METAL SPRAY FORMING USING MULTIPLE NOZZLES

Abstract: A method of spray casting forming a metal or metal alloy resulting in a finished product, which has a minimum porosity. The method comprises directing a stream of metal or metal alloy at a collecting member to form a deposit. The solidification rate of the deposited metal or metal alloy is controlled on the collecting member to produce a highly dense product which may not require hot working or reduces the amount of hot working.

Description: METAL SPRAY FORMING USING MULTIPLE NOZZLES BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to the formation of metal or metal alloy products by using spray casting techniques. The metal or metal alloy products which are produced according to this invention have a minimum of porosity. 2. Description of Related Art It is well known in the art that a metal or metal alloy can be made by casting, spray casting into a die or by spray casting onto a substrate to form a particular shape. Casting a metal into a desired shape can be achieved by several different techniques, for example, sand casting, die casting, centrifugal casting, shell molding or investment casting. Articles produced by these methods, however, may possess poor mechanical properties mainly as a result of relatively large grain sizes, structural weaknesses and defects arising from the casting process, eg. shrinkage and segregation. The formation of a particular shape by casting involves the casting of a metal or metal alloy as an ingot, followed by a hot working step, eg. hot rolling, forging, pressing or extruding. The formation of the finished shape is usually completed by a cold working process, eg. cold rolling, pressing, coining or spinning. In either case, semi-finished products (ie. plates and bars) often have to be manufactured before subsequent processing to produce finished articles. In the formation of particular shapes by spray casting, complex shaped articles can be manufactured having mechanical properties generally superior to those articles produced by casting the shapes by the first method described above. However, porosity is a major problem in the formation of shapes by spray casting. Spray casting molten metal into a desired shape is achieved by atomization of the molten metal into a spray which is collected on a suitable substrate or die. In the past, almost all products produced with this process required hot working because of the high degree of porosity in the finished product. The problem with porosity is a major concern in this process. The process can produce products of a controlled degree of porosity as shown in U.S. Patent No. 3826301 to Brooks, column 2, lines 55-60. The use of powder metallurgy in the production of metal or metal alloy shape is also well known. Metal powder can be compacted by the use of dies to produce a number of desirable shapes. The produced shapes may be further worked to obtain, as far as it is possible, the desired physical properties. However, one of the limitations to this process is that the final product tends to exhibit undesirable amounts of porosity. Thus, in order to remove the porosity, it has been proposed to subject the finished shape to cold and/or hot working. A process has been proposed for the direct fabrication of metal shapes of long length and relatively thin cross section by spray casting. The process comprises depositing a plurality of coherent layers of metal onto a substrate by directing sprays of atomized particles of molten metal onto the substrate. Then, a single layer is formed, while the metal is at a temperature above its recrystallization temperature. The metal layer is usually hot worked to provide for improved physical properties. This process is disclosed in U.S. Patents Nos. 3670400 and 4579168 to Singer and is particularly applicable to the production of strip. The Singer patents disclose that atomized aluminum can be spray cast onto a moving target, such as a steel belt and the spray formed strip, while still hot, removed and hot rolled to the desired gauge. In this process, metal strip thicknesses of up to about 0.5" may be produced, with the thickness generally ranging from about 0.01 to 0.375". The Singer patent also states that the porosity of the deposit layers ranges from about 15% to about 20%. When porosity is greater than 15%, a finished product would require hot working before further cold working steps can be performed. Another prior art method that attempts to deal with the problems of porosity is described in U.S. Patent No. 3826301 to Brooks. The Brooks patent teaches the production of shaped precision metal articles from molten metals and alloys by spray casting onto a die contoured to the shape of the desired article. The method disclosed in Brooks comprises directing an atomized stream of molten metal or metal alloy onto a collecting member to form a deposit and then directly working the deposited material on the collecting member by means of a die to form the desired shape. The purpose of the working is to density the metal deposit which is porous. This is brought out in column 2, lines 50-61 of the Brooks patent. Brooks states that the forming operation is normally carried out as soon as the required mass of metal has been deposited onto the die or collecting member. The patent also states that the spray deposit can be cold formed after it has been cooled. Another process for producing elongated metal articles is disclosed in U.S. Patent No. 4114251 to Southern et al. The Southern et al patent discloses a process for producing elongated metal articles by atomizing molten metal