Patent Publication Number: US-2019186034-A1

Title: Electrocomposite coatings for hard chrome replacement

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This application is a Continuation of U.S. patent application Ser. No. 13/111,314, filed May 19, 2011, now U.S. Pat. No. 8,202, 627, which in turn is a continuation-in-part of and claims the benefit of priority to U.S. patent application Ser. No. 12/331,623, filed Dec. 10, 2008, now U.S. Pat. No. 8,168,056, which in turn is a continuation of and claims the benefit of priority to U.S. patent application Ser. No. 11/510,417, filed Aug. 26, 2006, which in turn claims the benefit of priority to U.S. Provisional Patent Application Ser. No. 60/761,445, filed Jan. 24, 2006. This application also claims the benefit of priority to U.S. Provisional Patent Application Ser. No. 61/346,165, filed May 19, 2010. The disclosure of each of the aforementioned applications is incorporated by reference herein in its entirety. 
    
    
     BACKGROUND OF THE DISCLOSURE 
     Field of the Disclosure 
     The present disclosure relates to improved methods and systems for coating materials as well as improved protective coatings for materials. Particularly, the present disclosure is directed to methods and systems for making coatings including cobalt, phosphorous and particles of material having superior tribological characteristics. 
     Description of Related Art 
     Electroplated hard chrome coating is widely used as a wear resistant coating to prolong the life of mechanical components. However, conventional hard chrome electroplating processes generate hexavalent chromium ion which is a known carcinogen. Hence, there is a major effort throughout the electroplating industry to replace hard chrome coatings with an environmentally benign, non-carcinogenic coating having characteristics similar or superior to those of hard chrome. 
     Thermal spray hard coatings of chromium carbide, tungsten carbide, tribaloy, aluminum oxide and the like, using Plasma Spray, High Velocity Oxy Fuel (HVOF) and other similar processes are currently being used to replace hard chrome coatings. However, these processes have not been able to be used for non line of sight (NLOS) applications, such as the inner diameter (ID) of cylinders, bearing cavities and the like. Even for the outer surface applications, thermal-spray coatings are generally deposited in thick layers and later ground to a desired thickness. Hence, thermal sprayed coatings are generally more expensive than electroplated hard chrome. 
     For NLOS applications, a number of electroplated coatings have been evaluated. These include electroplated Ni—P and Ni—W alloy coatings, Ni—SiC electrocomposite and other similar coatings. However, none of these coatings have all the desired characteristics of hard chrome. Also, nickel base coatings are now considered undesirable because it has been found that in some cases they can cause severe allergic reactions. 
     Recently, a new nanocrystalline Co—P base coating has been developed by pulse plating processes. The resulting nanocrystalline Co—P coating appears to be a very promising replacement for hard chrome as its characteristics are either equal or superior to those of hard chrome. However, the electroplating process for this nanocrystalline Co—P base coating is based on pulse plating. In pulse plating, the applied voltage between the anode and cathode is pulsed at different amplitudes and at various frequencies. This pulse plating process used to produce nanocrystalline Co—P coatings requires special power supplies which are currently available only for laboratory research and development. Large scale affordable pulsed power supplies for the production environment are not currently available. 
     In another aspect, engineered components are typically coated to provide wear resistance, corrosion resistance, and oxidation resistance of the base material. The most widely used coating is hard chrome because of its excellent wear resistance, low cost and ease of application. Hard chrome also has its own deficiencies, among them is adverse effects on the fatigue strength of base materials. Because of this undesirable impact on fatigue resistance or a “fatigue debit”, base materials are appropriately derated requiring heavier cross sections, weight and cost penalty. Fatigue debit results from micro cracks inherent in the hard chrome deposition that act as crack initiation sites. As a result, engineers have to design plated hardware susceptible to fatigue accordingly. This usually requires larger, stronger cross sections to compensate for the fatigue debit induced by the plating. 
     Hard chrome is not the only coating that creates a “fatigue debit.” Electroless nickel and High Velocity Oxy Fuel (HVOF thermal spray) coatings also have “fatigue debits”. High phosphorous electroless nickel has an amorphous, glassy brittle micro-structure, which is susceptible to cracking which causes a fatigue debit, while mid phosphorous electroless nickel and HVOF coatings contain porosities in their coatings. The riot fully dense structure is similar to a cracked structure resulting in fatigue debit. Table A demonstrates typical fatigue debit data for electroless nickel and hard chromium. 
     
       
         
           
               
             
               
                 TABLE A 
               
             
            
               
                   
               
               
                 Typical “Fatigue Debit” results for Hard 
               
               
                 Chromium and Electroless Nickel 
               
            
           
           
               
               
               
               
            
               
                   
                 Bar, Coating Type 
                 Avg. Fatigue Cycles 
                 Fatigue Debit, % 
               
               
                   
                   
               
               
                   
                 Uncoated 4130* 
                 117,426 (4 pcs)  
                 — 
               
               
                   
                 Hard Chromium 
                 34,370 (3 pcs) 
                 70% 
               
               
                   
                 (0.002″) 
               
               
                   
                 Uncoated 4130* 
                 75,185 (2 pcs) 
                 — 
               
               
                   
                 Hard Chromium 
                 27,468 (3 pcs) 
                 64% 
               
               
                   
                 (0.002″) 
               
               
                   
                 Uncoated 4130* 
                 156,252 (3pcs)  
                 — 
               
               
                   
                 Electroless Nickel 
                 85,019 (3pcs) 
                 46% 
               
               
                   
                 Uncoated 4130 
                 75,185 (2 pcs) 
                 — 
               
               
                   
                 Cr over Electroless 
                 39,059 (3 pcs) 
                 48% 
               
               
                   
                 Ni 
               
               
                   
                   
               
               
                   
                 *Different manufactured lots of fatigue specimens give different baselines for fatigue 
               
            
           
         
       
