GB2154902A - Atomization nozzle with boron nitride surfaces - Google Patents

Abstract

The method of producing fine powder molten metal comprising providing a source of the molten metal to be atomized, delivering molten metal from said body to an atomization zone through a melt delivery tube, the portion of said delivery tube which is exposed to said atomization zone consisting essentially of boron nitride, directing a stream of atomizing gas against said stream in said zone to atomize said molten metal. The invention also describes a high temperature atomization nozzle, said nozzle having a melt delivery tube of boron nitride and said nozzle having a gas orifice surrounding said melt delivery tube. <IMAGE>

Description

SPECIFICATION Atomization nozzle with boron nitride surfaces BACKGROUND OF THE INVENTION Rapid Particle Solidification This invention relates generally to the production of powders from a liquid melt by atomization and solidification. More psrticu- larly it relates to the preparation of higher temperature materials in finely divided form by fluid atomization and to the apparatus in which such process is performed and the product obtained by the process.

For example it may be applied to the production of powders from melts of superalloys.

There is a well established need for an economic means of producing powders of superalloys. Such powders can be used in making superalloy articles by powder metallurgy techniques. The present industrial need for such powders is expanding and will continue to expand as the demand for superalloy articles expands.

Presently only about 3% of powder produced industrially is smaller than 10 microns and the cost of such- powder is accordingly very high.

A major cost component of fine powders, prepared by atomization and useful in industrial applications, is the cost of the gas used in the atomization. At present the cost of the gas increases as the percentage of fine powder sought in an atomized sample is increased. Also as finer and finer powders are sought the quantity of gas per unit of mass of powder produced increases. The gases consumed in producing powder, particularly the inert gases such as argon, are expensive.

There is at present a growing industrial demand for finer powders. Accordingly there is a need to develop gas atomization techniques and apparatus which can increase the efficiency of converting molten alloy into powder, and to conserve the gas consumed in producing powder in a desired size range, particularly where the desired size range are growing smaller and smaller.

The production of fine powder is influenced by the surface tension of the melt from which the fine powder is produced. For melts of high surface tension production of fine powder is more difficult and consumes more gas and energy. The present typical industrial yield of fine powder of less than 37 micrometers average diameter from molten metals having high surface tensions is of the order of 25 weight % to about 40 weight %.

Fine powders of less than 37 micrometers (or microns) of certain metals are used in low pressure plasma spray applications. In preparing such powders by presently available industrial processes as much as 60-75% of the powder must be scrapped because it is oversize. This need to selectively remove only the finer powder and to scrap the oversize powder increases the cost of usable powder.

Fine powder also has uses in the quickly changing and growing field of rapid solidification materials. Generally the larger percentage of finer powder which can be produced by a process or apparatus the more useful the process or apparatus is in rapid solidification technology.

It is known that the rate of solidification of a molten particle of relatively small size in a convective environment such as a flowing fluid or body of fluid material is roughly proportional to the inverse of the diameter of the particle squared.

The following expression is accordingly pertinent to this relationship:

where Tp is the rate of cooling of the particle and Dp is the particle diameter.

Accordingly, if the average size of the diameter of the particles of the composition is reduced in half then the rate of cooling is increased by a factor of about four. If the average diameter is reduced in half again the overall cooling rate is increased sixteen fold.

It is desirable to produce powders of small particle size for some applications particularly those in which the rate of cooling of the particle is significant to the properties achieved. For example there is a need for rapidly solidified powders of size smaller than 37 microns and particularly for the production of such powders by economic means.

In addition, for certain applications it it important also to have particles which have a small spectrum of particle sizes. Accordingly, if particles of a 100 micron size are desired for certain applications a process which produces most of the particles in the 80-120 micron range would have a significant advantage for many applications of such particles as compared for example to a process which produces most particles in the 60 to 140 micron range. There is also a significant economic advantage in being able to produce powder having a known or predictable average particle size as well as particle size range.

The present invention improves the capability for producing such powder on an industrial scale.

If particles of 100 micron size are produced by a first process from a given molten liquid metal for a given application, and it is then learned how to produce particles with a 50 micron average size, this second process would permit a much more rapid cooling and solidification of the particles formed from the same molten liquid metal. The present invention teaches a method by which smaller particles may be formed in higher percentage from melts, including molten liquid metal. A more rapid solidification rate of such particles is achieved by this novel process partly because the particles produced are themselves smaller on the average and also because the production is repeatable and reproducible on an industrial scale.

The achievement of small particle size is advantageous for rapid cooling and for the attendant benefits which derive from rapid cooling of certain molten materials. Novel amorphous and related properties may be achieved in this way. The present invention makes possible the production of powders with such small particle size with attendant rapid cooling.

The powder metallurgy technology presently has a need for fine and ultrafine particles and particles in the size range of 10 to 37 microns in diameter. Particles having average particles in the particle size range of 10 micron to 37 micron are produced by this novel process of this invention.

