US3600163A - Process for producing at least one constituent dispersed in a metal - Google Patents

Process for producing at least one constituent dispersed in a metal Download PDF

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US3600163A
US3600163A US715937A US3600163DA US3600163A US 3600163 A US3600163 A US 3600163A US 715937 A US715937 A US 715937A US 3600163D A US3600163D A US 3600163DA US 3600163 A US3600163 A US 3600163A
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graphite
particles
metal
aluminum
alloy
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Frank Arthur Badia
Pradeep Kumar Rohatgi
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Huntington Alloys Corp
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International Nickel Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C22C21/04—Modified aluminium-silicon alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12486—Laterally noncoextensive components [e.g., embedded, etc.]

Definitions

  • Alloys containing at least one constituent dispersed in metal in which the constituent is normally insoluble or incompatible when the metal is in the molten state are produced utilizing melt processing in which the constituent in particulate form and having a coating, particularly metal, is injected into a molten bath of incompatible metal and the melt is thereafter solidified.
  • aluminum has many desirable characteristics, e.g., light weight, resistance to the corrosive effects of many media and relatively high strength in relation to weight.
  • aluminum surfaces are quite susceptible to surface damage such as galling and scoring when subjected to sliding contact with other aluminum surfaces.
  • silicon carbide in nonferrous metals e.g., aluminum, zinc or copper
  • diamond in metals such as aluminum and zinc
  • mica in such incompatible low melting point metals as zinc, lead, aluminum and magnesium
  • heavy oxides in lead silica, magnesia, alumina and other oxides in metals such as copper and nickel
  • silica, magnesia and others in aluminum etc.
  • alloys having improved characteristics having dispersed substantially throughout a constituent (dispersoid) normally incompatible with the base metal when the latter is in the molten condition.
  • a particular object is to provide aluminum alloy products characterized by improved resistance to scoring, galling and/ or seizure when used in sliding contact against aluminum alloys under conditions of poor lubrication.
  • FIGS. 1 and 2 are reproductions of photomicrographs (magnification diameters), of etched sections of an aluminum alloy casting in accordance with the invention.
  • FIG. 3 is a chart illustrating frictional characteristics of alloys both within and outside of the invention.
  • the present invention contemplates production of compatible compositions of matter by a process comprising injecting particles of at least one constituent, e.g., graphite, in loose powder form into a molten bath predominantly of metal in which the constituent is, as a practical matter, insoluble, e.g., metal from the group consisting of aluminum, magnesium and zinc in the case of graphite, the constituent particles being characterized by coatings effective to impart compositional stability to the molten bath, and thereafter solidifying the resulting alloy with the constituent particles (dispersoids) distributed therein.
  • the coating should act much in the manner of a barrier layer for a period sufiicient to accomplish suitable introduction and dispersibility of the constituent particles throughout the bath.
  • the coating coacts to confer or, in effect, it contributes to imparting sufiicient wettability between the otherwise incompatible materials such that dispersion one in the other is retained until solidification can be achieved.
  • the integrity of the coating should be substantially maintained while dispersing the particles within the melt.
  • the particles In carrying the invention into practice, it is advantageous to propel or otherwise force the coated particles into the molten bath by gas pressure. Especially rapid and efficient injection and dispersion is achieved by propelling the particles in a non-reactive gas stream flowing through a conduit and exiting into the lower extremity of the melt, advantageously at the maximum depth of the melt.
  • the particles can be injected with an inert gas stream in a tube at a positive pressure of about 2 pounds per square inch (p.s.i.) to about 5 p.s.i.
  • the nonreactive gas functions in the manner, inter alia, as a protective medium for the coatings up through at least the point of introducing the coated particles into the melt and for a period thereafter to enable the metal to be cast, since upon coming into contact with the melt the gas forms bubbles which in turn contain or envelop the coated particles.
  • Inert gases including nitrogen, argon, helium and other gases that are nonreactive with the particle coating and which are not detrimental to the bath metal at the injection temperature, can be used for the gas pressurized injection. Accordingly, particularly in respect of metal coatings, gases which would be oxidizing or chlorinating to the coating or bath metal during injection should generally be avoided.
  • Gas pressure may also be provided by heating and volatilizing a gas-forming material.
  • the coated particles may be introduced below the surface of the bath using a capsule containing a loose powder mixture of the coated particles and a nonreactive gas-forming agent which is rendered volatile by the heat of the bath to propel and disperse the particles in the bath metal.
  • the temperature of the bath In order to obtain and retain satisfactory uniform dispersion of the constituent particles, at least in the case of graphite, it is beneficial to control the temperature of the bath from about 200 F. to about 300 F. above the liquidus temperature thereof during and after injection.
  • the injection temperature is excessively low, e.g., less than 100 F. above the bath metal liquidus.
