Deposition method and products
This is a continuation of application Ser. No. 702,435, filed July 6, 1976 and now abandoned. 
     Which is a continuation-in-part of application Ser. No. 588,391 filed June 19, 1975, now abandoned, which was a continuation in part of application Ser. No. 358,110 filed May 7, 1973 also abandoned. This invention relates to the production of hard deposits on substrates. More particularly, the invention relates to the production of deposits on substrates as coatings, or the production of free standing objects made from a deposit after removal of substrate. The deposits of the invention have physical characteristics which are substantially improved over those presently known to those skilled in the art. 
     The production of high hardness materials for wear or cutting purposes has been approached in a variety of ways. High carbon steel has often been employed, frequently utilizing alloying ingredients such as chromium, vanadium, tungsten, molybdenum, cobalt, and others to improve hardness, toughness and strength at various operating temperatures. Cast cobalt alloys, such as &#34;Stellites&#34; and similar materials, have also been used for wear and cutting products. Another type of material has been composites of tungsten carbide or other carbides cemented with cobalt or nickel. 
     High carbon steel, with or without other alloying ingredients, has excellent bend strength, particularly at use temperature near room temperature, and quite high impact strength. High carbon steel, however, does not offer satisfactory hardness for wear-resistant and cutting tool products, its hardness being about Vickers nunmber 900 (Vickers hardness numbers are in kg/mm 2  and are designated in the Claims herein as VHN) or a Rockwell C hardness of about 65 to 70. Thus, high carbon and similar tool steels have certain limits on their use. 
     Cast cobalt alloys, particularly those having high percentages of carbon metal alloying species such as chromium, tungsten and others, have hardness values similar to those of high carbon steel. Moreover, they maintain good hot hardness. However, these materials are more difficult to fabricate than high carbon steel, generally cost more, and are quite brittle. 
     In order to overcome the physical and mechanical shortcomings of the aforementioned products and the difficulty in manufacturing them, attempts have been made to produce these materials by deposition. High hardness materials are used as coatings on various types of substrates or are formed into free standing objects to produce wear parts or tool products. For example, commercially successful products having coatings of titanium carbide over cemented tungsten carbide have been produced. Hardnesses of over 3000 Vickers with improved friction characteristics have been achieved. By way of further example, some small diameter tubing of tungsten carbide has been produced by deposition on a mandrel which is subsequently removed. 
     Deposits which have been produced commercially thus far, both for coating substrates and for producing free standing objects, have suffered certain drawbacks. Although hardness appears to be satisfactory in some cases, the strength and toughness of the material has often been lower than desired. Typically, such deposits have been produced by chemical vapor deposition techniques and have resulted in columnar grain structures wherein the grain size is relatively large. Because of the grain size and the columnar distribution of the grains, such deposits have tended to be relatively brittle and mechanically weak. Moreover, the production of hard coatings has generally required the use of a relatively high substrate temperature and relatively low deposition rate during the chemical vapor deposition process. 
     It is an object of the present invention to provide an improved method for producing coated substrates and free standing hard metal products. 
     Another object of the invention is to provide coated substrates and free standing hard metal products having improved physical characteristics. 
     Another object of the invention is to provide, on substrates, improved deposits of superior strength and quality. 
     It is another object of the invention to provide coated substrates with the coating having extremely high hardness and strength, and free standing hard metal objects of great strength. 
    
    
     Other objects of the invention will become apparent to those skilled in the art from the following description taken in connection with the accompanying illustrations wherein: 
     FIG. 1 is a schematic diagram of a chemical vapor deposition system which may be employed in the practice of the method of the invention; 
     FIG. 2 is a photomicrograph at about 200 times magnification of a cross section of a deposit produced in accordance with prior art chemical vapor deposition techniques; and 
     FIG. 3 is a photomicrograph at about 500 times magnification illustrating a cross section of a deposit produced in accordance with the invention. 
    
    
     Very generally, the method of the invention comprises providing a volatile halide to tungsten or molybdenum. The volatile halide is reacted, off the surface of the substrate in the presence of carbon monoxide and water gases to form a first intermediate compound of tungsten or molybdenum. The first intermediate compound is reacted in the presence of gaseous hydrogen and gases of carbon monoxide and water to cause the deposition of the substrate of a second intermediate compound of the metal which is in a liquid phase. (The term substrate is used herein in its broadest sense and is intended to include any form upon which the coating is deposited, whether subsequently used in the bonded condition or dispensed with after deposition such as a mandrel or die.) The liquid phase second intermediate compound is then reacted on the substrate surface to produce a hard deposit containing tungsten or molybdenum and carbon. 