and collecting the atomized particles on a moving support. The collected particles are then consolidated by, for example, passing the metal through rolls to form an elongated metal strip. Another well-known technique for producing a continuous strip of metal is shown in U.S. Patent No. 3576207 to Grenfell. The Grenfell patent discloses a process for continuous casting of metal strip by imparting an electrostatic charge of at least 80,000 volts to a stream of molten metal. The stream of metal is then passed through a nozzle into an inert gas flow and allowed to atomize into a fine spray. The spray droplets are then collected on a receiving surface to form a layer of metal on the collecting member. This is followed by continuously stripping the layer of metal from the collecting member. In almost all of the above disclosed prior art references, metal articles are produced as either strip, ingots, discs or other shapes, but porosity is a problem in the spray cast products. Other patent publications relating to the spray casting process include United Kingdom Patent Applications Nos. 2172827A and 2172900A, European Patent Applications Nos. 0225732 and S 0225080, and Patent Co-operation Treaty Patent Application No. WO87/03012. The present invention is directed to the process for spray casting a metal or metal alloy wherein the finished product has a minimum of porosity. Thus, the process described by the present invention should reduce the amount of hot working that may be required. The porosity expected in the spray cast products made in accordance with this invention should be less than 15% and, preferably, less than about 10% by vo1ume. The process of the instant invention utilizes the techniques taught in Brooks, U.S. Patents Nos. 3826301 and 3909921, to atomize molten metal and to deposit the atomized metal onto a collecting member. In performing the instant process, particular care is taken to control the volume fraction of solid of the atomized metal or metal alloy particles as they deposit on the collecting member. In accordance with the instant invention, a process and apparatus for spray casting a metal or metal alloy is provided wherein the porosity of the produced metal or metal alloy should be substantially minimized. At least one supply of metal or metal alloy is held in a molten state. Then, at least first and second streams of the molten metal or metal alloy are allowed t.o issue from the supply. Each of the first and second sprays of partially solid particles. Each of the first and second sprays is deposited onto a collecting member. The particles deposited onto the collecting member solidify into a desired shape. The collecting member moves in at least one desired direction. The second spray is arranged to deposit onto the collecting member downstream of the first spray in the desired direction. The first spray deposits onto the collecting member with a first volume fraction of solid. The second spray deposits onto the collecting member with a second volume fraction of solid. The second volume fraction of solid is greater than that of the first volume fraction of solid. The process of the instant invention may be used to spray cast a metal or metal alloy, to form ingots, to coat articles and to form any desirable shape, especially strip, bar, tube or compound tube or bar. Preferably, the metal or metal alloy is formed by atomizing the streams of metal or metal alloy by directing respective gas flows at the streams. The temperatures of the gas flows are less than the temperature of the streams of metal or metal alloy. Any suitable gas may be used to atomize the stream of molten metal, but preferably the gas is non-oxidizing and inert. For example, nitrogen or argon would be acceptable. However, if oxidation of the particles is not undesirable, compressed air can be used as an atomizing medium. The atomizing step in the process for the present invention will be consistent with that taught in U.S. Patent No. 3826301 to Brooks, which patent is incorporated herein by reference. Accordingly, it is an object of this invention to provide a process and apparatus for spray casting a metal or metal alloy to obtain a finished product with a minimum amount of porosity. It is a further object of the invention to provide a process and apparatus for forming metal or metal alloy which should reduce the need for hot working of the product produced by this process. These and other objects of this invention will become apparent by the following description and drawing. Embodiments of the process in accordance with the instant invention are shown in the drawings wherein like or primed numerals depict like parts. Figure 1 depicts schematically a spray casting apparatus in accordance with the present invention; Figure 2 depicts schematically another embodiment of a spray casting apparatus in accordance with the present invention; and, Figure 3 depicts schematically another embodiment of a spray deposition apparatus in accordance with the present invention. Referring to the drawings and particularly Figure 1, the instant invention is directed to a process and apparatus (10) for spray casting a metal or metal alloy which has a minimum of porosity and which should not require hot working after it has been produced. The process comprises holding at least one supply (11) of metal or metal alloy in a molten state. Then, allowing at least first (12) and second (13) streams of the metal or metal alloy to issue from the supply (11). Each of the first (12) and second (13) streams of metal or metal alloy are atomized by atomizers (14) and (15) into first (16) and