The attainment of the smaller particle size may be found important in consolidation of the material by conventional powder metallurgy inasmuch as it has been observed that powder of smaller particle size can result in higher sintering rate. Also it can be significant in the consolidation of the small particle size material with a material of larger particle size where such consolidation is found desirable based on higher packing density.

Present trends in powder metallurgy are creating great interest in fine metal powders, that is, in powders having diameters less than 37 microns in diameter and also in ultrafine powders specifically powders having diameters of less than 10 microns. High surface tension in a melt material makes the formation of smaller size particles more difficult.

Conventional apparatus for producing powder from molten metals by atomization results in products depending on preparation methods and materials which have relatively broad spectra of particle sizes. The broad spectra of particle sizes are represented in Fig.

2 by the curves A, B, C and D. From examination of these curves it is evident that the particles range all the way from particle sizes of less than 10 micron to more than 100 microns. The percentage of particles of fine powder, i.e. less than 37 micron) produced by conventional technology is the range of about 0 to 40%, and the percentage of ultrafine powder, i.e. less than 10 micron, produced is in the range of ~0-3%. Because of the low yield of the smaller particle powder which is formed in such products the cost of the production of the ultrafine powder can be excessie ranging up to hundreds and even thousands of dollars per pound.

The graphs of Fig. 2, and illustratively curve E of Fig. 2, shows that the range of particle sizes produced by the methods of this invention when operated in a fine powder mode are significantly better than the particle size range of existing conventional processes.

The data on which the curves A, B, C and D of Fig. 2 is based is from a review article by A. Lawly, "Atomization of Specialty Alloy Powders" which appeared in the January 1981 issue of Journal of Metals.

The data in the Journal of Metals article, and for the Curves A, B, C and D is for powder formed from melts of superalloys. The data from which Curve E was prepared was also data from the preparation of powder for a superalloy melt so that the two sets of data are quite comparable.

It is known that there are large differences in the ease with which powder can be prepared from different families of alloys.

PARTICLE SIZE.RANGES Fig. 2 contains typical powder particle distributions for superalloy powders produced by different atomization technologies. Curve A is for Argon gas atomized powder. Curves B, C and D are for powder produced by the rotating electrode process, rapid solidification rate process, and vacuum atomization, respectively.

The shaded area or band bordered by Curves E and F indicates the range of powder size distributions that are produced utilizing this invention when operated in the fine powder mode.

It is readily evident from the plot of the various curves of Fig. 2 that the powder prepared pursuant to the present process, and using the present apparatus has a range of particle sizes and cumulative particle sizes which are much smaller than those prepared by the conventional methods particularly in the smaller size range of about 60 microns and smaller.

The shaded area of the graph between lines E and F is an envelope displaying the region of the graph in which powder products may have been produced employing the methods and techniques of this invention to make fine powder.

From this chart it is evident that the method of the present invention makes possible the formation of powder having between 10 and 37% of particles of 10 microns and under and makes possible the formation of powders having between 44 and 70 cumulative percent of particles less than 37 microns.

Higher yield of fine powder may be produced by the methods and apparatus of the present invention than are produced by other gas atomization methods and devices because practice of the invention results in transfers of energy more efficiently from the atomizing gas to the liquid metal to be atomized. One way in which this improved production of fines may be accomplished is by bringing the melt stream into unprecedented close proximity with the atomizing gas nozzle. This close proximity of the gas nozzle to the melt stream orifice is designated herein as close coupling.

The advantages of the principle of close coupling has been recognized in the literature as discussed below, however, until now no invention has allowed the use of this principle for high temperature materials. This is due at least in part to the problem of accretion of solidified high temperature melt on the atomizing gas nozzle as well as elsewhere on the atomizing apparatus.

ACCRETION ON PRIOR ART NOZZLES A major problem associated with prior art gas atomization nozzles and methods has been the solidification of specks and globules of the atomized high temperature alloy on the nozzle surface. The resulting buildup on the nozzle has sometimes caused the termination of the atomization process. This termination has resulted from closing off of the hole through which the melt is poured or by at least partially diverting the atomizing gases from direct impingement at high energy onto the emerging steam of liquid metal. In severe cases the buildup of solid deposit at the nozzle tip has caused the buildup deposit to break away from the nozzle. In such case the result has sometimes been a contamination of the powder being formed with material from the nozzle or from the melt delivery system.

In conventional apparatus the problem of the build up of solidified high temperature material at the gas nozzle or at the molten metal orifice is solved by keeping the gas nozzle fairly remote from the atomization region as explained more fully below.

The problems of a progressive accretion of numerous specks and globules of solidified melt on the atomizing nozzle is most acute for the very high temperature melts and particularly for the molten metals which have high melting temperatures.

LOWER TEMPERATURE PRIOR ART ATOMI ZATION There is a great deal of difference between the practices which may be employed with low temperature materials in forming sprays by means of impingement of streams of gas on streams of liquid and the phenomena which occurs at elevated temperatures. In general the idea of a low temperature spray may include materials which are liquid at room temperature and those which become liquid at temperatures up to about 300"C.