  • Detrimental segregation of the graphite particles often occurs with unfavorable rapidity if the bath temperature becomes excessively high, e.g., more than 450 F. above the liquidus.
  • the constituent particles are metal coated.
  • such coatings have exterior surfaces which are essentially metal, i.e., are in the metallic condition characterized by being essentially uncombined metal and essentially devoid of oxides or other compounds, and are effective to provide sufiicient compositional stability to the molten metal or alloy containing the constituent particles to enable producing a casting of satisfactory particle or dispersoid distribution.
  • the coated particles must be injected below the surface of the bath with sufficient positive pressure, i.e., pressure above atmospheric pressure, to penetrate the bath metal and any surface film thereon and to overcome the static pressure of the molten metal at the depth of the injection. As mentioned above, the integrity of the coatings must be maintained to successfully introduce and disperse the normally incompatible constituent.
  • the coatings become partially or even wholly dissolved or otherwise incorporated in the molten bath and in certain advantageous embodiments ultimately impart enhanced, useful characteristics.
  • the alloy is chill cast, e.g., permanent mold cast or die cast, or is similarly rapidly solidified such as in the continuous casting of ingot stock that is continuously solidified and withdrawn from the mold.
  • the coatings on the particles should be completely continuous over the entire surface of each particle. While, for practical purposes, the coatings need not be entirely perfect, it is to be emphasized that in this connection the particles must be substantially surrounded by the coatings, e.g., coatings over at least advantageously of the surface of the particle.
  • Coatings particularly metal, about 0.2 to about 50 microns thick applied by known methods, including vapor or chemical deposition, e.g., nickel deposition from the decomposition of nickel carbonyl, deposition of copper by galvanic or other chemical methods, etc., are particularly satisfactory.
  • Coating thickness should be at least about 2 microns to insure the particle is essentially covered. To avoid introducing excessive amounts of coatings the thickness is preferably not greater than about 5 microns; however, thickness is not as important as the requirement that the coating cover essentially the entire particle and satisfactory results may be obtained with thicknesses of as little as 0.05 micron.
  • Nickel-coated graphite powder such as nickel-coated graphite comprising about 75% nickel and 25% carbon with average particle size about 80 nicrons.
  • Metal coatings may also comprise, or consist essentially of, in addition to nickel, copper, cobalt, iron aluminum or zinc and alloys thereof.
  • Particles injected in accordance herewith are preferably at least about 40 microns in average cross-section size, particularly in the case of graphite.
  • excellent results have been and can be attained with smaller particle sizes, say, a mean particle size of about 20 microns, but it is deemed easier to coat larger particle sizes and this should contribute to some extent to the ease of achieving a substantially continuous coating about the graphite particles.
  • ease of mechanically handling the particles is facilitated through larger particle size, and there is also the built-in virtue of minimizing fiowability difficulties that might otherwise possibly ensue should extremely fine particle sizes (e.g., sub-micron) be used.
  • Particle size advantageously should not exceed about 200 microns, inasmuch as larger particles may tend to segregate too rapidly. With respect to graphite particularly, especially good recovery and uniform dispersion obtains with an average particle size of about 40 or 60 to microns. In some exceptional instances, if solidification can be brought about very quickly after injection, e.g., in about 3 to about 30 seconds, satisfactory results can be obtained with particles as large as 2000 microns.
  • the particles should be of sizes which average about 40 to about 200 microns. It should also be mentioned that fluidity for producing castings is benefited by having, at least in the case of graphite, particles of generally equiaxcd configurations, e.g., relatively spheroidal or lumplike and thus not acicular or flake-like.
  • the graphitic aluminum should contain at least 0.6% graphite, advantageously at least about 1.2% graphite, in order to have satisfactory frictional characteristics under conditions of poor lubrication, such as the mixed film condition where the fluid film partially breaks, and to be slidably operable to a substantial extent in the boundary lubrication region.
  • the graphite content should be controlled to be not greater than and advantageously not higher than 2.5%.
  • a molten bath was established of an aluminum-base alloy which contained 9.26% silicon, 2.94% copper, 1.11% magnesium, 0.24% iron, 0.01% manganese, 0.02% zinc, 0.12% titanium, 0.01% nickel, less than 0.005% carbon and balance aluminum.
  • Nickel-coated graphite particles were introduced into the bath in a stream of nitrogen gas while the bath was maintained at a temperature of about 1400 F., which was about 300 F. above the liquidus temperature.
  • the average particle size (including coating, which 'was about 2 microns thick) was about 80 microns with essentially all of the particles fine enough to pass through a number U.S. Series 100 screen. (Screen size mesh numbers hereinafter are US.
  • the particles were introduced into the melt from a batch feeder assembly comprising a gas pressurized hoppeer with a valve at the bottom of the hopper for regulating flow from the hopper, a steel tube connected to the valve exit and leading downward from the hopper, and a graphite nozzle attached at the lower end of the tube.