     
     One solution to counter the “fatigue debit” of plated coatings often used on fatigue sensitive hardware is the use of shot peening. Shot peening imparts a compressive stress on the surface of the material to be coated which retards the initiation of fatigue cracks. The need to shot peen hardware which will be electroplated adds expense to the overall manufacturing process. Therefore, there exists a need for coatings used on engineered stress-bearing components which provide wear and corrosion resistance without a “fatigue debit” of base materials. 
     As set forth above, there is a continued need for improved coatings and associated processes for replacing hard chrome. The present disclosure provides a solution for these and other problems. 
     SUMMARY OF THE DISCLOSURE 
     The purpose and advantages of the presently disclosed embodiments will be set forth in and become apparent from the description that follows. Additional advantages of the disclosed embodiments will be realized and attained by the methods and systems particularly pointed out in the written description and claims hereof, as well as from the appended drawings. 
     As embodied herein, in one aspect, the disclosure includes a method for electrolytically coating an article. The method includes providing an article to be coated and disposing the article in an electrolytic cell. The cell includes an anode, a cathode in operable communication with the article, and an electrolyte bath. During electrolysis, the electrolyte bath comprises cobalt ions, phosphorous acid, and tribological particles selected from the group consisting of refractory materials, solid lubricants and mixtures thereof, dispersed therein. The method further includes applying steady direct electric current through the anode, the electrolyte bath and the cathode to coat the article with cobalt, phosphorous and the tribological particles. 
     In accordance with a further aspect of the disclosure, the electrolyte bath may include, for example, tribological particles of refractory material selected from the group consisting of ceramics, diamond and mixtures thereof. In accordance with one aspect of the disclosure, the electrolyte bath may include ceramic tribological particles selected from the group consisting of silicon carbide, chromium carbide, boron carbide, tungsten carbide, titanium carbide, silicon nitride, aluminum oxide, chromium oxide, and mixtures thereof. In accordance with another aspect of the disclosure, the electrolyte bath may include solid lubricant tribological particles selected from the group consisting of graphite, boron nitride, polytetrafluoroethylene (“PTFE”), molybdenum disulfide, tungsten disulfide, and mixtures thereof. 
     In accordance with another aspect of the disclosure, the phosphorous acid may be present in the electrolyte bath in a concentration from about 3 grams per liter to about 35 grams per liter. In accordance with another embodiment of the disclosure, the phosphorous acid is present in the electrolyte bath in a concentration from about 3 grams per liter to about 25 grams per liter. In accordance with a preferred embodiment of the disclosure, the phosphorous acid is present in the electrolyte bath in a concentration from about 3 grams per liter to about 15 grams per liter. 
     If desired, the anode may include a portion formed from consumable cobalt material adapted to release cobalt ions into the electrolyte bath as cobalt is deposited on an article to be coated. The consumable cobalt anode may comprise a cobalt plated electrode, and/or may include pieces of cobalt disposed in a basket or other suitable container in communication with the electrolyte bath. The source of cobalt ions may additionally or alternatively include, for example, a soluble cobalt salt selected from the group consisting of CoSO 4 , CoCl 2 , CoCO 3 , Co(SO 3 NH 2 ) 2  and mixtures thereof disposed in the electrolyte bath. If desired, an inert anode may be provided formed from a material selected from the group consisting of graphite, platinized copper, platinized titanium, platinized columbium or combinations thereof. 
     It is also possible to perform electroforming operations to produce cobalt parts in accordance with the disclosure. In accordance with this aspect of the disclosure, the cathode acts as a master, whereby a substrate, or coating, may be formed on the cathode and then removed from the cathode as a separate piece. The cathode may accordingly be made from a material that does not adhere significantly to the coating to facilitate its removal, such as passivated stainless steel. In accordance with a further aspect of the disclosure, the article to be coated may be the cathode of the cell. 
     In accordance with another aspect of the disclosure, the tribological particles in the electrolyte bath may have an average dimension between about 0.1 micrometers and about 20 micrometers. In accordance with a preferred embodiment of the disclosure, the tribological particles may have an average dimension between about 1.0 micrometers and about 5.0 micrometers. 
     In accordance with yet a further aspect of the disclosure, the electrolyte bath may further comprise a dissolution promoter for promoting the dissolution of the consumable cobalt material. The dissolution promoter may include, for example, a metal halide salt. In accordance with certain specific embodiments of the disclosure, the dissolution promoter may be selected from the group consisting of sodium chloride, cobalt chloride, metal bromide salts and combinations thereof. If desired, the electrolyte bath may further comprise a buffering agent, such as boric acid to help maintain the pH within a desired tolerance. Moreover, a pH adjustor may also be employed to control the pH of the system, such as cobalt carbonate, sodium hydroxide and sulfuric acid. 
     In accordance with one embodiment of the disclosure, the pH of the electrolyte bath may be between about 0.5 and about 2.0. In accordance with a preferred embodiment of the disclosure, the pH of the electrolyte bath is between about 0.8 and about 1.2. The temperature of the electrolyte bath may be between about 50° C. and about 90° C. In accordance with a preferred embodiment of the disclosure, the temperature of the electrolyte bath may be between about 70° C. and about 80° C. The electric current applied to the electrolyte bath may have a current density between about 0.2 Amps/in 2  to about 2.0 Amps/in 2 . In accordance with one embodiment of the disclosure, the electric current may have a current density between about 0.5 Amps/in 2  to about 1.5 Amps/in 2 . 
     In accordance with still another aspect of the disclosure, the concentration of cobalt in the electrolyte bath may be between about 50 grams per liter and about 200 grams per liter. In accordance with a preferred embodiment of the disclosure, the cobalt concentration in the electrolyte bath may be about 100 grams per liter. The tribological particles may be present in the electrolyte bath in a concentration from about 10 grams per liter to about 200 grams per liter. Specifically, the silicon carbide tribological particles may be present in the electrolyte bath in a concentration from about 10 grams per liter to about 200 grams per liter. In accordance with a preferred embodiment of the disclosure, the silicon carbide tribological particles are present in the electrolyte bath in a concentration from about 30 grams per liter to about 60 grams per liter. By way of further example, the chromium carbide tribological particles may be present in the electrolyte bath in a concentration from about 10 grams per liter to about 200 grams per liter. In accordance with a preferred embodiment of the disclosure, the chromium carbide tribological particles are present in the electrolyte bath in a concentration from about 35 grams per liter to about 100 grams per liter. The tribological particles may have an average dimension, for example, between about 0.1 micrometers and about 20 micrometers. 