second (17) sprays, respectively, of partially solid particles. Each of the first and second spray (16) and (17) are deposited onto a collecting member (18) with the particles solidifying into a desired shape. The collecting member (18) moves in a desired direction shown by arrow (19) during deposition. The second spray (17) is arranged to be deposited onto the collecting member (18) downstream of the first spray (16) in the specified desired direction (19). The first spray (16) which is deposited onto the collecting member (18) has a first volume fraction of solid as it deposits. The second spray (17) that is deposited onto the collecting member (18) has a second volume fraction of solid as it deposits. The second volume fraction of solid is greater than the first volume fraction of solid. With this arrangement the initial deport on the substrate has a sufficient fraction of liquid to fill the inherent interstices between the splatted droplets on the substrate and provide a proper interface with subsequent deposits. The deposit from the second spray has sufficient solid to ensure that the shape is maintained. Thus, the metal or metal alloy product (20) produced in accordance with this process should contain a minimum amount of porosity. The product (20) should be very high in density. The porosity of the product (20) most preferably is less than about 10%. In the present invention, a metal or metal alloy may be atomized in the manner taught by U.S. Patents Nos. 3826301, 3909921 and RE 31767 to Brooks and U.S. Patents Nos. 3670400 and 4579168 to Singer or any other desired spray casting technique. The present invention is particularly directed to the spray casting of a metal or metal alloy into strip but may be applicable to forming or coating products (20) of any desired shape. For example, the process of the instant invention is particularly useful for making metal or metal alloy strip that can be removed from a collecting member (18) with the collecting member moving at a continuous rate. The present invention comprises spray casting either a metal or metal alloy and controlling the volume fraction of solid of the particles depositing onto a collecting member (18) to minimize porosity in the finished product (20). The spray (16) and (17) of metal or metal alloy particles being deposited onto the collecting member (18) should have different volume fractions of solid. In accordance with this invention, a first spray of particles (16) is deposited onto the collecting member (18). It has a first volume fraction of solid at the time it deposits or impacts thereon. A second spray (17) is subsequently deposited onto the collecting member (18) downstream of the first spray (16). The volume fraction of solid of the second spray of partially solid particles (17) is greater than that of the first spray (16). The process of making metal or metal alloy products (20) in accordance with the instant invention has several advantages over the prior art methods. First, the deposition techniques should result in a substantial reduction or elimination of the porosity in the product (20). Secondly, the product (20) which is formed by the process of the present invention should not require further hot working. Referring again to Figure 1 , an apparatus (10) for spray casting the metal or metal alloy is shown. The molten metal or metal alloy (21) is prepared or melted in a furnace (22). It is then poured at a desired rate into trough (23). The molten metal or alloy (21) passes from the trough (23) to the tundish (24) via downspout (25). The flow rate of molten metal (21) into the tundish (24) is controlled by a conventional pin type valve (26) which moves up or down'above the downspout (25) to respectively increase or decrease the flow of molten metal (21). The tundish (24) shown is a holding vessel which is capable of holding the metal or metal alloy at depths up to 20" or more. A preferred depth for the metal or metal alloy in the tundish (24) is from about 6 to 12", depending upon the deposition rate to be employed. The tundish (24) should preferably be heated by an external heating mechanism (27) in order to maintain the metal or metal alloy at a desired temperature. Advantageously, the temperature should be up to 200°C above the melting temperature of the metal or metal alloy. The heating mechanism (27) can be any suitable means for heating the tundish (24), ie. an induction heating coil attached to the external walls of the tundish (24) would suffice. It might be mentioned that the temperature of the metal or metal alloy in the tundish (24) is important. The temperature should be sufficiently high to prevent freeze up in the nozzles (28) and (28') attached to the tundish (24). The temperature should be low enough so that the atomized particles solidify rapidly with fine grains and low oxygen pickup. It is important that the tundish (24) be preheated before pouring the metal or metal alloy (21) therein. The temperature of the metal or metal alloy (21) in the tundish (24) is monitored by conventional means (not shown) for controlling the external heating mechanism (27). The furnace (22) and trough (23) will continuously or semi-continuously deliver metal or metal alloy to the tundish (24), as desired. The streams (12) and (13) issue from the tundish (24) through openings referred to as plenums (29). The plenum (29) is an opening in the bottom of the tundish (24). The plenums (29) provide a passageway for the streams (12) or (13) of metal or metal alloy (21) to flow to the nozzles (28) and (28* ). At the exit of the plenums (29), there are nozzles (28) and (28') positioned to receive streams (12) or (13). The nozzles (28) and (28') are supported by the tundish (24). The streams (12) or (13) exit the tundish (24) through the plenums (29) and flow into the nozzles (28) and (28'). The streams (12) or (13) are atomized by conventional means as, for example, those illustrated in U.S. Patents Nos. 3826301 and 3909921 to Brooks, 3670400 and 4579168 to Singer, or 4066117 to Clark et al . All of the above patents are incorporated by reference herein. The type of nozzles (28) and (28') used for atomization can be those set forth in the Clark, Singer or Brooks patents. The flow rate of the molten metal or metal alloy (21) from the tundish (24) is influenced by the throat diameter of the nozzles (28) and (28') and by the head of the metal or the metal alloy in the tundish (24). The flow rate is essentially proportional to the square root of the head height in the tundish (24). The flow rate is also approximately proportional to the throat diameter squared of the nozzles (28) and (28'). Lower flow rates product smaller atomized particles at a given atomizing gas flow rate. The nozzles (28) operate in a chamber (30) which preferably has an atmosphere of an inert or non-oxidizing gas. Sufficient space is provided below the tundish (24) for supporting the collecting member (18). When atomization of the streams (12) and (13) of the metal or metal alloy (21) is complete, they become sprays (16) and (17) of partially solid particles. The sprays (16) and (17) of partially solid particles issue from the nozzles (28) and (28') in a conical shape and are deposited onto the collecting member (18). By employing conically configurated atomized sprays (16) and (17), the bulk of the sprays of partially solid particles are captured by the collecting member (18). In carrying out the invention, the metal or metal alloy is generally atomized' under non- oxidizing conditions. The chamber is purged of oxygen using a non-oxidizing gas and/or a vacuum. The metal or metal alloy is poured into the tundish (24) while maintaining its temperature from about 50 to 200°C above its melting point. The metal or metal alloy then flows through the plenums (29) located in the bottom of the tundish (24) to form streams (12) and (13). An inert or non-oxidizing gas is supplied under pressure from source S and S' via conduits (31) and (31 ' ) to the atomizers (14) and (15) resulting in the atomization of the streams (12) and (13) of metal or metal alloy. In the atomizers (14) and (15), the gas is discharged under pressure. The gas is directed against the streams (12) and (13) to form conically configurated outwardly expanded atomized sprays (16) and (17) of partially solid particles which are directed to the collecting member (18) disposed in the path of the sprays. The collecting member (18) may be of any conventional design. Preferably, it is an endless surface (18) adapted for continuous operation. For example, a belt type design (32) as shown. The belt (33) may be of any desired material. The belt is driven by rolls (34). Idler rolls (35) support the belt during deposition. Overspray and exhaust gas are collected by suitable means and removed via an appropriate conduit for disposal, such as conduit (37). In accordance with the present invention, to minimize porosity the partially solid particles deposited on the collecting member (18) by the first spray (16) should preferably have a volume fraction of solid which is from about 20% to about 60% and, most preferably, from about 30% to about 60%. Preferably, the partially solid particles deposited by the second spray (17) on the deposit from the first spray would have a higher volume fraction of solid of from about 50% to about 90% and, most preferably, from about 60% to about 90%. There are many parameters for controlling the volume fraction of solid in the sprays (16) and (17) as they deposit. Among these parameters are the gas temperature and/or flow rate during atomization and/or the nozzle to collecting member distance and/or the metal temperature in the tundish and/or the flow rate of the metal or metal al loy. There are several ways to achieve the respective volume fractions of solid in the first and second sprays (16) and (17). A number of such approaches will be described as embodiments of the present invention although other approaches for achieving the varying volume fractions of solid could be employed as well as combinations of the described approaches. The following embodiments will be described by reference to Figure 1. DESCRIPTION OF THE PREFERRED EMBODIMENTS In accordance with one embodiment of this invention, a higher volume fraction of solid is provided in the spray (17) as compared to the spray (16) through the use of similar atomizing conditions, namely gas flow rates and temperatures, while having a higher volumetric flow rate of molten metal or alloy (21 ) passing through nozzle (28) as compared to nozzle (28'). The first spray (16) comprising a larger volume of metal requires a greater amount of heat to be extracted than the spray (16) to achieve the same volume fraction of solid as the spray (17). Since the rate of heat extraction from both sprays (16) and (17) is similar due to the use of similar atomizing conditions, the spray (16) will have a small volume fraction of solid than the spray (17). Achieving a difference in the volumetric flow rate through nozzle (28) as compared to nozzle (28') can be achieved in a variety of ways. The nozzle (28) could have a larger orifice throat diameter than the nozzle (28'). Alternatively, valves in the plenums (29) (not shown) could