  • Nitrogen was provided from a pressurized cylinder connected to the feeder assembly by two conduits, with one of the conduits leading from the cylinder into the hopper, thereby pressurizing the hopper, and with the second conduit leading into the steel tube below the hopper.
  • the graphite nozzle extended below the surface of the bath into the lower extremity of the melt and directed the flow of nitrogen and nickel-coated particles toward the bottom of the bath.
  • Injection was successfully accomplished with a positive pressure of about 2 p.s.i.
  • the weight of particles introduced into the bath was about of the initial weight of the bath. Dispersion and retention of the particles in the bath metal were very satisfactory and at least about 90% of the graphite particles were retained in the melt.
  • the bath metal was cast (Alloy 1) at a pouring temperature of about 1400 F. into iron chill molds for cast rods and other castings. Metallographic examination confirmed that the castings contained a great number of graphite particles dispersed uniformly throughout the matrix.
  • Alloy l The chemical composition of Alloy l is set forth in Table I along with the chemical compositions of Alloys 2-12, which were also prepared in the manner of Alloy 1.
  • the nickel coatings were about 2 microns average thickness, whereas for 7, 8 and 10 the coatings were about 15, 50 and 30 microns, respectively, in average thickness.
  • Chill mold castings containing graphite dispersed with satisfactory uniformity were thus produced, although the recovery of graphite in Alloy 10 (made with, for graphite, undesirably large particles of 400 microns size) was only marginally acceptable.
  • the extent, if any, to which the nickel coatings remained on the particles of Alloys 1 to 12 could not be determined. Optical and electron micrographic examination did not disclose any nickel coating around the graphite particles in the solidified alloys.
  • Graphite size The numeral 60 refers to particles which passed through a 200 mesh screen (opening about 74 microns) but retained by a 325 mesh screen (opening about 44 microns), and is thus a representative approximate average of the largest and smallest of such particles.
  • the numeral 120 denotes particles passing through a 100 mesh (opening about 149 microns) but retained by a 200 mesh (opening about 74 microns); the numeral 200 depicts particles passing through a 60 mesh (opening about 250 microns) and retained by an 80 mesh (opening about 177 microns); and the numeral 400 refers to particles passing through a 40 mesh (opening about 420 microns) but retained by a 45 mesh (opening about 350 microns).
  • the numeral 80 sets forth a particle size as previously described in connection with Example I. And the symbol 40 indicates that the particles all passed through a 325 mesh screen (opening about 44 microns) and the approximate average particle size as determined in accordance with the above would be approximately 20 microns.
  • Bal. Balance essentially.
  • FIGS. 1 and 2 Uniform dispersions of graphite particles in accordance with the invention are illustrated in FIGS. 1 and 2 by microstructures from a 7-inch long, 2-inch diameter chill cast bar of Alloy 3 cast in the vertical position.
  • FIG. 1 was taken from a section of the bar which was near the top during casting and solidification, FIG. 2 being taken from near the bottom. Accordingly, microstructures from the same casting at cross sections separated by a vertical distance of about 6 inches show that the graphite particles remained uniformly dispersed and did not detrimentally segregate by floating, sinking, agglomeration or otherwise.
  • FIGS. 1 and 2 also reflect the effectiveness of the nickel coatings in providing sufficient compositional stability to the molten alloy to enable casting and statically solidifying the alloy to thereby produce castings of a uniform graphitic alloy composition.
  • Nickel-coated graphite particles were also successfully injected with nitrogen into a molten bath containing about 6.5% tin, the balance being essentially aluminum. Metallographic examination showed a high recovery of uniformly distributed graphite.
  • Rate of injection was about 0.03 pound per minute and the weight of the injected powder was about 10% of the initial weight of the melt.
  • the alloy was cast at about 1250 F. into chill molds. Graphite particles were dispersed satisfactorily and the alloy contained 4.7% copper and 0.69% graphitic carbon.
  • Nickel-coated graphite particles (as described in Example I) and comprising about 75% nickel were also injected in a nitrogen gas stream into a melt containing about 4% aluminum and balance essentially zinc at about 1100" F. Microexamination of vertical cross sections of the castings showed a high recovery and uniform distribution of graphite. No sign of any nickel coating was observed around the graphite particles. Chemical analysis revealed that the alloy contained 1.15% graphitic carbon, 3.25% nickel and 4.16% aluminum. Similarly, metalcoated graphite particles can be injected in the same manner into other known zinc alloys, including alloys containing up to about 30% aluminum, up to about 4% copper, up to about 0.4% lead, up to about 0.3% cadmium, up to about 0.5% magnesium and balance essentially zinc.
  • Graphitic magnesium alloys containing 0.05% or more graphite can also be produced in accordance with the invention by gas injection of metal-coated graphite into molten magnesium baths containing up to aluminum, up to 6% zinc, up to 4% rare earth metals, up to 3.3% thorium and up to 0.75% zirconium.