     In accordance with still a further aspect of the disclosure, the article may be heat treated after the article has been coated to cause the precipitation of cobalt-phosphides. The article may be heat treated at a temperature between about 150° C. and about 500° C. In accordance with one example, the article is heat treated at a temperature between about 200° C. and about 400° C. The article may be heat treated for a length of time between about 15 minutes and about 180 minutes. The heat treatment temperature and duration are interrelated, in that a longer heat treatment may be appropriate at a lower temperature, and a shorter heat treatment may be appropriate at a higher temperature. 
     In further accordance with the disclosure, a system for electrolytically coating an article is provided comprising an electrolytic cell. The cell includes an anode, a cathode capable of being placed in operable communication with an article to be coated, and an electrolyte bath. The electrolyte bath is in operable communication with the anode and the cathode. During electrolysis, the electrolyte comprises cobalt ions, phosphorous acid, and tribological particles selected from the group consisting of refractory materials, solid lubricants and mixtures thereof dispersed therein. The system also includes a direct current power supply adapted to apply steady direct current across the anode, electrolyte bath and cathode to coat an article with cobalt, phosphorous and the tribological particles. The system can include all of the attributes needed to carry out the method steps of the invention described herein. 
     In further accordance with the disclosure, a composition of matter is provided. The composition of matter comprises cobalt, phosphorous and tribological particles selected from the group consisting of refractory materials, solid lubricants and mixtures thereof dispersed therein. The composition of matter may be formed according to the processes described herein. In accordance with one aspect of the disclosure, the coating may have a hardness of about 650-700 VHN. If the composition of matter is heat treated to form cobalt phosphides, the composition of matter may be harder. For example, the composition may include chromium carbide tribological particles and the coating may accordingly have a hardness of about 500 VHN prior to heat treatment. In accordance with another embodiment of the disclosure the coating may include silicon carbide tribological particles and the coating may have a hardness of about 1150 VHN subsequent to heat treatment. 
     In accordance with a further aspect, the disclosure provides a coating for improving the fatigue performance of an article. The coating includes a cobalt material matrix. The cobalt material matrix includes, and preferably consists of, a cobalt phosphorous alloy, wherein the phosphorous in the final coating is present in an amount between about 7 weight percent and about 12 weight percent. 
     In accordance with one embodiment, the cobalt material matrix can be substantially free of tribological particles. In this embodiment, the phosphorous in the final coating is preferably present in an amount between about 10 weight percent and about 12 weight percent. In accordance with another embodiment, the coating cab further include a plurality of tribological particles throughout the cobalt material matrix, the particles having an average particle size in the range of from about 2 to 10 microns. In this embodiment, the phosphorous in the final coating preferably present in an amount between about 7 weight percent and about 8 weight percent. 
     In accordance with a further aspect, the coating preferably has an as-plated hardness of about 650-700 VHN and has a fatigue life that is greater than an otherwise identical but uncoated article. More preferably, the article has a fatigue life that is at least twice as great as an otherwise identical but uncoated article. Even more preferably, the article has a fatigue life that is at least three, four, five, six, seven, eight, nine or ten times as great as an otherwise identical but uncoated article. 
     In accordance with further aspects, the tribological particles include ceramic material selected from the group consisting of silicon carbide, chromium carbide, boron carbide, tungsten carbide, titanium carbide, silicon nitride, aluminum oxide, chromium oxide, and mixtures thereof. The tribological particles include solid lubricant material selected from the group consisting of graphite, boron nitride, PTFE, molybdenum disulfide, tungsten disulfide, and mixtures thereof. 
     In accordance with another aspect, the disclosure provides a method for electrolytically coating an article to enhance its fatigue performance. The method includes providing an article to be coated, and disposing the article in an electrolytic cell. The cell including a soluble anode, a cathode in operable communication with the article, and an electrolyte bath. The electrolyte bath, during electrolysis, includes cobalt ions from the soluble anode and phosphorus obtained by separately introducing phosphorous acid into the bath, wherein the pH of the electrolyte bath is between about 1.2 and about 2.2. The method further includes applying steady direct electric current through the anode, the electrolyte bath and the cathode at a current density of about 0.3 Amps/in2 and about 0.8 Amps/in2 to coat the article with a coating that is essentially free of nickel and contains cobalt and phosphorous. The weight percent of phosphorus in the resulting coating is between about 7% and about 12%. 
     In accordance with one embodiment, the weight percent of phosphorus in the resulting coating is between about 7% and about 8%, wherein the coating is substantially free of tribological particles. In accordance with another embodiment, the electrolyte bath further includes tribological particles selected from the group consisting of refractory materials, solid lubricants and mixtures thereof dispersed therein, wherein the resulting coating includes the tribological particles after coating the article, and further wherein the weight percent of phosphorus in the resulting coating is between about 10% and about 12%. 
     In accordance with still a further aspect, the temperature of the electrolyte bath is between about 70° C. and about 75° C. In one embodiment, the phosphorous acid is introduced in a granular form. However, the phosphorus content of the bath and resulting article can be enhanced by introducing phosphoric acid into the bath as well. 
     It is to be understood that both the foregoing general description and the following detailed description are exemplary and are intended to provide further explanation of the invention claimed. The accompanying figures, which are incorporated in and constitute part of this specification, are included to illustrate and provide a further understanding of the methods, systems and articles of manufacture resulting from the invention. Together with the description, the drawings serve to explain the principles of the invention. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a schematic representation of an electroplating system made in accordance with the present invention. 
         FIG. 2  is a photomicrograph showing the microstructure of a typical Co—P—SiC electrocomposite coating containing about 5-6 weight percent phosphorous made in accordance with the present invention. 
         FIG. 3  is a photomicrograph showing the microstructure of a typical Co—P—Cr 3 C 2  electrocomposite coating containing about 5-6 weight percent phosphorous made in accordance with the present invention. 
         FIG. 4  is a schematic representation of a plating arrangement for plating articles in accordance with one aspect of the disclosure. 
         FIG. 5  is a chart describing the relationship between pH of a coating bath as it relates to incorporation of phosphorus in the final coating. 
         FIG. 6  is a photomicrograph of a high fatigue cobalt phosphorus coating incorporating tribological particles. 
         FIG. 7  is a chart describing the relationship of phosphorus content in a coating with as plated hardness. 
     