be used to adjust the respective volumetric flow rates. Alternatively, a pin type valve similar to the valve (26) in the trough (23) could be used in association with each of the streams (12) and (13). In accordance with an alternative embodiment of this invention, the volumetric flow rates of molten metal (21) through the nozzles (28) and (28') are maintained at essentially similar levels. The atomizers (14) and (15) are connected via separate conduits (31 ') and (31x) to different sources (S') and (Sx) of atomizing gas. The volumetric flow rate of gas through the conduit (31) is adjusted by valve (38) to be higher than the volumetric flow rate of gas through the conduit (31' ). The lower flow rate through the conduit (31) is provided by adjusting the valve (38). The use of a higher volume of atomizing gas for atomizing and cooling the metal issuing from nozzle (28') will result in a higher volume fraction of solid as compared to the spray (16) issuing from nozzle (28). In accordance with yet another embodiment the atomizing gas provided through conduit (31') is at a higher temperature than the atomizing gas provided through conduit (31x). This may be achieved by the use of respective heating or cooling systems (39') and (39x) arranged about the respective conduits (31') and (31x). If the gas flowing through conduit (31 ') is at a higher temperature than the gas flowing through conduit (31x), then the spray (16) issuing from nozzle (28) will have a lower volume fraction of solid than the spray (17) issuing from nozzle (28'). This occurs since the higher temperature gas will have a reduced cooling effect. Three different approaches have been illustrated for varying the volume fraction of solid between the respective sprays (16) and (17) using the apparatus (10) of Figure 1. These approaches can be used individually or in combination as desired to achieve the desired volume fractions of solid in the respective sprays (16) and (17). Referring now to Figure 2, additional alternative embodiments for varying the volume fractions of solid between the respective sprays (16) and (17) will be described. The apparatus (10') in Figure 2 is similar to the apparatus (10) shown in Figure 1, except that the direction of movement of the collecting member (18) is opposite. The most significant change in the apparatus of (10* ) versus (10) is the use of two separate tundishes (24) and (24'), one for each respective nozzle (28) and (28') in the apparatus (10* ). The use of two tundishes (24) and (24*) allows the temperature of the molten metal supply (11) in the first tundish (24) to be varied from the temperature of the molten metal supply (11') in the tundish (24'), if desired. Further, the use of two tundishes (24) and (24') allows the respective distance of travel of the spray (17) to be different from the distance travelled by the spray (16). Since two tundishes (24) and (24') are employed, it is necessary to have two pin valves (26) and (26') controlled by float sensors (40) for controlling the height of the molten metal supply (11) in each tundish (24) and (24'). Further, two downspouts (25) and (25') are employed. When the tundish (24') is in its lowest position, as shown in phantom, which would be employed if it were only desired to vary the temperature of the respective melts (11) and (11 '), then the downspout (25' ) would be essentially the same as that shown at (25). However, when the tundish (24') is raised up by jack (41) via crank (42), as shown in solid lines, then the downspout (25') is shorter than the downspout (25). The purpose of the downspouts is to prevent oxidation of the molten metal as it is poured from the trough (23') into the respective tundishes (24) and (24'). A bellows (44) or other suitable means may be provided about the nozzle (28') and spray (17) extending from the bottom of the tundish (24') to the top of the chamber (30) to prevent oxidation of the spray (17) due to expanse to the atmosphere. If the apparatus (10') is operated under constant conditions of atomization for the respective nozzles (28) and (28 1 ), then in accordance with yet another embodiment of this invention the first spray (16) is made to travel a shorter distance from the nozzle (28) to the collecting member (18) than the distance the second spray travels from the nozzle (28') to the depositing product (20). This increase in distance travelled by the second spray (17) will cause its volume fraction of solid to be greater than the first spray since it is subject to cooling for a longer period of time. In accordance with yet another embodiment of the present invention, the tundishes (24) and (24') would be at the same level (as shown in phantom) and the atomizing conditions essentially the same except that the temperature of the molten metal in supply (11) would be higher than the temperature of the molten metal in the supply (11'). This could be achieved by any desired means and, in particular, by changing the power applied to the heating coil (27) as compared to the heating coil (27*) in a manner to provide the desired temperature differential. Since the spray (16) issuing from the nozzle (28) 'would be at a higher initial temperature than the spray (17) issuing from the nozzle (28'), the spray (17) would be expected to have a higher volume fraction of solid as it deposits on the collecting member (18). As with the embodiments of Figure 1 , the approaches demonstrated in- Figure 2 can be used individually or in combination. Further, they can be used in combination with any or all of the approaches described by reference in Figure 1. The ranges of volume