  • argon was used in injecting nickel-coated graphite particles (of the type used in Example I) through a tube into an aluminum- 1l.5% silicon alloy bath at about 1350 F. Chemical analysis indicated that the alloy contained '1.4% graphite and 4.65% nickel. Graphite recovery was about 70%, which was of the order of good recoveries, e.g., 70% to 90%, frequently obtained using nitrogen in otherwise similar injection processes.
  • Graphitic aluminum castings made by the process of the invention have also been induction melted, stirred and recast without excessive loss of graphite, thereby demonstrating that for commercial purposes, master alloys or scrap castings, gates, risers, etc., can be used as melting stock for making graphitic aluminum cast articles and other products. Good compositional and microstructural stability at room temperature and elevated temperatures is another favorable attribute of the alloy.
  • Alloys 1-10 were chill cast and wear tested using a Hohman tester.
  • circular discs were rotated in contact with shoe specimens having concave surfaces which mated with the peripheral surfaces of the disc specimens.
  • the specimens were submerged in lubricating mineral oil (Aturbn'o).
  • the testing cycle except when specimens galled so greatly that binding caused rotation to cease and necessitated discontinuance of the test, was to rotate the specimens at 830 revolutions per minute (rpm) and to increase the bearing pressure in steps until the pressure forcing the mating surfaces together reached a maximum level of 2480 psi.
  • the rotational speed was decreased (without decreasing the load) in steps until rotation ceased due to binding or else, if galling did not occur, until the heat and friction increased to about the limiting capacity of the test apparatus.
  • ZN P where Z is the oil viscosity in centipoises, N is the rotation speed in r.p.m. and P is the pressure in p.s.i. at the mating surface, was used as an index of lubrication conditions at the mating surfaces of the specimens.
  • the bearing parameter is inversely proportional to the pressure, which increases during test, and is directly proportional to the viscosity and the speed, which decrease during test, the specimens were subjected to progressively deteriorating lubricating conditions during test.
  • the maximum coefiicient of friction at which sliding contact operation was successfully maintained during test i.e., the maximum coefficient of friction prior to seizure (if seizure occurred) was determined.
  • High maximum friction coeffiicients (Max. Mu) show good frictional characteristics and vice versa.
  • the alloys were satisfactory under boundary lubrication. If less than 0.07, the alloy failed to reach a boundary lubrication condition characterized by a bearing parameter not greater than 3.0 and could be operated only in mixed or full film lubrication.
  • Results of the Hohman tests are set forth in Table II. Except for Alloys 2 and 3, the bearing shoes were made from chill castings of an alloy which is commercially used in cast cylinder blocks for internal combustion engines and nominally contains about 12% silicon, less than 0.005% carbon with the balance being aluminum. As to Alloys 2 and 3, the shoes were made of the same alloy as the rotating disc.
  • the lubricating oil for the aluminumsilicon alloy shoes was a No. 50 oil having a viscosity of 29 centipoises at 100 F. and the oil for the selfmated tests was a No. 60 oil having a viscosity of 60 centipoises at 100 F.
  • the numbers in the columns "Average Max. Mu. and Average Min. B in Table II show the average values of the highest friction coefiicients and the lowest values of the bearing parameter, respectively, that were reached at the finish of each test.
  • incompatible systems include those in which a constituent is insoluble in alloys as well as the base metals which might form the alloys.
  • aluminum bath metals include not only pure aluminum (both commercially pure and high purity) but also aluminum alloys containing, in addition to a major proportion of aluminum, up to about 25% silicon, up to about 25% tin, up to about 15% copper, up to about 15% magnesium, up to about 20% zinc, up to about 10% nickel, up to about 8% cobalt, up to about 5% manganese, up to about 1% chromium and up to about 1.5% iron.
  • Such alloys preferably contain at least 5%, e.g.
  • silicon to promote uniform distribution of graphite in the melt and to avoid detrimental segregation of graphite during solidification.
  • silicon is beneficial.
  • the silicon should be controlled in relationto any nickel so that the total percentage thereof does not exceed about 20% in order to avoid alloy embrittlement.
  • Small amounts of optional elements e.g., titanium, boron, zirconium, vanadium, antimony and cadmium, may be included for purposes such as grain refinement, strengthening, raising the recrystallization temperature, improving weldability, etc. (The amount by weight of aluminum in an aluminum-base alloy herein is greater than that of any other element. This applies to other alloy base metals as well.)
  • the amount and nature of coating metal is taken into account.
  • up to 10% nickel, e.g., 0.05% to 10% nickel can be added and is particularly advantageous for producing graphitic aluminum alloys since it melts, dissolves or is otherwise incorporated into the alloy, e.g., as a nickel aluminide, and provides, especially in amounts of at least 4%, e.g., 4% to 7%, hardness, strength and wear resistance at room temperature and at elevated temperatures, and high retention and uniform distribution of the graphite particles.