     Chemical vapor deposition, or CVD, is a well known process for producing a coated substrate. In FIG. 1, one common apparatus is illustrated which is used for coating a substrate 11, the latter being shown as a generally cylindrical rod. The rod 11 is supported in a work holder or fixture 12 supported from a rod 13 resting on a disc shaped base 14. The disc shaped base 14 is supported on a reactor base 15 which is provided with an annular groove 16 therein. 
     The reactor is completed by a heat proof cylindrical walled tube 17 of quartz or similar material which seats in the annular groove 16 and is sealed therein by an annular seal 18. The top of the quartz tube 17 is closed by a rubber stopper 19 of conventional design removably secured therein. There is, therefore, defined a reaction chamber 21 in which the deposition process takes place. 
     In order to heat the substrate 11 to the desired temperature, as will be explained, an induction heating coil 23 is provided surrounding the outer wall of the glass or quartz tube 17. The induction heating coil 23 is supported by means not shown and is provided with leads 25 and 27 to which the induction heating current is conducted from a suitable source, also not shown. 
     In order to regulate the pressure within the reaction chamber 21 and removed reaction product gases, the lower wall or base 15 of the reactor is provided with an opening 29 therein through which a tube 31 is passed. The tube 31 is suitably connected to a vacuum pump 33 and a vacuum gauge 35 is connected in the line thereto for indicating the pressure within the chamber 21. By properly operating the vacuum pump 33, the pressure within the chamber 21 may be regulated as desired. 
     A gas inlet tube 37 is provided in the rubber stopper 19 through a central opening 39 therein. The tube 37 is connected through a plurality of tubes 43, 45, 47 and 49 to regulator valves 51, 53 and 57 and flowmeters 59, 61, 63 and 65, respectively. 
     Sources of reactant gases 67, 69, 71 and 73 are connected to the flowmeters 59, 61, 63 and 65, respectively, for introducing the desired reactive gases for producing the chemical vapor deposition reactions within the chamber 21, as will be subsequently described. 
     A known method in which a coating of high hardness is produced on a substrate by chemical vapor deposition involves the introduction to the reaction chamber 21 of a volatile compound of the metal species desired in the deposit. Typically, this is a metal halide. This material, in gaseous form, is passed over a heated substrate, on which heated surface it is decomposed to deposit the metal of interest. A gaseous reducing agent, such as hydrogen, may be mixed with the volatile compound of the metal to assist in reducing it on the heated surface of the substrate. Other gaseous compounds may be added to the gas stream, such as carbon bearing gases, whereby compounds of the metal, such as carbides, are formed by chemical reaction on the heated surface. A more complete explanation of the chemical vapor deposition process may be found in Chapter 13 of the book &#34;Vapor Deposition&#34; editd by Powell, Oxley and Blocker, published by Wylie &amp; Sons, 1966. 
     In FIG. 2, a cross sectional photomicrograph, magnified 200 times, shows a coated substrate produced by typical prior art CVD techniques, more specifically set out in Example 3 below. The specimen was etched in a mixture of dilute nitric and dilute hydrofluoric acid for about 30 seconds at room temperature. It may be seen that the deposit is comprised of relatively large columnar grains which are oriented perpendicularly of the substrate surface. Such deposits are typically quite brittle. 
     In each case involving the practice of chemical vapor deposition, effort is made to insure that the chemical reactions which cause the deposition take place on the surface of the substrate. In other words, a reaction is caused which directly produces a solid deposit from the gaseous reactant or reactants on the surface of the substrate or mandrel. Heretofore, if the reaction was allowed to proceed in the gas stream away from the heated surface, powdery non-adherent and non-coherent deposits were made. 
     The method of the present invention, although similar to chemical vapor deposition, is not truly that. The method of the invention employs a deposition apparatus essentially similar to a chemical vapor deposition apparatus, however, the apparatus is operated in such a manner that the typical chemical vapor deposition process does not take place. 