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Reference will now be made in detail to the present preferred embodiments of the disclosure, examples of which are illustrated in the accompanying drawings. The methods and corresponding steps of the disclosed embodiments will be described in conjunction with the detailed description of the compositions of matter and associated systems. 
     The devices and methods presented herein may be used for producing improved coatings for articles that do not suffer from the deficiencies of coatings known in the prior art. The present invention may be practiced using a generally conventional DC power supply to produce cobalt-phosphorous base electrocomposite coatings having hardness, bend ductility and corrosion resistance similar or superior to those of hard chrome. Unlike nickel and chromium, cobalt does not present significant environmental considerations when used in electroplating. As such, it presents significant benefits over the use of techniques employing significant quantities of chromium or nickel. 
     In accordance with the invention, a system and associated method for electrolytically coating an article is provided comprising an electrolytic cell. The cell includes an anode, a cathode capable of being placed in operable communication with an article to be coated, and an electrolyte bath. The electrolyte bath is in operable communication with the anode and the cathode. During electrolysis, the electrolyte comprises cobalt ions, phosphorous acid, and tribological particles selected from the group consisting of refractory materials, solid lubricants and mixtures thereof dispersed therein. The system also includes a direct current power supply adapted to apply steady direct current across the anode, electrolyte bath and cathode to coat an article with cobalt, phosphorous and the tribological particles. 
     For purpose of explanation and illustration, and not limitation, a partial view of an exemplary embodiment of the system in accordance with the invention is shown in  FIG. 1  and is designated generally by reference character  100 . Other embodiments of a system in accordance with the invention, or aspects thereof, are provided in  FIGS. 2-3 , as will be described. 
     For purposes of illustration and not limitation, as embodied herein and as depicted in  FIG. 1 , system  100  is provided with a cell  110 . Cell  110  includes a container  112  adapted and configured to house an electrolyte bath  114 . Cell further includes an anode  116  and a cathode  126  in electrical communication with a power supply  130 . 
     The anode  116  may be formed from a variety of materials, for example, such as graphite, platinized copper, platinized titanium, platinized columbium and combinations thereof. If desired, the anode  116  may include a consumable portion (e.g.,  118 ,  120 ) made from cobalt, wherein the anode  116  is adapted to release cobalt ions into the electrolyte bath  114  as cobalt is depleted from the bath, and deposited on an article to be coated. Suitable anodes  116  with consumable portions (e.g.,  118  and/or  120 ) may be made in a variety of ways. For example, the anode  116  may be coated with cobalt to form a consumable portion  118  of any desired geometry, such as by electroplating cobalt onto a titanium or stainless steel anode. Additionally or alternatively, pieces  120  of cobalt may be disposed in a basket  122  or other suitable container made at least in part, for example, from titanium or other suitable conductive substantially non reactive material in communication with the electrolyte bath  114 . The pieces  120  of cobalt dissolve when a voltage is applied across the anode  116  and cathode  126  to release cobalt ions into the electrolyte bath  114 . Specifically, electrical current flows through the titanium basket  122  and to the cobalt, which in turn oxidizes and goes into solution in bath  114 . Pieces  120  of cobalt metal are commercially available, for example, from Atlantic Metals and Alloys, Inc. in Stratford, Conn. The source of cobalt ions may additionally or alternatively include an additional soluble cobalt source selected, for example, from the group consisting of CoSO 4 , CoCl 2 , CoCO 3 , Co(SO 3 NH 2 ) 2  and mixtures thereof. Thus, for example, an inert anode  116  may be used, and additional CoSO 4  may be added to bath  114  to replace cobalt in the bath as it is depleted due to deposition on the article to be coated and/or the cathode, as described in detail below. Suitable cobalt salts, such as cobalt sulfate, are commercially available, for example, from Shepherd Chemical Co., of Norwood Ohio, and distributed, for example, by Gilbert and Jones Co., Inc., of New Britain, Conn. 
     The cathode  126  may be made from a variety of materials as are known in the art. In accordance with one embodiment of the invention, the cathode  126  will generally include or otherwise be electrically attached to an article to be coated  128 . 
     In accordance with a further aspect of the invention, an article may be electroformed by coating cathode  126  with a coating material and then releasing the coating from the cathode  126 . In accordance with this aspect of the invention, the cathode  126  acts as a master, or mandrel, such that a “mirror” article is formed on the cathode by electroplating material onto the cathode  126 . A variety of articles can be made in this manner, such as leading edge blades for helicopters, complex, difficult to machine shapes such as small bellows, among others. Accordingly, in accordance with this aspect of the invention, the cathode  126  can be made from a material that does not adhere strongly to the coating, such as passivated stainless steel. Stainless steel may be passivated by any known suitable method, for example, by exposure to hot chromic acid, nitric or citric acid to form an oxide layer on the cathode  126  to render it less reactive with a coating formed thereon. 
     It will be recognized that any suitable number of anodes  116  and cathodes  126  may be used, depending on what is being manufactured. For example, racks of articles  128  may be disposed in the electrolyte bath  114  to be coated. Each article  128  is in conductive communication with, and effectively acts as a cathode  126 . Any suitable number of soluble and/or inert anodes  116  can be used, as desired. It will also be recognized that the anode(s)  116  should be located suitably with respect to the cathode(s)  126 . If it is desired to coat the interior of a cylindrical article with a coating, it will be recognized that it is suitable to locate anode  116  within the cavity formed by the article. 
     The electrolyte bath  114  is in operable communication with the anode  116  and the cathode  126 . During electrolysis, the electrolyte bath  114  comprises an electrolyte having cobalt ions, phosphorous acid and tribological particles selected from the group consisting of refractory materials, solid lubricants and mixtures thereof dispersed therein. The cobalt ions can be introduced in a variety of ways, as described above. The concentration of cobalt in the electrolyte bath may be between about 50 grams per liter and about 200 grams per liter, most preferably about 100 grams per liter. 
     The electrolyte bath  114  may further comprise a dissolution promoter for promoting the dissolution of the cobalt material. The dissolution promoter may include a halide salt. While a variety of salts can be used as dissolution promoters, suitable dissolution promoters may include, for example, sodium chloride, cobalt chloride, bromide salts and combinations thereof. In accordance with one embodiment, sodium chloride is used as a dissolution promoter in electrolyte bath  114  in an amount of about 20 grams per liter. 
     The pH of the electrolyte bath  114  may be between about 0.5 and about 2.0. In accordance with a preferred embodiment, the pH of the electrolyte bath is between about 0.8 and about 1.2. During the electroplating process, the pH of the electrolyte bath  114  increases. In order to maintain the pH within a desired range, one or more of a variety of buffering agents can be added to the electrolyte bath  114  to help maintain the pH within a desired tolerance. For example, a suitable buffering agent is boric acid. If used, the boric acid can act to buffer bath  114 , particularly in the region of the cathode  126 , where hydroxide tends to form, since some hydrolysis can potentially occur at high current densities. However, a buffering agent need not be used since the pH of bath  114  is generally very low, resulting in ample available hydrogen ions in bath  114  that are available to readily combine with any hydroxide formed by the cathode  126 . If desired, pH adjustors may also be employed to increase or decrease the pH of the system. Suitable pH adjustors may include, for example, sulfuric acid, cobalt carbonate and sodium hydroxide. Cobalt carbonate is particularly attractive for increasing the pH since it dissociates to form cobalt, which can be used in plating, and carbon dioxide, which bubbles out of the bath  114  and is released to the atmosphere. It has been discovered that, while a variety of factors affect the efficacy of the electroplating process embodied herein, pH plays a significant role. As such, careful control of the pH of the electrolyte bath can lead to improved quality of the end-product. 