  • beneficial improvements in frictional and/or machinability characteristics of metals such as aluminum, zinc or magnesium are obtainable through utilizing the process of the invention to incorporate graphite in amounts of at least 0.2%, and upwards to 5%, 10% or even 15% or more in these metals.
  • improvement is obtainable with as little as 0.05% graphite, the characteristics of such alloys are greatly less desirable. Accordingly, it is of considerable benefit to have substantially greater amounts of graphite, e.g., at least 0.2%, or, more advantageously, at least 0. 6% or 1.8% dispersed throughout the matrix metal.
  • An especially advantageous alloy contains about 1.2% to about 2.5% graphitic carbon, about 4% to about 7% nickel, about 8% to about 13% silicon, up
  • the constituent to be injected into the molten bath of the dispersion medium should not be one which decomposes at the bath temperature.
  • the constituent to be dispersed can be selected from the group consisting of oxides, carbides, nitrides and borides. Molybdenum disulfide would be another such constituent, particularly for lubricity qualities.
  • Various intermetallic compounds are also contemplated. Too, among other coatings that might be used, in addition to those previously given herein, and this depends, of course, upon what might be desired in the final product, are silicon, tin, cadmium, antimony, chromium and tungsten.
  • graphite specifically, while the foregoing discussion has centered about producing graphitic alloys of aluminum, zinc or magnesium, particularly aluminum, the invention contemplates injecting coated graphite into other molten bath metals in which graphite is virtually insoluble or otherwise metallurgically incompatible, including copper and copper-base alloys, advantageously brass and bronze, lead alloys and tin alloys.
  • the densities of the respective incompatible constituents should be such that one does not exceed the other by a factor of about three; otherwise, there is the possibility of encountering immediate or rapid segregation as by sinking or floating.
  • the difference in respective densities should not exceed a factor of two.
  • Incompatible systems include those in which the mutual insolubility obtains and there is nonreactivity at temperatures up to several hundred degrees above the melting point of the dispersion medium.
  • the subject invention is particularly applicable in the production of graphitic alloys for sliding contact elements including pistons, bearings, cylinder liners and blocks, sliding valves, internal combustion engine rotors, electrical pick-up shoes, etc.
  • the invention is also applicable to the production of wrought articles including rods, bars, tubes, plates, etc., made by working cast, including continuously cast, graphitic alloys provided herein.
  • a graphitic aluminum alloys containing 0.51% carbon and 4.1% nickel was hot forged, hot rolled, cold rolled into rod and thereafter cold drawn to produce wire.
  • the new graphitic alloy, particularly of aluminum is useful for providing wear and/or gall resistant surface claddings or overlays, e.g., welded overlays, on composite articles.
  • Graphitic alloys of the present invention are not to be confused with carbidic alloys which contain carbon in combined form, e.g., carbides such as molybdenum carbide or tungsten carbide, rather than in uncombined graphitic form.
  • a process for producing a graphitic alloy comprising providing a molten bath predominantly of metal selected from the group consisting of aluminum, magnesium and zinc, injecting under positive pressure into the bath graphite particles of average particle sizes of about 40 microns to about 2000 microns and having surrounding metal coatings effective to impart compositional stability to the molten alloy containing the particles and thereby provide retention of the particles in the bath, pouring molten metal from said bath having retained graphite particles into a mold and thereafter solidifying said metal to provide a graphitic alloy casting.
  • particle coatings are of metal selected from the group consisting of nickel, copper, cobalt, iron, aluminum, zinc and alloys thereof.
  • graphite particles are about 40 microns to about 200 microns in average cross section size.
  • a process for producing a solidified graphitic alloy comprising providing a molten metal bath predominantly of a metal selected from the group consisting of aluminum, magnesium and zinc at a temperature about F. to about 450 F. above the liquidus temperature of the bath metal, injecting into said bath nickel-coated graphite particles of average particle sizes from about 40 microns to about 200 microns having surrounding metal coatings about 0.2 micron to about 50 microns in thickness and having exterior surfaces in the essentially metallic condition by flowing said particles in a nonreactive gas stream through a tubular conduit exiting below the surface of the bath while maintaining said exterior surfaces in the metallic condition at least until the coated particles are in the bath metal, pouring from said bath molten metal having said injected particles retained therein into a mold and thereafter solidifying the metal to provide a graphitic alloy casting.
  • a process for producing a graphitic alloy comprising providing a molten bath predominantly of metal characterized by metallurgical incompatibility with graphite, injecting under positive pressure into the bath graphite particles of average particle sizes of about 40 microns to about 2000 microns and having surrounding metal coatings effective to impart compositional stability to the molten alloy containing the particles and thereby provide retention of the particles in the bath, pouring molten metal from said bath having retained graphite particles into a mold and thereafter solidifying said metal to provide a graphitic alloy casting.