The atomization of materials at these lower temperatures and particularly of materials which are liquid at room temperature is not attended by the occlusion of frozen metal on the spray nozzle to anywhere near the degree which occurs when high temperature molten metals or other high temperature materials are employed. Accretion of lower temperature material on an atomization nozzle does not lead to destruction of elements of the nozzle itself.

Also at the lower temperatures there is far less reaction and interaction between the metal being atomized and the melt delivery tube or the materials of other parts of the atomization nozzle. A metal melt delivery tube can be used to atomize materials at or below 300"C but ceramic delivery systems must be used at the higher temperatures of 1000"C, 1500"C and 2000"C and above.

Another difference is that the thermal gradient through the wall of a melt delivery tube from the melt to the atomizing gas increases as the temperature of the melt to be atomized increases. For an atomization system of constant geometry greater gas flow is required as the heat of the melt is increased because of the greater quantity of heat to be removed. A greater quantity of gas per unit volume of melt atomized can cause greater tendency toward spattering and splashing of the melt in the apparatus. Where the melt is very hot, of the order of a thousand degrees centigrade or more a droplet can solidify and adhere instantly to a lower temperature surface. At the higher temperatures materials are more active chemically and can form stronger bonds at surfaces which they contact than molten materials at lower temperatures.

CONVENTIONAL GAS ATOMIZATION REMOTE COUPLING While the Applicant does not wish to be bound by the accuracy of the representation or description which is given here it is believed that it will be helpful in bringing out the nature and character of the present invention to provide a general description of atomization mechanisms as have been referred to and described in reference to the prior art and to provide a graphical representation of the phenomenon which occurs as prior art atomization takes place. For this purpose reference is made to Fig. A which is a schematic representation of a prior art atomization phenomenon as it is understood to have occurred as prior art methods were employed. In the figure two gas orifices 30 and 32 are shown positioned relative to a melt stream 34 in a manner which has been conventional in the prior art.Specifically the jet gas nozzles 30 and 32 are spaced a distance from the melt stream and are also angled so that they are directed toward the melt stream at a substantial distance from the nozzles. This figure is somewhat schematic and it will be understood that the nozzles 30 and 32 could in fact form a single annular nozzle surrounding the melt delivery apparatus and could be fed from a conventional gas plenum. The melt delivery apparatus 36 is also shown in a schematic form.

There is a phenomena recognized in the prior art of the formation of an inverted hollow cone in the melt stream as it descends to the area where the confluence of the gas from the respective gas jets 30 and 32 occurs. The point of confluence 38 is the point at which two center lines or aimpoints of the two streams of gas could meet if there were no interference between them. They do, however, act on the melt stream as it descends and part of this action is the formation of the inverted hollow cone illustrated at 40 in the figure.

The next phenomena which occurs in the conventional atomization process is the disruption of the cone wall into ligaments or globules of melt. This phenomena occurs in the zone shown as 42 in the figure.

The next phenomena which occurs in conventional atomization is the breaking up or atomization of the ligaments into droplets.

This is shown in the figure as occurring generally in the zone below that in which the ligaments are formed. The individual droplets or particles are represented as formed from larger droplets or globules.

According to this schematic representation the conventional atomization is a multi-step multi-phenomena process, the first phenomena of which is the formation of the inverted cone; and the second phenomena of which is the disruption of the cone wall into the ligaments; and the third phenomena of which is the disrupting of the ligaments into droplets.

So far as the droplet formation is concerned it is seen from this description to be a secondary phenomena in the sense that a very high percentage of the droplets are formed by disruption of the ligaments or globules.

The most definitive work on the remotely coupled atomization of liquid metals cited in the technical literature is entitled "The Disintegration of Liquid Lead Streams by Nitrogen Jets" by J.B. See, J. Rankle and T.B. King, Met. Trans. 4 (1973) p. 2669-2673 which describes the atomization phenomena based on studies made with the aid of speed photography.

What is distinct and novel about the process of the subject invention is that the process has a greatly reduced secondary particle formation and has a very high degree of primary direct formation of particles immediately from the melt and without the need to go through a second stage of subdivision of the melt as is illustrated in schematically in Fig. A and described above.

CONVENTIONAL ATOMIZATION LOSS OF GAS ENERGY To avoid having such high temperature droplets adhere to the portion of the apparatus which is cooled by the gas supply mechanism, prior art high temperature atomization apparatus has supplied the gas from a jet or jets which are relatively remote from the surface of the stream itself impacted by the jets.