     It is also preferred to maintain a sufficient level of phosphorous acid in the electrolyte bath  114  suitable for electroplating a coating having sufficient amounts of phosphorous. Preferably, the weight percent of phosphorous in the resulting coating is between about 3% and 12%, preferably between about 4% and 7%. Accordingly, the phosphorous acid may be present in the electrolyte bath in a concentration from about 3 grams per liter to about 35 grams per liter. More preferably, the phosphorous acid is present in the electrolyte bath in a concentration from about 3 grams per liter to about 25 grams per liter. Most preferably, the phosphorous acid is present in the electrolyte bath in a concentration from about 3 grams per liter to about 15 grams per liter. If an inert anode  116  is used, the electroplating process is relatively less efficient resulting in slower cobalt deposition on the cathode  126 . In this example of an inert anode  116 , a lower concentration of phosphorous acid is needed. Specifically, since the reaction depositing cobalt is proceeding at a slower pace, relatively more phosphorous is deposited for a given concentration of phosphorous acid. In contrast, when a soluble (e.g., consumable) anode  116  is used, the reaction to deposit cobalt is relatively more efficient. Accordingly, to obtain suitable amounts of phosphorous in the coating, the concentration of phosphorous acid is correspondingly increased. 
     For purposes of illustration and not limitation, as embodied herein, electrolyte bath  114  also includes tribological particles  102  dispersed therein. The tribological particles  102  have superior tribological characteristics (i.e., characteristics that tend to cause a reduction in friction, an increase in lubrication and resulting decrease in the wear of surfaces containing the tribological particles  102 ) and preferably include refractory materials and/or solid lubricants. These particles are thus referred to as tribological particles herein. The refractory materials can include, for example, ceramics, diamond and mixtures thereof. More specifically, ceramic tribological particles may be selected from the group consisting of silicon carbide, chromium carbide, boron carbide, tungsten carbide, titanium carbide, silicon nitride, aluminum oxide, chromium oxide, and mixtures thereof, among others. Solid lubricant tribological particles, such as graphite, boron nitride, PTFE, molybdenum disulfide, tungsten disulfide, and mixtures thereof may also be used. It will be recognized that certain tribological particles, such as boron nitride, have both ceramic and lubricious properties. 
     The tribological particles  102  in the electrolyte bath  114  may have an average dimension, for example, between about 0.1 micrometers and about 20 micrometers. In accordance with a preferred embodiment of the invention, the tribological particles have an average dimension between about 1.0 micrometers and about 5.0 micrometers. If silicon carbide tribological particles are employed, they may be present in the electrolyte bath in a concentration from about 10 grams per liter to about 200 grams per liter, preferably from about 30 grams per liter to about 60 grams per liter. If chromium carbide tribological particles are used, they may be present in the electrolyte bath in a concentration from about 10 grams per liter to about 200 grams per liter. In accordance with a preferred embodiment of the invention, the chromium carbide tribological particles are present in the electrolyte bath in a concentration from about 35 grams per liter to about 100 grams per liter. 
       FIG. 2  is a cross-sectional photomicrograph of a coating showing the microstructure of a typical Co—P—SiC electrocomposite coating containing about 5-6 weight percent phosphorous. Similarly,  FIG. 3  is a cross-sectional photomicrograph of a coating showing the microstructure of a typical Co—P—Cr 3 C 2  electrocomposite coating containing about 5-6 weight percent phosphorous. The tribological particles occupy about 25% of the volume of each of the coatings depicted in  FIG. 2  and  FIG. 3 . The samples depicted in  FIGS. 2 and 3  have not been heat treated. As can be seen in the Figures, the tribological particles  102  are dispersed throughout the coating  200 . As further depicted, the coating  200  is metallurgically sound and crack-free. In contrast, a chromium coating generally demonstrates many micro cracks throughout the coating which degrade its corrosion resistance. 
     The temperature of the electrolyte bath  114  may be between about 50° C. and about 90° C. Temperatures below about 50° C., while possible, can be disadvantageous because of lower deposition rates of the coating and inefficient incorporation of phosphorous into the coating. On the other hand, temperatures in excess of about 90° C. generally results in excessive loss of material from the electrolyte bath  114  by way of evaporative mechanisms. In accordance with a preferred embodiment of the invention, the temperature of the electrolyte bath may be between about 70° C. and about 80° C. 
     As depicted in  FIG. 1 , direct current power supply  130  is adapted to apply steady direct current across the anode  116 , electrolyte bath  114  and cathode  126  to coat an article (e.g.,  128 ) with cobalt, phosphorous and the tribological particles. In operation, the electric current applied to the electrolyte bath may have a current density between about 0.2 Amps/in 2  to about 2.0 Amps/in 2 . In accordance a preferred embodiment of the invention, the electric current may have a current density between about 0.5 Amps/in 2  to about 1.5 Amps/in 2 . Power supply  130  can be similar to rectifiers as are known in the art, such as Model P-106-.25CF rectifier commercially available from Aldonex, Inc. in Bellwood, Ill., among others. 
     Prior art, such as U.S. Pat. No. 5,352,255 to Erb et al. describe nano crystalline cobalt phosphorous coatings with a grain size smaller than 100 nm. Such coatings have characteristics either similar or superior to hard chrome and can be used as a replacement of hard chrome. However, to form nanocrystalline cobalt phosphorous coatings, it is necessary to use complex and expensive pulsed DC power supplies. Applicants have discovered that the addition of tribological particles  102  as described herein to the electrolyte bath has made it possible to produce a metallurgically sound, crack free coating with high hardness and ductility which can be used to replace hard chrome. Unlike the teachings of Erb et al., the systems made in accordance with the invention are capable of using the conventional steady DC power supplies known in the art. 
     In accordance with still a further aspect of the invention, the coating formed on the article coated during the electroplating process may be heat treated to cause the precipitation of cobalt-phosphides within the coating. To cause this precipitation, the article may be heat treated in an oven, for example, in the presence of air. Suitable ovens can be obtained from Lindberg/Blue of Thermo Electron Corp, located in Asheville, N.C. A Lindberg furnace Type No. 51662 was used to perform the heat treatments described in the Examples below, but it will be recognized that other similar furnaces are suitable. 
     The heat treatment can occur, for example, at a temperature between about 150° C. and about 500° C. for a length of time between about 15 minutes and about 180 minutes. In accordance with one embodiment, the article is heat treated at a temperature between about 200° C. and about 400° C. The heat treatment temperature and duration are interrelated, in that a longer heat treatment may be appropriate at a lower temperature, and a shorter heat treatment may be appropriate at a higher temperature. 
     In further accordance with the invention, a composition of matter is provided comprising cobalt, phosphorous and tribological particles selected from the group consisting of refractory materials, solid lubricants and mixtures thereof dispersed therein. The composition of matter may be used as a protective coating applied to an article, or may constitute a separate member electroformed on a mandrel as described herein. The composition of matter may be formed, for example, according to the processes described herein. 
     Prior to heat treatment, the cobalt-phosphorous-tribological particle coating generally has a hardness of about 650-700 VHN. If this coating is heat treated to precipitate cobalt phosphides, the resulting coating is harder. Experience has resulted in coatings comprising cobalt, phosphorous and chromium carbide tribological particles having a hardness of about 1000 VHN or greater. Coatings using silicon carbide instead of chromium carbide have been formed having a hardness of about 1150 VHN or greater. The desired characteristics of coatings disclosed herein are maintained by controlling electroplating parameters and electrolyte bath composition as described herein. 
     The following Examples further illustrate the present invention. Unless otherwise indicated, stated percentages are by weight. 
     EXAMPLE I 
     Carbon steel samples were plated in accordance with the present invention. An electroplating bath was provided having the following composition:
         Cobalt sulfate: 520 g/l   Boric acid: 40 g/l   Sodium chloride: 20 g/l   Granular phosphorous acid: 15 g/l   Silicon carbide particles(2-5 microns): 25 g/l       