  • a process for producing an alloy containing graphitic carbon and at least one metal normally characterized in the molten condition by metallurgical incompatibility therewith which comprises, establishing a molten bath predominantly of graphitic incompatible metal, injecting below the surface of the molten bath graphite particles the surface areas of which are substantially enveloped by coatings of essentially uncombined metal devoid of detrimental oxides, said coated particles being injected under positive pressure while substantially maintaining the metallic condition of the metal coating until introduced into the molten bath, and thereafter solidifying the molten metal whereby a gr-aphitic alloy characterized by a significant percentage of retained graphite is produced.
  • a process for producing a composition of matter containing at least one constituent dispersed in metal normally characterized in the molten condition by metallurgical incompatibility therewith which comprises, establishing a molten bath predominantly of such metal, introducing into and dispersing within the molten bath said constituent in particulate form by injecting such particles under positive pressure below the surface of the molten bath, said particles being characterized in that the outer surface areas thereof are substantially enveloped by a coating effective to impart substantial compositional stability between the molten metal and particles, the integrity of the coating being maintained during injection for a period sufiicient to achieve dispersibility and retention of the particles throughout the melt, and thereafter solidifying the molten bath.
  • a process for producing a dispersoid composition of matter having a matrix of dispersant metal and containing dispersoid particles normally characterized by metallurgical incompatibility therewith when the metal is in the molten state which comprises, establishing a molten bath predominantly of such metal, introducing into and dispersing within the molten bath particles of an incompatible material selected from the group consisting of graphite, oxides, carbides, nitrides, and borides by injecting the particles under positive pressure below the surface of the molten bath, said particles being characterized in that the exterior surface areas thereof are substantially enveloped by coatings of essentially uncom- 14 bined metal effective to impart substantial compositional stability between the molten metal and particles, the integrity of the coating being maintained during injection for a period sufficient to achieve dispersibility and retention of the particles throughout the melt and thereafter solidifying the molten bath.
  • a process for producing a composition of matter containing at least one constituent dispersed in a metal normally characterized in the molten condition by metallurgical incompatibility therewith which comprises introducing under positive pressure and dispersing particles of the constituent material within a molten bath containing said metal, the particles being characterized in that the outer surfaces thereof are substantially enveloped by a coating sufficient to impart compositional stability between the molten metal and the constituent particles, said coated particles being introduced while maintaining the integrity of the coatings for a period suflicient such that the ability of the coating to confer compositional stability is not detrimentally impaired and thereafter solidifying the molten bath.
  • metal coating is from the group consisting of nickel, copper, cobalt, iron, aluminum and zinc and alloys thereof.
  • a process in accordance with claim 26 in which metal incompatible with silica, alumina and silicon carbide is from the group consisting of aluminum, aluminum alloys, zinc and zinc alloys.

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Cited By (37)

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US3753694A (en) * 1970-07-06 1973-08-21 Int Nickel Co Production of composite metallic articles
US3827129A (en) * 1972-01-06 1974-08-06 British Railways Board Methods of producing a metal and carbon fibre composite
US3856583A (en) * 1972-01-20 1974-12-24 Ethyl Corp Method of increasing hardness of aluminum-silicon composite
US3907514A (en) * 1972-10-19 1975-09-23 Pure Carbon Company Inc Aluminum carbon composite seal material
US3927991A (en) * 1969-07-15 1975-12-23 Toyo Kogyo Co Wear-resistant sliding member
US3961945A (en) * 1972-01-20 1976-06-08 Ethyl Corporation Aluminum-silicon composite
US3997340A (en) * 1973-07-02 1976-12-14 Ethyl Corporation Method of preparing an aluminum-silicon composite
