US1987/001251 patent/WO1987007311A1/en not_active Application Discontinuation

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