     The bath was made by mixing the above ingredients in water to a total volume of 3.5 liters. Electroplating was performed with cobalt pieces in a titanium basket used as an anode and plain carbon steel panels as cathode. One side of each carbon steel panel was masked and the side facing the anode was plated with a cobalt-phosphorous-silicon carbide coating. 
     Plating Conditions 
     The bath pH was maintained at about 0.9 with sulfuric acid to lower pH and sodium hydroxide to raise pH. The bath temperature was maintained between about 70° C.-80° C. The samples were plated at a current density of 2 Amperes/square inch. The panels were plated for about an hour which produced a coating thickness around 0.005 inch. 
     Coating Properties 
     Phosphorous content of the coating was about 9 wt %. As-plated hardness of the coating was 720 VHN. The coating was heat treated in air at 400° C. for 1.5 hrs. The as heat treated hardness was 1150 VHN. 
     EXAMPLE II 
     Comparison with Hard Chrome 
     Materials made in accordance with the invention have properties equaling or even exceeding those of hard chrome as shown in Table I, below. Table I compares conventional hard chrome processing with exemplary parameters provided by the present invention. As can be seen, materials made in accordance with the present invention compare favorably with chrome and significantly surpass chrome in corrosion prevention. 
     
       
         
           
               
             
               
                 TABLE I 
               
             
            
               
                   
               
               
                 Comparison of Co—P—SiC and Hard Chrome 
               
            
           
           
               
               
               
            
               
                 Feature 
                 Co—P—SiC 
                 Hard Chrome 
               
               
                   
               
               
                 Power supply 
                 Conventional DC 
                 Conventional DC 
               
               
                 Plating rate 
                 Up to 0.005″/hr 
                 Up to 0.0016″/hr 
               
               
                 Thickness 
                 Plated up to 0.02″ 
                 Typically &lt;0.02″ 
               
               
                 As-plated condition 
                 Crack free 
                 Micro cracked 
               
               
                 Micro structure 
                 ~50 nm grains with 2-5 μm SiC 
                 Normal grain size, 
               
               
                   
                 particles 
                 &gt;1000 nm 
               
               
                 As-plated hardness 
                 650 
                 800-1200 
               
               
                 As heat treated hardness, 
                 760 
                 — 
               
               
                 200° C./.1.5 hrs 
               
               
                 As heat treated hardness, 
                 1200 
                 — 
               
               
                 400° C./1.5 hrs 
               
               
                 Bend ductility, 0.003″ thick, 
                 A few fine cracks at the bend 
                 No visible cracks at the 
               
               
                 90° bend 
                   
                 bend 
               
               
                 Threshold strain* 
                 Similar to HVOF T-400** 
                 Much lower than 
               
               
                   
                 coating 
                 HVOF T-400 coating 
               
               
                 Corrosion resistance 
                 No visible rust even after 200 hrs 
                 Rust after 24 hrs 
               
               
                 Salt fog test (ASTM B117) 
               
               
                   
               
               
                 *Total strain to initiate a crack. 
               
               
                 **T-400 is tribaloy 400 coating deposited by using HVOF thermal spray process 
               
            
           
         
       
     
     EXAMPLE III 
     Effect of Phosphorous Acid Concentration on Hardness 
     It has also been discovered that the amount of phosphorous acid in the electrolyte bath has a measurable effect on the hardness of the produced coating. For example, lowering the concentration significantly below 5 grams per liter or raising it significantly above 25 grams per liter begins to show a drop off in coating hardness, as shown in Table II and Table III, below. 
     
       
         
           
               
             
               
                 TABLE II 
               
             
            
               
                   
               
               
                 As-plated and as-heat treated hardness of Co—P—SiC* coatings 
               
               
                 as function of H 3 PO 3  in the plating electrolyte bath. 
               
            
           
           
               
               
               
            
               
                 H 3 PO 3   
                   
                 As-heat treated hardness. 
               
               
                 concentration 
                 As-plated hardness 
                 HT @ 400° C. for 1.5 hours 
               
               
                   
               
               
                  0 g/L 
                 360 VHN 
                  350 VHN 
               
               
                  5 g/L 
                 669 VHN 
                 1012 VHN 
               
               
                 15 g/L 
                 720 VHN 
                 1147 VHN 
               
               
                 25 g/L 
                 736 VHN 
                 1236 VHN 
               
               
                 35 g/L 
                 660 VHN 
                 1150 VHN 
               
               
                   
               
               
                 *Concentration of SiC is 25 g/L in plating bath. 
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE III 
               
             
            
               
                   
               
               
                 As-plated and as-heat treated hardness of Co—P—Cr 3 C 2 * 
               
               
                 coatings as a function of H 3 PO 3  in the plating bath. 
               
            
           
           
               
               
               
            
               
                 H 3 PO 3   
                   
                 As-heat treated hardness. 
               
               
                 concentration 
                 As-plated hardness 
                 HT @ 400° C. for 1.5 hours 
               
               
                   
               
               
                  0 g/L 
                 360 VHN 
                  350 VHN 
               
               
                  9 g/L 
                 663 VHN 
                 1008 VHN 
               
               
                 15 g/L 
                 670 VHN 
                 1053 VHN 
               
               
                 25 g/L 
                 681 VHN 
                 1089 VHN 
               
               
                 35 g/L 
                 636 VHN 
                 1019 VHN 
               
               
                   
               
               
                 *Concentration of Cr 3 C 2  is 50 g/L in plating bath. 
               
            
           
         
       
     
     EXAMPLE IV 
     Increase in Hardness By Adding Tribological Particles 
     Table IV compares the as plated and as heat treated hardness of cobalt-phosphorous with composite cobalt-phosphorous coatings further including chromium carbide and silicon carbide. Tables V and VI below show the relative increase in hardness of the cobalt-phosphorous coating with the composite coatings. As can be seen, the addition of the carbide tribological particles results in a surprising increase in the hardness of the material after the precipitation of cobalt-phosphides. 
     
       
         
           
               
             
               
                 TABLE IV 
               
             
            
               
                   
               
               
                 As-plated and as-heat treated hardness of Co—P, Co—P—Cr 3 C 2  and 
               
               
                 Co—P—SiC coatings with 5 g/L H 3 PO 3  in the plating bath. 
               
               
                 Samples were heat treated at 325° C. for 0.5 hours. 
               
            
           
           
               
               
               
               
            
               
                   
                 As-plated 
                   
                   
               
               
                   
                 hardness 
                 As-heat treated hardness 
                 Hardness 
               
               
                 Coating 
                 (VHN) 
                 HT @ 325° C. for 0.5 hours 
                 increase 
               
               
                   
               
               
                 Co—P 
                 650 
                  700 VHN 
                  50 VHN 
               
               
                 Co—P—Cr 3 C 2 * 
                 670 
                 1010 VHN 
                 340 VHN 
               
               
                 Co—P—SiC** 
                 669 
                 1150 VHN 
                 480 VHN 
               
               
                   
               
               
                 *50 g/L Cr 3 C 2  in plating bath 
               
               
                 **25 g/L SiC in plating bath 
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE V 
               
             
            
               
                   
               
               
                 As-plated and as-heat treated hardness of Co—P and Co—P—SiC 
               
               
                 with 5 g/L H 3 PO 3  in the plating bath. Samples were 
               
               
                 heat treated at 205° C. and 400° C. for 1.5 hours. 
               
            
           
           
               
               
               
               
            
               
                   
                   
                 As-heat treated 
                 As-heat treated 
               
               
                   
                   
                 hardness 
                 hardness 
               
               
                   
                   
                 HT @ 205° C. 
                 HT @ 400° C. 
               