Where the nozzle is remote from the atomization region there is an appreciable reduction in the energy of the gas as it moves from the nozzle from which it is delivered to the point of impact with the liquid metal to be atomized. There are substantial diffusion and entrainment losses as the gas traverses the distance from the nozzle to the melt stream. The energy loss has been estimated to be in excess of 90% of the initial energy for certain designs of the molten metal atomizing equipment currently in use. Accordingly the processes employing gas jets remote from contact with a stream or body of molten material to be atomized are uneconomical in usage of gas as much gas is needed to overcome the loss of energy which occurs in the stream of gas before the molten metal stream is contacted.

Such remote coupling of a melt stream to atomizing gas supply orifices are illustrated and described in U.S. Patents 4,272,463; 3,588,951, 3,428,718, 3,646,176, 4,080,126; 4,191,516 and 3,340,338 although not described in terms of remote coupling.

DISCUSSION OF THE PRIOR ART Use of metal and even plastic nozzles having the gas jet very closely proximate the liquid supply tube or orifice has been known heretofore. For example atomization of liquid at room temperature can be accomplished without serious freezing and build up of the liquid on the nozzle. Some paint spray nozzles for example have this type of construction.

In the book entitled "The Production of Metal Powders by Atomization" authored by John Keith Beddow and printed by Hayden Publishers, there is a reference made on page 45 to various designs of nozzles for the production of powder metal from a molten metal stream. Such atomization involves high temperature gas atomization.

The Beddow nozzles are annular nozzles in that they have a center port for the development and delivery of a liquid metal stream.

The gas is delivered from an annular gas jet surrounding the center port. The Beddow nozzles have a superficial similarity to that illustrated in Fig. 1 of this specification. The problem of buildup on annular nozzles such as those disclosed in Beddow is pointed out immediately beneath the figures on page 45 as follows: "One important problem with annular nozzles is that of 'build-up' on the metal nozzle body. This is caused by splashing of molten metal onto the inside of the nozzle, especially near the rim at the bottom. This splashed metal freezes, more liquid metal accretes and at some later stage of this process the jet of air causes the hot metal build-up to ignite.In this way the operator can lose a nozzle block rather easily." Thus although such nozzle design has been known, prior art practitioners of this art have not been able to overcome the problem recited by Beddow in the gas atomization of high temperature material and particularly metals.

Other sources of information on the configuration of nozzles for use in atomization technology are found in U.S. patents. In U.S.

Patent 2,997,245 a method of atomizing liquid metal employing so-called "shock waves" is described.

In U.S Patent 3,988,084 a scheme for generating a thin stream of metal on a hollow inverted cone and intercepting the stream by an annular gas jet is described. In the scheme of patent 3,988,084 the atomization gas stream is directed against only one side of the cone of molten metal, i.e. the exterior of the cone, and no gas is directed against the other side of the cone of molten metal, i.e. the inside surface of the cone of molten metal. In the practice of certain modes of the present invention atomizing gas is directed against all surfaces of the melt stream. The inverted cone of the 3,988,084 patent resembles the inverted cone formed during conventional remotely coupled gas atomization of a descending liquid metal stream described above in that the gas acts on only one side of the web of liquid metal at the lower edge of the inverted cone.The web spreads over the inverted cone to its edge and the gas sweeps metal from the edge into a hollow converging cone.

The inventor of this application prepared a thesis entitled "The Production and Consolidation of Amorphous Metal Powder" and submitted the thesis to the Department of Mechanical Engineering at Northeastern University, Boston, Massachusetts in September, 1 980. The thesis describes the use of an annular gas nozzle with a ceramic and/or graphite metal supply tube. In this thesis improvements in the production of powder having a higher proportion of finer powder from the atomization of molten metal with an annular jet of gas is reported.

BRIEF SUMMERY OF THE INVENTION An object of the present invention is to produce fine metal powder directly from the liquid state and without necessarily employing a secondary process such as commutating or otherwise subdividing material formed initially in a ribbon or foil or strip of similar solid state.

Another object is to produce powder from a melt with a substantially higher percentage of finer particles.

Another object is to produce powder directly of more uniform particle size.

Another object is to produce powder by gas atomization more efficiently.

Another object is to provide a method and apparatus for more efficient production of powder of desired particle size by gas atomization.

Another object is to produce powder from higher temperature melts at low cost.

Another object is to produce useful articles of powder derived from alloys which cannot be made by conventional techniques into useful articles.

Another object is to make possible production of powder by rapid solidification techniques for use in forming novel articles of manufacture.

Another object is to produce new and distinct powder from a melt by gas atomization and to do so economically.

Another object is to provide an atomization nozzle and method which is self cleaning.

Another object is to provide a nozzle which has a long service period.

Another object is to provide a nozzle which is reusable.

Another object is to provide a nozzle which is not as subject to accretion and attack by liquid metals as prior art nozzles.

Another object is to provide a method of limiting the accretion of melt on atomizing apparatus.

Another object is to provide a method which permits long term continuous runs of atomizing apparatus.

Other objects will be in part apparent and in part pointed out in the description which follows.