     In accordance with the method of this invention, a sequence of events is made to take place which is different from what has been believed desirable by those skilled in the art. It has been discovered that superior deposits can be produced by causing a chemical reaction off of the surface of the substrate resulting in a first intermediate product in a gaseous phase. This product is further reacted to result in a second intermediate product which is deposited on the substrate or mandrel in a liquid phase. The liquid phase on the substrate is further reacted to form the desired solid phase. 
     Such reactions may be possible with compounds of a number of metals, including the Group IVB, VB and VIB metals. However, the present invention is directed to producing a deposit comprised of tungsten or molybdenum, and carbon. The general chemical characteristic required is that the volatile halide of the metal portion of the compound must be able to be reacted off the surface of the substrate to produce a first intermediate metallic compound in a gaseous or vaporous phase. This first intermediate compound must then be able to be reacted to form a second intermediate compound having the proper vapor pressure and melting temperature such that this second intermediate compound is deposited on the substrate or mandrel as a liquid. The reaction to produce this second intermediate and relatively non-volatile compound must be relatively fast. The compound must then be able to be converted on the heated surface of the substrate, by disproportionation or reaction with a gaseous species, or both, to the desired solid deposit. 
     The first intermediate compound is produced off of the surface of the substrate and is observable as a fog or white halo slightly upstream with respect to the substrate. Raising the reactor temperature, however, can prevent visible formation of the fog although the reaction still occurs. Although not entirely understood, it is known that for this reaction to take place, there must be present hydrogen and oxygen, and possibly also carbon. The hydrogen should be in some other form than pure hydrogen gas because pure hydrogen does not readily react at room temperature in the diatomic state. Pure hydrogen, however, is required for the later reactions as explained below. The volumetric ratio of the total amount of hydrogen present to the volatile halide should be equal to or less than stoichiometric amounts. In other words, the ratio of the flow rate of hydrogen to the flow rate of the volatile halide should be equal to or less than the ratio of the number of gram-atoms hydrogen to the number of gram-atoms of volatile halide in the balanced reaction. At hydrogen ratios higher than this, conventional chemical vapor deposition tends to take place, with the resultant brittle, columnar grained product. Preferably, the hydrogen to volatile halide volume ratio should be greater than about 0.5 to 1 for adequate yield in the reaction. The first intermediate compound is believed to be some form of the metal in the same valence state as it exists in the initial halide (for example hexavalent tungsten). 
     The first intermediate compound is then reacted in the vicinity of the substrate surface due to the high heat of the substrate and the presence of hydrogen. The result is the deposition on the substrate of a low vapor pressure liquid in a very thin and highly viscous layer. The nature of this liquid second intermediate compound is not understood, however, it is believed to be the metal in some intermediate valence state combined with oxygen, carbon, or both as well as a halogen. For example, the liquid may be an inorganic polymer. The liquid nature of the second intermediate compound is often apparent on the surface of the substrate during the deposition process. It is, however, believed that the liquid always forms even though not always easily observed. 
     The liquid second intermediate compound is then reacted to form the desired solid deposit. This reaction is believed to involve reduction, disproportionation, or both. In any event, the oxygen and any remaining halogen are removed, possibly by reaction with the hydrogen or merely by being carried away with the flow of the hydrogen. The resultant deposit contains the metal and at least about 0.1% and not greater than about 1% carbon by weight. The deposite is a very fine-grained, non-columnar structure, often glass-like in appearance. Some layering is detectable in the deposit under high magnification and is believed to be related to variations in the reaction rates relative to each other. It is postulated that the fine-grained structure results from the extremely rapid conversion of the intermediate liquid phase to a solid by chemical reaction. X-ray diffraction analysis shows the deposit is akin to tungsten but with a very finely dispersed carbide, probably in the form WC. 
     The carbon level is significant. Too much carbon results in a product which is too hard or too brittle. It is believed that all of the carbon exists in the deposit as a dispersed carbide. For higher quantities of carbide in the deposit, the hardness tends to increase, but at the expense of also increasing the brittleness of the deposit. The total volume of the carbon bearing gases relative to the volatile halide of the metal serves to control the proportion of carbon in the solid deposit. Too much carbon results in a brittle deposit. Too little carbon results in the deposition of pure tungsten with columnar grains. It is preferred, for the best operation of the process, that in the gas stream the ratio of gram atoms of carbon to gram atoms of the metal should not exceed unity, and should be greater than 0.03 to 1. 