fraction of solid for each of the sprays (16) and (17) are of importance. If the volume fraction of solid is below the respective lower limit for the sprays (16) or (17), then the product which is deposited is too liquid making it difficult to maintain its shape. It is also subject to gas porosity. If the upper limit for the respective volume fractions of solid of the sprays (16) and (17) is exceeded, then interconnected porosity is formed which is highly detrimental to the soundness of the product (20). While the mechanism of this invention is not fully understood, it is believed that the different volume fractions of the solid required for the respective first and second sprays (16) and (17) is associated with the fact that the first spray (16) deposits on the collecting member (18); whereas, the second spray deposits on the hot deposit from the first spray. It is preferred in accordance with this invention that the collecting member surface (18) be preheated prior to receiving the deposit (20) by any desired means such as torch (43). It is believed that preheating the collecting member (18) helps to further reduce porosity in the deposit (20 ) . To reduce melt oxidation, conventional melt covers or protective atmospheres should be provided over the melt (21) in the furnace (22), trough (23) or (23') and tundish (24) or (24'). Strip type products which can be formed in accordance with this invention should have a minimum of porosity throughout the bulk of their structure. It is possible, however, that the surface region formed adjacent the collecting member (18) may have an undesirable level of porosity as compared to the remainder of the structure. Any such undesirable surface region can be easily removed by conventional machining, such as milling or skiving techniques to leave a bulk structure having a minimum or no porosity. . While this invention should be applicable to any desired metal or alloy, it is particularly applicable to copper or copper alloys. In Figure 3, the embodiment is very similar to the embodiment of Figure 2 except that, . instead of forming strip, a tubular product is formed about a rotating mandrel (50) being withdrawn in the direction of arrow (19). In this embodiment, in order to minimize base porosity adjacent the mandrel (50), the first spray (16) is deposited in such a way as to raise the temperature of the surface of the mandrel as rapidly as possible to a temperature whereby there is sufficient heat remaining in the newly formed deposit (51) so that the deposit from the second spray (17) will have a minimum heat loss to the newly formed deposit surface. Thus, the gas from the first spray (16) does not extract all the superheat and latent heat from the metal in the first spray (16) and therefore allows the temperature of the deposit to rapidly increase to form a thin semi-1 iquid/semi- solid surface layer. Subsequently, in order to maintain this layer and prevent it becoming unstable, the second spray (17) deposits with substantially all superheat and latent heat removed. With this invention, the condition of the first spray (16) is therefore adjusted to match the thermal characteristics of the mandrel (50). Although the present invention reduces porosity, it may be desirable to hot work the tubular product formed. The present invention is also applicable to the formation of bar and compound bar or tube products where the mandrel (50) is retained to form part of the final product. In this case, densification of any porosity present by hot work would be essential and the method of the present invention minimizes the extent of base porosity. The mandrel may be tubular or solid and may be the same composition as the deposited material or different. In this aspect of the invention, we have therefore provided spray depositing first and second sprays onto a collecting member moving in a desired direction during deposition, the second spray being arranged to deposit onto the collecting member downstream of the first spray. The first spray is provided with a latent or superheat greater than the capacity of the collecting member to absorb heat from the depositing metal or metal alloy whereby a surface layer of semi-solid/semi-liquid metal or metal alloy is formed on the collecting member and substantially all of the latent heat of the second spray is extracted by the time the second spray deposits onto the collecting member. In this way, the surface layer is maintained without instability and subsequent partially solid droplets are deposited into the layer. The greater latent heat of the first spray minimizes the base porosity of the metal or metal alloy at the interface with the collecting member which can be removed substantially completely by machining or, if the collecting member is retained by hot working. The different latent heats of the first and second sprays may be provided by controlling at least one of the conditions of: the atomizing gas temperatures of the first and second streams; the spray height between the supply and the collecting member of the respective stream; the metal flow rate of the first and second streams; and the atomizing gas flow rate. While the invention has been described above with reference to specific embodiments thereof, it is apparent that many changes, modifications and variations can be made without departing from the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications and variations that fall within the spirit and broad scope of the appended claims. All patent applications, patents and other publications cited herein are incorporated by reference in their entirety.