In one of its broader aspects the objects of the invention can be accomplished by providing a melt supply tube to deliver melt directly to an atomization zone, delivering atomizing gas to said zone from at least one gas orifice immediately proximate said zone, and forming the surfaces of the apparatus subject to spatter from said zone of boron nitride.

BRIEF DESCRIPTION OF THE FIGURES The description of the invention to follow will be better understood by reference to the accompanying drawings in which: Figure 1 is a vertical sectional view of one type of gas atomization nozzle useful in the practice of the present invention.

Figure 3 is a plot of certain parameters relating to particle size distribution of the cumulative fraction of particles in powder samples prepared by different methods.

Figure 4 is a schematic illustrating of a prior art atomization phenomena; Figure 2 is a detail of the atomization tip as in Fig. 1 illustrating certain dimensions A and B.

DESCRIPTION OF A PREFERRED EMBODI MENT ILLUSTRATIVE ATOMIZATION NOZZLE Referring to Fig. 1, there is illustrated in vertical section one form of a atomization nozzle 10 as provided pursuant to the present invention. Numerous modifications of the forms of atomization nozzles may also be employed in practicing this invention, all as described elsewhere in this specification.

The nozzle 10 is illustrated as having an inner ceramic liner 1 2 having an upper end 14 into which liquid metal to be atomized is introduced, and a lower end 1 6 from which the metal to be atomized may emerge as a descending stream. The lower end is provided with a lower tip 1 7 having tapered outer surface 1 8 in the shape of an inverted truncated cone. The molten metal emerging from tube 1 2 at end 1 6 is swept by gas from an annular gas orifice portion of the nozzle 10.

The annular gas jet is made up of gas streaming from a plenum chamber 20 downwardly through an opening 22 formed between an inner beveled surface 24 and the inverted conical or beveled surface 1 8 of metal supply tube 1 2. The annular orifice or port 22, for exit of jets of gas may have surfaces formed in a beveled shape to conform generally to the beveled surface 1 8 of the liner 1 2. Accordingly, the opening 22 may be defined by the outer beveled surface 1 8 of liner 12, the corresponding beveled surface 26 of the upper portion of the annular gas plenum 20 and the confronting and opposite surface 24 on plate 32 forming the lower closure of plenum 20.The lower surface 1 8 of liner 11 forms one side of a small land 1 9. The other side of land 19 is formed by the melt orifice 1 5 also contained in 12.

By supplying a gas at high pressure through the gas conduit 30 from a source not shown, the gas enters the annular plenum chamber 20 and emerges from the annular gas orifice 22 to impinge on the stream of molten metal descending through the tube 1 2 and emerging from the end 1 6 of the liner 1 2 at tip 17.

Exit surface 24 may conveniently be formed on the inner edge of a plenum closure plate 32. Plate 32 may have external threads to permit it to be threaded into the lower internally threaded edge 36 of plenum housing sidewall 34. The raising and lowering of plate 32 by turning the plate to thread its inner edge further into or out of plenum 20 has the effect of moving surface 24 relative to surface 18 and accordingly opening or closing annular orifice 22 as well as raising the orifice relative to the lower tip 1 7 of melt delivery tube 12.

The plenum housing 34 is made up of an annular top 38 having an integrally formed inner shelf 40. An annular cone 42, which may suitably be a ceramic, or metal, and is part of melt guide tube 12, is supported from shelf 40 by flange 44. The shape of outer surface 26 of cone 42 is significant in forming the inner annular surface of plenum 20 from which gas is delivered to annular orifice 22. The outer surface 26 of cone 42 may be aligned with the outer conical lower end surface 1 8 of tube 1 2 so that the two surfaces form one continuous conical surface along which gas from plenum 20 passes in being discharged through annular orifice 22.

As indicated tube 1 2 has bottom tip 1 7 and an outer lower surface 18 conforming to the inner surface 26 of annular cone 42. It also has a mid-flange 46 which permits its vertical location to be precisely determined and set relative to the overall nozzle 10 and to conical surface 26.

An upper annular ring 48 has an inner depending boss 50 which presses on flange 46 to hold the tube and cone parts of the device in precise alignment.

The means for holding the nozzle assembly in the related apparatus in which molten metal is atomized is conventional and forms no part of this invention.

The configuration and form of gas orifice useful in practice of the present invention is not limited to the form illustrated in Fig. 1.

For certain applications a nozzle in the form of a Laval nozzle will be preferred to control expansion of gas released from the orifice 22 of Fig. 1.

Further the annular jet of gas need not be formed solely by an annular orifice although such orifice is preferred. Rather the annular jet can be created by a ring of individually supplied tubular nozzles each directed toward the melt surface. The gas of such a ring can form a single annular gas jet as the gas from the individual nozzles converge at or near the melt surface.

Further the angle at which gas is directed from a gas orifice toward a melt stream surface is not limited to that shown in the figure.