               
                 Coating 
                 As-plated hardness 
                 for 1.5 hours 
                 for 1.5 hours 
               
               
                   
               
               
                 Co—P 
                 650 VHN 
                 688 VHN 
                 1000 VHN 
               
               
                   
                   
                 (Δ = 38 VHN) 
                 (Δ = 350 VHN) 
               
               
                 Co—P—SiC** 
                 669 VHN 
                 756 VHN 
                 1216 VHN 
               
               
                   
                   
                 (Δ = 87 VHN) 
                 (Δ = 547 VHN) 
               
               
                   
               
               
                 **25 g/L SiC in plating bath 
               
            
           
         
       
     
     EXAMPLE V 
     Comparative, Enhanced Bend Ductility 
     The Co—P—SiC and Co—P—Cr 3 C 2  coatings also have superior bend ductility compared to the Co—P coating having similar wt % P and coating thickness. For example, steel panels 4″×1″×0.04″, were plated with about 0.002″ coatings using coating conditions described herein. Panels were coated on one side only by masking the other side. The panels were held in a vice and bent through 180° in the middle of the panels with the coating on the convex side of the bend. The coating was examined for cracks and delamination. The majority of the panels coated only with cobalt and phosphorous (i.e., without tribological particles) showed large cracks or complete delamination at the bent convex surface. 
     In surprising contrast, the Co—P—SiC and Co—P—Cr 3 C 2  coatings did not delaminate. To the contrary, only fine cracks were observed at the bend. This simple bend test, although qualitative, does indicate an enhanced ductility of the Co—P—SiC and Co—P—Cr 3 C 2  coatings. Generally, it would be expected that inclusion of tribological particles would make the coating more brittle. However, the Co—P—SiC and Co—P—Cr 3 C 2  coatings possess an unexpected combination of high hardness and ductility. It has generally been discovered that the heat treatment temperatures to emphasize ductility are lower than those used to increase hardness. 
     Some of the deficiencies in the prior art vis-à-vis the fatigue debit that accompanies plating articles are set forth in the background section above. It is thus appreciated that a wear/corrosion resistant plated coating that does not induce a fatigue debit to the ferrous material substrate (or other substrate) would be advantageous. Hardware cross sections could be reduced, thus reducing weight and size of components since the plated coating would not impart a fatigue debit. In another aspect, the present disclosure provides electroplated Co—P and Co—P—SiC coatings that provide corrosion and wear resistance without affecting fatigue characteristics or inflicting a “fatigue debit”. These coatings are generally fully dense without any inherent micro-cracks that form the nucleation sites of fatigue cracks. These coatings can be electroplated using conventional DC power and therefore they are drop-in replacements for hard chrome without the adverse environmental impact of hard chrome. 
     In accordance with one aspect, a high strength steel AISI 4130, commonly used for engineered applications is selected as the base material to demonstrate the unique no “fatigue debit” characteristics of electroplated Co—P and Co—P—SiC. It is believed that similar effects can be demonstrated for other materials such as superalloys, titanium alloys, aluminum alloys and the like. 
     EXAMPLE VI 
     Fatigue strength was determined using the four-point rotating beam test method, ISO 1143. Appropriate round bar samples with a 0.250″ minimum diameter at the center were coated with Co—P—SiC. The composition of the plating bath can be found in Table 6. The fatigue bars were heat treated to a hardness of 32-34 HRC, stress relieved at 375° F. for 3 hours min and polished to a surface finish of 2-4 μinch Ra. Coating thickness was about 0.002″. After coating, the samples were again polished to a 2-4 μinch Ra surface finish. Electroplating conditions were as follows: 
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 Electroplating bath composition 
               
            
           
           
               
               
               
            
               
                   
                 Component 
                 Concentration 
               
               
                   
                   
               
               
                   
                 Cobalt sulfate 
                 500 g/L  
               
               
                   
                 Phosphorus acid 
                 12 g/L 
               
               
                   
                 Silicon carbide particle, 2-5um 
                 50 g/L 
               
               
                   
                 Boric acid 
                 35 g/L 
               
               
                   
                 Sodium chloride 
                 20 g/L 
               
               
                   
                   
               
               
                   
                 Electroplating process parameters: pH = 1.25; current density = 0.3 Amperes/square inch; voltage = 3.5-4.0 v; temperature = 72-78° C. 
               
            
           
         
       
     
     Samples were plated with soluble cobalt anodes. Samples (i.e., the cathodes) were attached to a rotating fixture, as shown in  FIG. 4  which maintained electrical contact during rotation. This rotating arrangement was expected to provide uniform coating microstructure all throughout the gage length of the test bars. To determine effects of coating on fatigue strength, uncoated bars were also tested. The results are summarized in Table 7: 
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                 Cycle Life of Co—P—SiC Electroplated and Uncoated 4130 
               
               
                 Steel Rotating Beam Fatigue Bars with Maximum 
               
               
                 Bending Stress of 100,000 psi 
               
            
           
           
               
               
               
            
               
                   
                   
                 Average of 
               
               
                 Fatigue Testing Bars 
                 Fatigue Cycles 
                 Fatigue Cycles 
               
               
                   
               
            
           
           
               
               
               
            
               
                 Uncoated 4130 bar 1 
                 187,289 
                 Uncoated bar: 156,252 
               
               
                 Uncoated 4130 bar 2 
                 130,432 
               
               
                 Uncoated 4130 bar 3 
                 151,035 
               
               
                 Co—P—SiC coated 4340 bar 1 
                 638,757 
                 Coated bar: 884,903 
               
               
                 Co—P—SiC coated 4340 bar 2 
                 1,065,222 
               
               
                 Co—P—SiC coated 4340 bar 3 
                 744,179 
               
               
                 Co—P—SiC coated 4340 bar 4 
                 1,091,453 
               
               
                   
               
            
           
         
       
     
     It is evident that the Co—P—SiC coated samples had a significantly superior average fatigue life compared to that of uncoated samples. Unlike hard chrome, the novel Co—P—SiC coating plated with above process parameters demonstrated no “fatigue debit” for the base material. 
     EXAMPLE VII 
     Rotating bar samples, coated with Co—P, were prepared the same way as the Co—P—SiC coated samples. The solution composition used can be found in Table 8. Electroplating process parameters: pH=1.3-1.4; current density=0.7-0.8 amps/square inch; voltage=3.5-4.0 v; temperature=72-78° C. After the samples were plated they were subjected to a 10 hr 375° F. hydrogen embrittlement relief bake. Table 9 summarizes the results. 
     
       
         
           
               
             
               
                 TABLE 8 
               
             
            
               
                   
               
               
                 Electroplating bath composition 
               
            
           
           
               
               
               
            
               
                   
                 Component 
                 Concentration 
               
               
                   
                   
               
               
                   
                 Cobalt sulfate 
                 450 g/L  
               
               
                   
                 Phosphorus acid 
                 30 g/L 
               
               
                   
                 Boric acid 
                 35 g/L 
               
               
                   
                 Sodium chloride 
                 20 g/L 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 9 
               
             
            
               
                   
               
               
                 Fatigue Life of Co—P Electroplated and Uncoated 4130 
               
               
                 Steel Rotating Beam Fatigue Bars with Maximum Bending 
               
               
                 Stress of 100 KSI 
               
            
           
           
               
               
               
            
               
                 Fatigue Testing Bars 
                 Fatigue Cycles 
                 Average of Fatigue Cycles 
               
               
                   
               
               
                 Uncoated 4130 bar, #205 
                 187,289 
                 156,252 
               
               
                 #206 
                 130,432 
               
               
                 #207 
                 151,035 
               
               
                 Co—P coated 4130 bar, 
                 488,763 
                 665,763 
               
               
                 #250 
               
               
                 #251 
                 842,762 
               
               
                   
               
            
           
         
       
     
     EXAMPLE VIII 
     Rotating bar samples, coated with Co—P, were prepared in the same way as described in Example VII, but the bars were made of 15-5 PH stainless steel. All the samples were exposed to a hydrogen embrittlement relief bake for 10 hrs at 375° F. after plating. The bars were run at 90, 100, 110 and 120 KSI stress levels and the results are tabulated in Table 10. As is evident with all the stress levels, no fatigue debit was observed for the Co—P plated samples. 
     