Claims: WHAT IS CLAIMED IS:- 1. A process of spray casting a metal or metal alloy comprising the steps of: holding at least one supply of metal or metal alloy in a molten state; allowing at least first and second streams of said molten metal or metal alloy to issue from said supply; atomizing each of said first and second streams into a respective first and second sprays of partially solid particles; depositing each of said first and second sprays onto a collecting member wherein said particles solidifying into a desired shape; moving said collecting member in at least one desired direction during deposition; said second spray being arranged to deposit onto said collecting member downstream of said first spray in said desired direction; providing said first spray as it deposits onto said collecting member with a first volume fraction of solid; and, providing said second spray as it deposits onto said collecting member with a second volume fraction of solid, said second volume fraction of solid being greater than said first volume fraction of solid; whereby the porosity of said metal or metal alloy is substantially minimized. 2. A process as in claim 1 , wherein the step of providing said first and second volume fractions of solid comprises adjusting the respective temperatures of said first and second streams so that said first stream is hotter than said second stream. 3. A process as in claim 1, wherein the step of providing said first and second volume fractions of solid comprises arranging said streams so that said second stream travels a greater distance from said supply to said collecting member than said first stream. 4. A process as in claim 1, wherein the step of providing said first and second volume fractions of solid comprises adjusting the respective flow rate of the particles of said first and second streams so that the flow rate of said first stream is greater than that of said second stream. 5. A process as in claim 1, wherein said first volume fraction of solid is about from 20 to about 60%. 6. A process as in claim 1, wherein said second volume fraction of solid is from about 50 to about 90%. 7. A process as in claim 5, wherein said second volume fraction of solid is between 60 to 90% . 8. A process as in claim 1, wherein said atomizing comprises directing respective gas flows at said first and second streams, with the temperature of said gas being less than the temperature of said first and second streams. 9. A process as in claim 8, wherein said gas is an inert gas. 10. A process as in claim 8, wherein said gas is non-oxidizing. 11. A process as in claim 9, wherein said gas is non-oxidizing. 12. A process as in claim 8, wherein the step of providing said first and second volume fractions of solid comprises adjusting the flow rate of said gas so that the gas flow rate directed at said second stream is greater than the gas flow rate directed at said first stream. 13. A process as in claim 8, wherein the step of providing said first and second volume fractions of solid comprises adjusting the temperature of said gas so that said temperature of said second spray is less than that of said first spray as they deposit onto said collecting member. 14. A process of spray casting a metal or metal alloy comprising the steps of: holding at least one supply of metal or metal alloy in a molten state; allowing at least first and second streams of molten metal or metal alloy to issue from said supply; atomizing each of the first and second streams into respective first and second sprays of metal or metal alloy droplets; extracting a controlled amount of heat from the droplets of the sprays in flight; depositing each of the first and second sprays onto a collecting member wherein the metal or metal alloy solidifies into a desired shape; moving the collecting member in at least one desired direction during deposition; the second spray being arranged to deposit onto the collecting member downstream of the first spray in said desired direction; providing the first spray with a latent heat greater than the capacity of the collecting member to absorb heat from the depositing metal or metal alloy whereby a surface layer of semi-solid/semi- liquid metal or metal alloy is formed on the collecting member; extracting substant ally all of the latent heat of the second spray by the time the spray deposits onto the collecting member whereby said surface layer is maintained into which subsequent partially solid droplets are deposited, the greater latent heat of the first spray minimizing the base porosity of the metal or metal alloy at the interface with the collecting member. 15. A process according to claim 14, wherein the different latent heats of the first and second sprays is provided by controlling at least one of the conditions of: the atomizing gas temperatures of the first and second streams; the spray height between the supply and the collecting member of the respective stream; the metal flow rate of the first and second streams; and the atomizing gas flow rate of the first and second streams. 16. A process according to any one of the preceding claims, wherein the collecting member is rotatable about an axis extending in said desired direction whereby an annular deposit is formed about the collecting member. 17. A process according to claims wherein the formed deposit is hot worked to substantially eliminate any residual porosity. 18. A process according to claim 17, wherein the collecting member is selectively either machined away to provide a tubular deposit or retained as part of a composite bar deposit. 