US4056874A (en) * 1976-05-13 1977-11-08 Celanese Corporation Process for the production of carbon fiber reinforced magnesium composite articles
US4152149A (en) * 1974-02-08 1979-05-01 Sumitomo Chemical Company, Ltd. Composite material comprising reinforced aluminum or aluminum-base alloy
US4207096A (en) * 1976-02-02 1980-06-10 Hitachi, Ltd. Method of producing graphite-containing copper alloys
US4357985A (en) * 1981-03-26 1982-11-09 Material Concepts, Inc. Method of isothermally forming a copper base alloy fiber reinforced composite
US4365997A (en) * 1979-05-15 1982-12-28 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Wear resistant compound material, method for manufacturing it and use of such compound material
US4383970A (en) * 1978-08-11 1983-05-17 Hitachi, Ltd. Process for preparation of graphite-containing aluminum alloys
US4473103A (en) * 1982-01-29 1984-09-25 International Telephone And Telegraph Corporation Continuous production of metal alloy composites
US4630665A (en) * 1985-08-26 1986-12-23 Aluminum Company Of America Bonding aluminum to refractory materials
US4720434A (en) * 1985-09-02 1988-01-19 Toyota Jidosha Kabushiki Kaisha Composite material including silicon carbide and/or silicon nitride short fibers as reinforcing material and aluminum alloy with copper and relatively small amount of silicon as matrix metal
US4731132A (en) * 1984-09-26 1988-03-15 Technical Research Associates, Inc. Oxide dispersion hardened aluminum composition
US4812289A (en) * 1986-09-02 1989-03-14 Technical Research Assoc., Inc. Oxide dispersion hardened aluminum composition
US4853182A (en) * 1987-10-02 1989-08-01 Massachusetts Institute Of Technology Method of making metal matrix composites reinforced with ceramic particulates
AU596723B2 (en) * 1984-09-26 1990-05-10 Technical Research Associates, Inc. Oxide dispersion hardened aluminum composition
US5385195A (en) * 1991-10-23 1995-01-31 Inco Limited Nickel coated carbon preforms
US5511603A (en) * 1993-03-26 1996-04-30 Chesapeake Composites Corporation Machinable metal-matrix composite and liquid metal infiltration process for making same
WO2010083826A1 (de) * 2009-01-20 2010-07-29 Nano-X Gmbh Verfahren zum modifizieren von metallschmelzen
US20150099102A1 (en) * 2013-10-08 2015-04-09 Lawrence Livermore National Security, Llc Multifunctional reactive inks, methods of use and manufacture thereof
US9707739B2 (en) 2011-07-22 2017-07-18 Baker Hughes Incorporated Intermetallic metallic composite, method of manufacture thereof and articles comprising the same
US9816339B2 (en) 2013-09-03 2017-11-14 Baker Hughes, A Ge Company, Llc Plug reception assembly and method of reducing restriction in a borehole
US9926766B2 (en) 2012-01-25 2018-03-27 Baker Hughes, A Ge Company, Llc Seat for a tubular treating system
US10016810B2 (en) 2015-12-14 2018-07-10 Baker Hughes, A Ge Company, Llc Methods of manufacturing degradable tools using a galvanic carrier and tools manufactured thereof
US10221637B2 (en) 2015-08-11 2019-03-05 Baker Hughes, A Ge Company, Llc Methods of manufacturing dissolvable tools via liquid-solid state molding
US10240419B2 (en) 2009-12-08 2019-03-26 Baker Hughes, A Ge Company, Llc Downhole flow inhibition tool and method of unplugging a seat
US10301909B2 (en) 2011-08-17 2019-05-28 Baker Hughes, A Ge Company, Llc Selectively degradable passage restriction
US10378303B2 (en) 2015-03-05 2019-08-13 Baker Hughes, A Ge Company, Llc Downhole tool and method of forming the same
US11090719B2 (en) 2011-08-30 2021-08-17 Baker Hughes, A Ge Company, Llc Aluminum alloy powder metal compact
US11167343B2 (en) 2014-02-21 2021-11-09 Terves, Llc Galvanically-active in situ formed particles for controlled rate dissolving tools
US11365164B2 (en) 2014-02-21 2022-06-21 Terves, Llc Fluid activated disintegrating metal system
US11649526B2 (en) 2017-07-27 2023-05-16 Terves, Llc Degradable metal matrix composite
US12018356B2 (en) 2014-04-18 2024-06-25 Terves Inc. Galvanically-active in situ formed particles for controlled rate dissolving tools

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2253282C2 (de) * 1972-10-31 1974-03-14 Mahle Gmbh, 7000 Stuttgart Warmfeste Aluminium-Sinterlegierung
EP0322475A1 (en) * 1987-12-29 1989-07-05 Technical Research Associates Inc. Oxide dispersion hardened aluminium composition
IT1219702B (it) * 1988-06-01 1990-05-24 Nuova Samin Spa Materiali compositi di piombo o sue leghe rinforzati con polveri e/o fibre ceramiche e usi degli stessi
GB9406513D0 (en) * 1994-03-31 1994-05-25 Brunel University Of West Lond Ceramic reinforced metal-matrix composites

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3927991A (en) * 1969-07-15 1975-12-23 Toyo Kogyo Co Wear-resistant sliding member