     The amount of carbon introduced is also dependent upon the oxygen in the system. Preferably, the ratio of gram atoms of carbon to gram atoms of oxygen in the accumulation of gases introduced should not exceed a ratio of about 3 to 1. If this ratio is exceeded, too much carbon is present in the system and the resultant deposit becomes too hard and brittle. 
     The preliminary reaction is caused to occur by reacting the volatile halide of the metal with a gaseous substance containing hydrogen and oxygen. The present invention employs carbon monoxide as both the source of oxygen for the intermediate liquid product and the source of carbon to form the final solid deposit. The hydrogen is provided by water vapor. 
     In order to assure that a liquid phase is deposited on the substrate, the deposition temperature is held between about 650° C. and 1100° C. Too high a temperature volatilizes the liquid, whereas too low a temperature makes the reaction rate unacceptably low. Using the oxygen from one of the above reactants to form the liquid phase deposition, the conversion to the solid hard metal is accomplished by disproportionation or by reacting this liquid phase with hydrogen and the carbon monoxide. A combination of both reactions may actually occur. 
     At higher temperatures in the aforementioned range, a lower hydrogen ratio is required, and conversely, at lower temperatures, a higher hydrogen ratio is required. Lower operating temperatures than the specified range typically result in columnar deposits or in non-adherent powder. The preferred opeating range is about 800° C. to 950° C. Since the reaction or reactions occurring are exothermic, heat builds up in the reactor very quickly. If the reactor is too hot, the reaction which causes the first intermediate compound to change to the second intermediate compound may occur off of the surface of the substrate, preventing deposition. 
     The operating pressure is preferably about 50 Torr or higher and successful deposits have been achieved up to one atmosphere pressure. Typically, the higher the pressure, the higher the deposition rate. If too low a pressure is used (or too high a temperature) the volatility of the liquid second intermediate compound may be exceeded, resulting in a failure of the deposition process. 
     The resultant thermochemically deposited product is substantially free of columnar grains. An example is shown in FIG. 3, which is a deposit produced under the conditions set forth in Example 2 set out below. The cross sectional photomicrograph was produced by etching in a mixture of dilute nitric and hydrofluoric acids for about 30 seconds at room temperature. In the case of tungsten-carbon deposits, the Vickers hardness number typically exceeds 1000 kg/mm 2  with a modulus of rupture in bending greater than 200 kg/mm 2  in the deposited and heat treated condition. The surface in the as-deposited condition is smooth and the grain size is generally equal to or less than 5 microns, typically less than one micron, giving a glass-like or vitreous appearance. 
     As may be seen from FIG. 3, the deposit is laminar in appearance, with the layers appearing to be of the order of 2000A thick. Although not yet understood, it is believed these layers are caused by varying conditions during deposition as evidenced by oscillating turbulence in the fog or halo off the substrate. It is postulated that such layers have different carbon content and may anneal at different rates during deposition. This may result in a complex internally stressed structure in which the layers closest to the substrate are prestressed to a substantial degree of compression. 
     To assist in the understanding of the invention, certain samples of the deposition techniques are given: 
     EXAMPLE 1 
     A molybdenum wire of 0.508 mm diameter was coated with a tungsten-carbon deposit by the following technique: the wire was heated to 925° C. and the flows set as follows: 
     Wf 6  =140 ml per minute 
     Hydrogen=325 ml per minute 
     Carbon Monoxide=200 ml per minute 
     Hydrogen saturated with water vapor at 20° C. and 300 Torr. 
     The reactor vessel was maintained at 300 Torr. The hard deposit was made at a rate of about 0.038 mm per minute for a period of 10 minutes. A white halo was observed surrounding the substrate during deposition, indicating the presence of the first intermediate compound, and a liquid deposit on the substrate was continuously detectable, indicating the second intermediate compound. Liquid droplets were observed to flow near the end of the test specimen. The resulting deposit had a Vickers hardness of 2200 kg/mm 2  and a rupture strength in bending of 220 kg/mm 2 . The specimen was heat treated for 15 minutes at a temperature of 1150° C. and retested. The hardness was observed to have been reduced to Vickers 2100 kg/mm 2  and the bend strength had increased to 280 kg/mm 2 . The molybdenum mandrel was leached in 50% nitric acid to produce a thin wall tube. 