While some angles are prepared for certain combinations of nozzle design and melt to be atomized, it is known that atomization can be accomplished with impingement angles from a fractional degree to ninety degrees. Applicant has found that atomization with a nozzle as illustrated in Fig. 1 at an angle of incidence of 22 is highly effective in producing higher concentrations of fine powder than prior art methods.

ADVANTAGES OF SMALL PARTICLES For many metals which are atomized a more rapidly solidified droplet or particle will show an improvement in some properties as compared to a more slowly cooled particle. As is pointed out in the background statement the rate of rapid solidification goes up as the particle size is going down. So finer powder involves getting increased solidification rates and not just finer powder per se. Finer powder per se has other advantages over conventional materials.

With respect to getting higher solification rates one of the common observances is a vast decrease in segregation of the constituents of an alloy from which the particle is formed. For example, as a result of that decrease in segregation one can raise the incipient melting point of the alloy. The incipient melting point is raised essentially because the present method makes possible a homogeneous nucleation event which means essentially that the solidification will occur virtually instantaneously so that the solidified front will move rapidly through the liquid material of the droplet without segregation occurring. The net effect of that is a homogeneous structure.

By getting a homogeneous structure the difference between the liquidus temperature of the alloy and the solidus temperature of the alloy is reduced and ultimately they can approach one another. The benefit of that is that ultimately the incipient melting is the solidus temperature. That has been moved up and also the potential operating temperature of the alloy has been raised. With powder prepared in this manner and pursuant to the present invention one can get successful consolidation with improved properties with the consolidation techniques that exist today.

If in trying to consolidate a rapidly solidified fine amorphous powder by the types of techniques that have been used in the past one goes above the transition temperature the material crystallizes. So one can't consolidate the material and retain the amorphous structure for most amorphous alloys. Some amorphous alloys have been consolidated but in the case of superalloys, these remain crystalline in the rapidly solidified form, these have been consolidated and some increase or beneficial properties have been observed in the consolidated material and especially in rapidly solidified tool steels.

Considering a sample of very finely divided powder, even if the effects of cooling rate are eliminated and just dealing in terms of particle size, the fact that each particle originates from the melt and assuming that the melt is homogeneous, and allowing segregation to occur if one has a very small particle one is going to see less segregation potentially than in a very large particle simply by the definition of the material available to segregate.

Secondly with respect to advantages of small particle size it has been shown in the literature that smaller metal particles tend to sinter sooner at lower temperatures and in shorter times than large powder particles.

There is a greater driving force for the sintering process itself. That is an economic advantage.

Thirdly one of the problems associated with powder metallurgy is contamination of the powder by foreign objects. These foreign objects get mixed into the powder and then pressed up into the part and ultimately represent a potential failure site in the part. If one has very fine powder the common belief that one can sift the powder and eliminate these big foreign objects so that by having a finer powder one can prepare a final specimen that will have potentially smaller defects in it than if you had coarse powder were used.

Further considering other advantages of fine powder if it were available at economic prices as proceeded pursuant to this invention if one assumes 10 micron spheres versus 100 micron spheres the packing factor is the same.

Accordingly it is desirable to have another set of smaller spheres to put into those voids. But there will be voids again between the smaller spheres and the big spheres so that one would like another set of smaller spheres to fill in the smaller voids essentially.

A relatively new area that has evolved because of rapid solidification is the development of whole new series of alloys. Because of the slower solidification rates of conventional materials the constitutents of the alloy segregate out as either brittle intermetallic compounds or as long grain boundaries. Such materials have properties which are inferior in some aspects to rapidly solidified material.

By means of rapid solidification some of these solute materials can be kept in solution and can act as strengtheners and as a result one is now looking at new alloy compositions through rapid solidification. These same alloys when made through conventional practices may have to be discarded because they were brittle. However it is now found that these alloys have useful properties if rapidly solidified. This phenomena varies from alloy system to alloy system, solidification rate. Ultimately consolidation techniques affect whether you can use the material or not as well.

An important feature of the present invention is that it permits the formation of powder from a melt with high efficiency in the utilization of gas. The improvement which is obtained is quite surprising in that the finely divided powder has a higher percentage of the fine particles and it might be reasonable to assume that in order to achieve such a fine subdivision a much higher gas flow would be needed. With a much higher gas flow there would of course be a reduction in the efficiency of gas utilization. However, surprisingly I have found that by the use of the processes taught in this specification the gas utilized actually decreases when the very fine particles are produced in the higher percentage made possible by this invention compared to conventional processes.

PARTICLE SIZE PARAMETERS NARROW RANGE OF SIZES In general there is an advantage in having powders having fine particles of relatively uni form size or with a smaller range of sizes. This is because the more uniform size particles will have seen a more uniform cooling history. The more uniform cooling history translates into the particles being more uniform in metallurgical properties.