       
         
           
               
             
               
                 TABLE 10 
               
             
            
               
                   
               
               
                 Fatigue Life of Co—P Electroplated and Uncoated 15-5 PH Stainless Steel Rotating Beam 
               
               
                 Fatigue Bars with Maximum Bending Stress of 90, 100, 110 and 120 KSI 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                 Fatigue 
                   
                 Fatigue 
                   
                 Fatigue 
               
               
                   
                 Fatigue 
                   
                 Cycles, 100 
                   
                 Cycles, 110 
                   
                 Cycles, 120 
               
               
                 Bar # 
                 Cycles, 90 KSI 
                 Bar # 
                 KSI 
                 Bar # 
                 KSI 
                 Bar # 
                 KSI 
               
               
                   
               
            
           
           
               
            
               
                 Uncoated Fatigue Testing Bars 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 #1 
                 674,107 
                 #7 
                 159,665 
                 #2 
                 163,969 
                 #3 
                 90,570 
               
               
                 #5 
                  753760 
                 #8 
                 275,601 
                 #11 
                 156,989 
                 #14 
                 72,917 
               
               
                 #6 
                  769961 
                 #9 
                 309,426 
                 #12 
                 221,508 
                 #15 
                 55,015 
               
               
                 #4 
                 1,035,103*  
                 #10 
                 401,332 
                 #13 
                 126,064 
               
               
                 Avg 
                 808,233 
                   
                 286,506 
                   
                 167,133 
                   
                 72,834 
               
               
                 cycles 
               
            
           
           
               
            
               
                 Co—P Coated Fatigue Testing Bars 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 #16 
                 1,005,065*  
                 #20 
                  850,145** 
                 #24 
                 1,053,171*  
                 #28 
                 398,642 
               
               
                 #17 
                 1,012,889*  
                 #21 
                 1,005,151*  
                 #25 
                 1,067,568*  
                 #29 
                 328,037 
               
               
                 #18 
                 551,285 
                 #22 
                 1,004,892*  
                 #26 
                 797,223 
                 #30 
                 180,141 
               
               
                 #19 
                 1,047,888*  
                 #23 
                 211,057 
                 #27 
                  787,687** 
               
               
                 Avg 
                 904,281 
                   
                 767,811 
                   
                 926,412 
                   
                 302,273 
               
               
                 cycles 
               
               
                   
               
               
                 *Bar was removed from test and did not break 
               
               
                 **Bar was removed from test because the collet slipped off the shank, bar did not break 
               
            
           
         
       
     
     Applicants believe that the extraordinary benefits described herein vis-à-vis enhanced fatigue life correlate, in one aspect, with the weight percent of phosphorus in the resulting coating. Applicants have experimentally arrived at a curve illustrated in  FIG. 5  that provides a means for controlling the weight percent of phosphorus in the resulting coating as a function of pH. It will be noted that this curve correlates directly with a Co—P coating. It is believed that similar behavior is encountered when incorporating tribological particles in the matrix. However, it is believed that the uptake of phosphorus in the coating is generally enhanced by the presence of such particles, such as particles of silicon carbide. 
       FIG. 5  illustrates Co—P bath pH vs. wt % P in the resulting coating at three levels of phosphorus acid, 10 g/l, 20 g/l and 30 g/l in the bath. The cobalt content was maintained at about 105-115 g/l, current density at 0.5 ASI, temperature at 70-75° C., and plating voltage at 9-11 v (rotating fixture and single anode piece). Coating wt % P linearly decreased as a function of pH. The phosphorous acid decreased at approximately 0.5 g/l after plating each panels for about 8-9 amp·hr and about 1.3 g of phosphorous acid is added after plating each panel. Cobalt increased after plating each 4″×1″ panels by about 2 g/l for 2.5 l bath after 8-9 amp·hr of plating. Plating baths were adjusted after plating 5-6 samples to maintain cobalt within a 105-115 g/l range. Baths were also analyzed frequently. Coatings were peéled off from 4″×1″ panels to analyze for % P. 
     Applicants have discovered that the optimum range of weight percent of phosphorus for high fatigue components is substantial, particularly from about 7 wt % to about 12 wt %, more preferably about 7 wt % to about 11 wt %. Correspondingly, the pH range is similarly quite wide, from about 1.2 to about 2.2 based on phosphorus acid concentration at a specific current density of 0.5 amperes per square inch and within a temperature range of 70-75° C. 
     Moreover, it has been discovered that long cycle life approaching 10× of an uncoated part, was obtained for both Co—P and Co—P—SiC coatings, although Co—P—SiC coatings had more long life samples. The composition and plating conditions that exhibited more frequent long cycle life (5×-10×) involves a bath having about 110 g/l of cobalt and 20 g/l of phosphorus acid at plating conditions of a current density of 0.5 amperes per square inch at a pH of about 1.8. For such a coating, based on  FIG. 5 , it is estimated that this coating has a weight percent of phosphorus of about 7.5 percent. For Co—P base coatings without SiC, the corresponding percent phosphorus uptake is about 11 weight percent phosphorus.  FIG. 6  presents an exemplary photomicrograph of a nanocrystalline Co—P matrix containing 2-5 micron diameter SiC particles. No cracks or pits are present, which are typically found in hard chrome. Thus, it is believed that using coatings as described herein helps extend fatigue live by providing a coating that is free or essentially free of imperfections that can act as crack initiation sites. It will be appreciated that the other tribological particles described earlier in this disclosure besides SiC can be incorporated individually or in combination. 
     Applicants believe that the micro-structure of the subject coatings are transition from nano-crystalline to nano-crystalline/amorphous hybrid, to amorphous substantially as set forth in  FIG. 7 .  FIG. 7  illustrates the increase in hardness with the increased incorporation of phosphorus in the coating, wherein the coating is as coated, before heat treatment. Hardness is improved with heat treatment of the Co—P matrix by precipitation of cobalt-phosphide. It is believed that the tribological particles add a synergistic effect and further improve hardness compared to Co—P matrix alone. Heat treatment temperatures can be selected to maximize hardness or toughness (lower temperatures for toughness, higher temperatures for hardness). 
     The compositions of matter, methods and systems of the present invention, as described above and shown in the drawings, provide for a material with superior properties including enhanced corrosion resistance, and hardness and other properties similar to hard chrome, without the environmental hazards associated with electroplating chromium, but also including enhanced fatigue resistance. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention include modifications and variations that are within the scope of the appended claims and their equivalents.