     EXAMPLE 2 
     Using a 0.5 mm molybdenum mandrel which was heated to 925° C., the tungsten hexafluoride rate was set at 150 ml/min, the hydrogen rate at 500 ml/min and the carbon monoxide rate at 200 ml/min. The hydrogen stream was saturated with water vapor at 20° C. and 300 Torr. The reactor pressure was maintained at 300 Torr. A 0.25 mm deposit was effected in ten minutes. The deposited material was determined to have a hardness of 900 Vickers and a bend strength of 90 kg/mm 2 . The material was extremely brittle and showed no improvement by heat treat. Metallographic examination showed a typical chemical vapor deposition columnar habit to the crystals. Since the hydrogen to WF 6  ratio was high, the deposit was essentially directly from the gas stream to the solid material on the mandrel and clearly out of the limits of the invention. 
     EXAMPLE 3 
     An experiment was conducted to compare the method of the invention with more conventional CVD techniques. Tungsten hexafluoride was flowed over a 0.508 mm diameter molybdenum wire at a rate of 140 ml/min with hydrogen at a flow of 420 ml/min and carbon monoxide at a flow of 560 ml/min. The wire was held at a temperature of 800° C. Deposition occurred at a rate of 20 μ/min. No fog was observed in the chamber nor was any liquid apparent on the wire. Rather, a finely divided black powder was deposited on the chamber walls. The resultant deposit had a fine-grained, dull, metallic appearance. A metallographic specimen showed fine grain columnar crystals extending radially from the surface with some cylindrical rings superimposed. Hardness of the material was 2,000 kg/mm 2  as measured with a 500 gram weight on a Vickers hardness tester. Modulus of rupture in bending was 110 kg/mm 2 . Failure on the Bend Test was intergranular, i.e. as compared with the typical diagonal, or near axial breaks of samples by the method of the invention. 
     EXAMPLE 4 
     A nichrome wire of 0.25 mm diameter was heated to 850° C. A flow rate of 300 ml/min was set for molybdenum hexafluoride along with a flow of 325 ml/min of hydrogen saturated at room temperature with water. Carbon monoxide was injected at 150 ml/min. Deposition was conducted at 200 Torr for 10 minutes. The deposite was 0.50 mm thick and had a hardness of 1900 kg/mm 2  VHN. Rupture strength in bending was 170 kg/mm 2 . 
     The tungsten-carbon deposits of the invention appear on the average to be slightly harder than equivalent tungstencarbide made by prior art techniques. This is dependent, of course, on the ratios of metal to carbon in the gas stream. At the highest preferred ratios, Vickers hardness numbers of up to 2500 kg/mm 2  are achieved. In addition, unusually high bend strengths are achieved. Typical bend strengths for hot pressed tungsten carbide rarely exceeds about 50 kg/mm 2 , whereas, tungsten-carbon deposits made by the method of the invention will frequently exceed 300 kg/mm 2 . This last strength number actually exceeds the strength of cemented tungsten carbides. The unusual high strength is believed to be related directly to the fine grain laminar grain structures such as illustrated in FIG. 3. The modulus of elasticity before or after heat treating is equal to or greater than 50,000 kg/mm 2 . 
     It may therefore be seen that the invention provides an improved method for producing a coated substrate, as well as improved quality coated substrates. The structure of the coating composition is such as to provide superior physical qualities. More particularly, in the case of tungsten carbide deposits, the deposits are smooth surface fine grained randomly distributed crystals essentially free of columnar orientation and having a very high modulus of rupture. By subsequent heat treating, such tungsten carbide deposits may be almost doubled in their modulus of rupture. Molybdenum-carbon alloy systems can also be effectively improved in their deposit quality in accordance with the invention. Parameters necessary to do this are readily determinable by those skilled in the art from the information contained herein combined with that contained in &#34;Techniques of Metals Research&#34;, R. F. Bunshah, Ed., Interscience Publishers, Div. of J. Wylie and Sons, New York, New York, 1968, Volume 1, Chapter 33. 
     Various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description and accompanying drawings. Such modifications are intended to fall within the scope of the appended claims.