Also, generally the smaller size particles are more rapidly cooled particles as set forth in the equation in the introduction to this application. Where a wide range of particle sizes is present in a powder and the powder is processed through powder metallurgy techniques there is a limit on the desirable properties which can be imparted to a composition and this limit is related to the composition and properties of the larger particles of the powder which goes into the composition. The larger particles will constitute a potential weak spot or spot at which lower values of incipient melting or other lower value of properties will occur.

As a general rule the smaller the particle size and the smaller the average particle size and the more uniform the size of smaller particle powder of an ingredient powder used to form a solid object the more likely that the product obtained will have certain combinations of desirable properties in solid objects prepared from the powder. Ideally if all particles formed were exactly 20 microns in diameter they would all have seen essentially the same thermal history and the objects formed from these particles would have properties which were characteristic of the uniform size particles from which they were formed.

It would, of course, be desirable to have larger particle bodies which have been rapidly solidified at the rates which are feasible with smaller particle bodies. However, because of the internal segregation of the metallurgical ingredients which occurs within a larger particle body as the larger bodies are solidified, and because there is a limit on the rate at which heat can be removed from the larger particle bodies in order to achieve such solidification, the formation of such larger particle bodies from molten metal as powder is formed by conventional atomization techniques presents a limitation on the character of powder which can be produced by conventional techniques as well as a limitation on the uses which can be made of such powder in forming larger bodies by powder metallurgy.

The use of powder metallurgy techniques is presently the principle route by which superior products are achieved using powder subjected to rapid solidification. The present invention improves both the formation of such smaller particles and the formation of larger bodies with the highly desirable combination of properties of rapidly solidified metals. Further, the articles formed have a more uniform set of properties because of the more uniform particle size of the particles of the powder from which the particle is formed.

One of the unique features of the technology made possible by the present invention is that it permits a closer control of a number of the parameters of a powder product produced by atomization as taught in this application.

For example, it has been found possible to alter the somewhat random distribution of particle sizes which is found in the powder products of prior art processes to permit a greater concentration of particle size of a selected value.

Secondly for a selected particle size the possibility of producing a higher yield of the size from a given run is made possible regardless of the size of particle which is selected. If, for example, particles of 10 micron is selected as the principle product size for a powder, the control of the variables of the subject invention will make possible an emphasis in the production of the particles of that selected size. Alfternatively if particles of 50 microns or 100 microns are selected as the desired product size then the process parameters can be altered in accordance with the teaching of this invention to produce powders which have higher concentrations of the particles within the selected size range.

By use of prior art processes it is possible to produce a wide range of particle sizes in any one lot or from any single run. The economic advantage, however, is in being able to produce a particle size with a relatively narrow standard deviation from a selected or preselected particle size product. Accordingly, the present invention makes possible the production of economically more valuable powders from a given run involving the consumption of a certain amount of energy and materials.

A derivative benefit of producing powder according to the teaching of this invention is that it not only makes possible the production of powder with a relatively tight particle size distribution but because of the tight distribution the particles will have a selected microstructure. Accordingly it is possible through use of this teaching to form particles having a relatively large particle size and a tight distribution of sizes within a given sample. The larger particles because they will have undergone slower cooling will have coarser crystalline structure than those which have more rapid cooling.

Alternatively, however, by selecting those conditions which produce the finer particle size it is possible to produce a powder which is amorphous because the smaller particles are cooled more rapidly as is explained above and also because there is a very tight size distribution around the preselected size for the sample being produced.

PREFERRED EMBODIMENT ILLUSTRATIVE ATOMIZATION An atomization zone is formed at the area of confluence of the molten metal stream and the annular stream of atomizing gas emerging from the annular opening 22 at the bottom of the gas supply plenum 28. Accordingly, the melt guide tube 1 2 delivers the liquid metal stream through the throat of the gas nozzle to the atomization zone. One feature of the present invention is the provision of a gas nozzle body which cooperates with a shaped end of a melt guide tube to form a gas nozzle having an annular gas jet which works in cooperation with the shaped exit end of the melt guide tube.

In other words, the provision of shaped and configured and cooperative ends at the lower part of the melt guide tube is one aspect of this invention as is explained more fully herein. As will be explained more fully below this is one of several independently functioning phenomena which are used in achieving superior atomization of a variety of melts.

The close positioning of the gas orifice and melt orifice permits the surface of the melt guide tube to form a part of the annular gas orifice and by doing so permits the jet of gas emerging from the gas plenum to escape over the formed end of the melt guide tube. This sweeping action of the gas jet on and against the lower end of the melt guide tube has been found to be effective in carrying off to a large degree particles of freezing or frozen metal which might otherwise tend to form or to deposit and accrete on the lower end of the melt guide tube. The Applicant has no knowledge that such particles do not in fact accrete on the lower end of the tube and it is known that such adherence occurred to prior art atomization nozzles as is discussed above relative to the Beddow reference.However, because of this measure which are taken in the practice of this invention, the adherence of such liquid or frozen particles is reduced and there is an ability of the sweeping gas to either prevent deposit of such particles or to cause their removal once they are deposited or accreted on the lower end of the melt delivery tube.