19. An apparatus for spray casting a metal or metal alloy comprising: a means for holding at least one supply of metal or metal alloy in a molten state; a means for allowing at least a first and second stream of said molten metal or metal alloy to issue from said supply; a means for atomizing each of said first and second streams into respective first and second sprays of partially solid particles; a means for collecting deposits of each of said first and second sprays, said means having a collecting member upon which said particles solidify into a desired shape; with said collecting means further including a means for moving said collecting member in at least one desired direction during deposition; said second spray being arranged to deposit onto said collecting member downstream of said first spray in said desired direction; a means for providing said first spray as it deposits onto said collecting member with a first volume fraction of solid; and a means for providing said second spray as it deposits onto said collecting means with a second volume fraction of solid which is greater than said first volume fraction of solid; whereby the porosity of said metal or metal alloy is substantially minimized. 20. An apparatus as in claim 19, wherein the means for providing said first and second volume fractions of solids comprise means for adjusting the respective temperatures of said first and second streams so that said first stream is hotter than that of said second stream. 21. An apparatus as in claim 19, wherein the means for providing said first and second volume fractions of solid comprises arranging said streams so that said second stream travels a greater distance from said holding means to said collecting member than that of said first stream. 22. An apparatus as in claim 19, wherein the means for providing said first and second volume- fractions of solid comprises means for adjusting the respective flow rates of said first and second streams so that the flow rate of said first stream is greater than that of said second stream. 23. An apparatus as in claim 19, wherein said first volume fraction of solid is from about 20 to about 60%. 24. An apparatus as in claim 19, wherein said second volume fraction of solid is from about 50 to about 90%. 25. An apparatus as in claim 19, wherein said second volume fraction of solid is from about 60 to about 90%. 26. An apparatus as in claim 19, wherein said means for atomizing comprises means for directing respective gas flows at said first and second streams and means for controlling said respective gas temperatures so that the temperature of the gas directed at said first stream is greater than the temperature of the gas directed at said second stream. 27. An apparatus as in claim 19, wherein said gas flows comprise an inert gas. 28. An apparatus as in claim 19, wherein said gas flows are non-oxidizing. 29. An apparatus as in claim 19, wherein said gas flows are non-oxidizing. 30. An apparatus as in claim 19, wherein said means for providing said first and second volume fractions of solid comprises means for adjusting the rate of flow of said respective gas so that the gas flow rate directed at said second stream is greater than the gas flow rate directed at said first stream. 31. A metal or metal alloy deposit made from the process described in claim 1 or 14. AMENDED CLAIMS [received by the International Bureau on 1 June 1992 (01.06.92); original claims 14 and 15 amended; other claims unchanged (2 pages)] alloy in a molten state; allowing at least first and second streams of molten metal or metal alloy to issue from said supply; atomizing each of the first and second streams into respective first and second sprays of metal or metal alloy droplets; extracting a controlled amount of heat from the droplets of the sprays in flight; depositing each of the first and second sprays onto a collecting member wherein the metal or metal alloy solidifies into a desired shape; moving the collecting member in at least one desired direction during deposition; the second spray being arranged to deposit onto the collecting member downstream of the first spray in said desired direction; depositing the first spray in a condition in which not all of the latent heat has been extracted and the remaining heat is greater than the capacity of the collecting member to absorb heat from the depositing metal or metal alloy whereby a surface layer of semi- solid/semi-liquid metal or metal alloy is formed on the collecting member; extracting substantially all of the latent heat of the second spray by the time the spray deposits onto the collecting member whereby said surface layer is maintained into which subsequent partially solid droplets are deposited, the greater remaining heat of the first spray at deposition minimizing the base porosity of the metal or metal alloy at the interface with the collecting member. 15. A process according to claim 14, wherein the different remaining heats of the first and second sprays at deposition is provided by controlling at least one of the conditions of: the atomizing gas temperatures of the first and second streams; the spray height between the supply and the collecting member of the respective stream; the metal flow rate of the first and second streams; and the atomizing gas flow rate of the first and second streams. 16. A process according to any one of the preceding claims, wherein the collecting member is rotatable about an axis extending in said desired direction whereby an annular deposit is formed about the collecting member. 17. A process according to claims wherein the formed deposit is hot worked to substantially eliminate any residual porosity. 18. A process according to claim 17, wherein the collecting member is selectively either machined away to provide a tubular deposit or retained as part of a composite bar deposit. 19. An apparatus for spray casting a metal or metal alloy comprising: a means for holding at least one supply of metal or metal alloy in a molten state;

Inventors: CHESKIS HARVEY P, CHESNEY PETER FRANK, COOMBS JEFFREY STUART, WATSON W GARY, CHESKIS, HARVEY, P., CHESNEY, PETER, FRANK, COOMBS, JEFFREY, STUART, WATSON, W., GARY
Applicants: OLIN CORP, OSPREY METALS LTD, OLIN CORPORATION, OSPREY METALS LIMITED
Application year: 1992
Main classification: C23C4
IPC codes: C23C4