In the particular configuration shown in the drawing there is a continuity, conformity and alignment between the formed lower surface of the melt guide tube 1 8 and the formed surrounding surface 26 of the gas supply plenum 20. It will be understood that the annular gas jet can, in fact, be made up in a number of configurations and in a number of ways. However, the important feature which must be provided pursuant to this aspect referred to herein as close coupling, is an annular gas jet which is at least in part formed by the lower formed end of the melt guide tube and proximate to the melt surface.

The principal criteria of a material for a melt guide tube are that the material be resistant to the high temperature melt and that it have a high resistance to thermal shock. Desirable characteristics are that the material be able to be machined or cast with a smooth surface to prevent mechanical interlocking with accreted material; that it be non-wetting with respect to the melt; and that it have a low coefficient of thermal conductivity.

Boron nitride meets all of these criteria. It has been found to be uniquely suitable as a nozzle material in forming nozzles useful in gas atomization of high melting metals.

A melt delivery tube such as Table 1 2 of Fig. 1 was made of boron nitride and was found to work very well in this function with particular reference to meeting the two principal criteria as set forth above. The material was found to be resistant to high temperature melts of metal at temperatures of 1350"C and 1750"C. Further the Boron Nitride delivery tube was found to be highly resistant to thermal shock when the 1750"C metal was poured into and through the interior of the tube, while the atomizing gas at a temperature of approximately - 200"C, flowed over the exterior surface. It has a low coefficient of heat transfer relative to most metals.

One source of material, a boron nitride sold commercially by Union Carbide Corporation under the trade designation HBR, a Union Carbide trademark, is machinable to the configuration shown in Fig. 1 and has smooth surfaces from the machining.

Another brand, HBC, also available commercially from Union Carbide Corporation is also useful as a nozzle material although it has only about half the fracture strength of the HBR grade.

The boron nitride used in fabricating the melt delivery tubes was apparently wet to a limited degree by the hot liquid metal but the wetting was not of such order as to prevent its use in a very satisfactory manner as a melt delivery tube and as a surface component exposed to the metal atomization atmosphere.

In this last respect the boron nitride performed exceptionally well. It resisted accretion of high temperature molten metal better than any other material tested.

The present invention contemplates forming any surfaces of an atomization nozzle of boron nitride to resist splash accretion, whether the nozzle is of the design or configuration of Fig.

1 or of some other design.

For example, forming individual gas nozzles with boron nitride surfaces to inhibit accretion is contemplated. Forming the number 32 of Fig. 1 of boron nitride to inhibit adhesion of molten metal specs or molten metal specs and the progressive accretion of such specs is contemplated.

In general use of boron nitride on surfaces which are exposed to splatter of the gas atomization process is contemplated where the surfaces are those which can receive accretions of frozen particles and where such accretion interferes with the progress of the atomization process.

The surface 1 8 of Fig. 1 is one illustrative such surface for reasons explained above. The gas from the annular nozzle can sweep such particles which may deposit at the surface from the surface because of the low order of adhesion between the melt deposit and the boron nitride surface.

Surfaces of a number such as 32 can be coated with boron nitride or inset with boron nitride to provide the non-adherence advantages where the other advantages of thermal shock resistance and the like are not essential to proper functioning of the part.

BORON NITRIDE It is within the scope of the present invention to form another aspect of an annular orifice made up entirely of the inert ceramic materials such as boron nitride. At the very least the inert ceramic such as boron nitride should be either provided or deposited at least at the surface where the accretion of the solidified metal is most likely to occur. The portion at which it is deemed most likely to occur is the portion closest to the emergence of the molten metal.This is at and on the beveled surface 1 8 at the lower end 1 6 of the melt guide tube.

Claims (8)

1. The method of producing fine powder from molten metal, which comprises providing a source of the molten metal to be atomized, delivering molten metal from said body to an atomization zone through a melt delivery tube, the portion of said delivery tube which is exposed to said atomization zone consisting essentially of boron nitride, directing a stream of atomizing gas against said stream in said zone to atomize said molten metal.

2. The method of claim 1 in which all surfaces exposed to spatter of molten metal are of boron nitride.

3. The method of claim 1 in which the melt delivery tube is of boron nitride.

4. The method of claim 1 in which exposed surfaces of the source of the stream of atomizing gas is of boron nitride.

5. A high temperature atomization nozzle, said nozzle having a melt delivery tube of boron nitride and said nozzle having a gas orifice surrounding said melt delivery tube.

6. The nozzle of claim 1 in which the orifice is closely coupled to the melt delivery tube.

7. The nozzle of claim 1 in which all surfaces swept by the gas from the gas orifice are of boron nitride.

8. A high temperature atomization nozzle said nozzle having melt delivery tube and peripheral gas delivery nozzle.

the surface of said nozzle which may receive melt emanating from said nozzle being at least coated with Boron Nitride.