US3753694A (en) * 1970-07-06 1973-08-21 Int Nickel Co Production of composite metallic articles
US3827129A (en) * 1972-01-06 1974-08-06 British Railways Board Methods of producing a metal and carbon fibre composite
US3856583A (en) * 1972-01-20 1974-12-24 Ethyl Corp Method of increasing hardness of aluminum-silicon composite
US3961945A (en) * 1972-01-20 1976-06-08 Ethyl Corporation Aluminum-silicon composite
US3907514A (en) * 1972-10-19 1975-09-23 Pure Carbon Company Inc Aluminum carbon composite seal material
US3997340A (en) * 1973-07-02 1976-12-14 Ethyl Corporation Method of preparing an aluminum-silicon composite
US4152149A (en) * 1974-02-08 1979-05-01 Sumitomo Chemical Company, Ltd. Composite material comprising reinforced aluminum or aluminum-base alloy
US4207096A (en) * 1976-02-02 1980-06-10 Hitachi, Ltd. Method of producing graphite-containing copper alloys
US4056874A (en) * 1976-05-13 1977-11-08 Celanese Corporation Process for the production of carbon fiber reinforced magnesium composite articles
US4383970A (en) * 1978-08-11 1983-05-17 Hitachi, Ltd. Process for preparation of graphite-containing aluminum alloys
US4365997A (en) * 1979-05-15 1982-12-28 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Wear resistant compound material, method for manufacturing it and use of such compound material
US4357985A (en) * 1981-03-26 1982-11-09 Material Concepts, Inc. Method of isothermally forming a copper base alloy fiber reinforced composite
US4473103A (en) * 1982-01-29 1984-09-25 International Telephone And Telegraph Corporation Continuous production of metal alloy composites
US4731132A (en) * 1984-09-26 1988-03-15 Technical Research Associates, Inc. Oxide dispersion hardened aluminum composition
AU596723B2 (en) * 1984-09-26 1990-05-10 Technical Research Associates, Inc. Oxide dispersion hardened aluminum composition
US4630665A (en) * 1985-08-26 1986-12-23 Aluminum Company Of America Bonding aluminum to refractory materials
US4720434A (en) * 1985-09-02 1988-01-19 Toyota Jidosha Kabushiki Kaisha Composite material including silicon carbide and/or silicon nitride short fibers as reinforcing material and aluminum alloy with copper and relatively small amount of silicon as matrix metal
US4812289A (en) * 1986-09-02 1989-03-14 Technical Research Assoc., Inc. Oxide dispersion hardened aluminum composition
US4853182A (en) * 1987-10-02 1989-08-01 Massachusetts Institute Of Technology Method of making metal matrix composites reinforced with ceramic particulates
US5578386A (en) * 1991-10-23 1996-11-26 Inco Limited Nickel coated carbon preforms
US5385195A (en) * 1991-10-23 1995-01-31 Inco Limited Nickel coated carbon preforms
US5511603A (en) * 1993-03-26 1996-04-30 Chesapeake Composites Corporation Machinable metal-matrix composite and liquid metal infiltration process for making same
WO2010083826A1 (de) * 2009-01-20 2010-07-29 Nano-X Gmbh Verfahren zum modifizieren von metallschmelzen
US10669797B2 (en) 2009-12-08 2020-06-02 Baker Hughes, A Ge Company, Llc Tool configured to dissolve in a selected subsurface environment
US10240419B2 (en) 2009-12-08 2019-03-26 Baker Hughes, A Ge Company, Llc Downhole flow inhibition tool and method of unplugging a seat
US9707739B2 (en) 2011-07-22 2017-07-18 Baker Hughes Incorporated Intermetallic metallic composite, method of manufacture thereof and articles comprising the same
US10697266B2 (en) 2011-07-22 2020-06-30 Baker Hughes, A Ge Company, Llc Intermetallic metallic composite, method of manufacture thereof and articles comprising the same
US10301909B2 (en) 2011-08-17 2019-05-28 Baker Hughes, A Ge Company, Llc Selectively degradable passage restriction
US11090719B2 (en) 2011-08-30 2021-08-17 Baker Hughes, A Ge Company, Llc Aluminum alloy powder metal compact
US9926766B2 (en) 2012-01-25 2018-03-27 Baker Hughes, A Ge Company, Llc Seat for a tubular treating system
US9816339B2 (en) 2013-09-03 2017-11-14 Baker Hughes, A Ge Company, Llc Plug reception assembly and method of reducing restriction in a borehole
US11370927B2 (en) * 2013-10-08 2022-06-28 Lawrence Livermore National Security, Llc Multifunctional reactive inks, methods of use and manufacture thereof
US10377090B2 (en) * 2013-10-08 2019-08-13 Lawrence Livermore National Security, Llc Multifunctional reactive inks, methods of use and manufacture thereof
US20150099102A1 (en) * 2013-10-08 2015-04-09 Lawrence Livermore National Security, Llc Multifunctional reactive inks, methods of use and manufacture thereof
US11167343B2 (en) 2014-02-21 2021-11-09 Terves, Llc Galvanically-active in situ formed particles for controlled rate dissolving tools
US11365164B2 (en) 2014-02-21 2022-06-21 Terves, Llc Fluid activated disintegrating metal system
US11613952B2 (en) 2014-02-21 2023-03-28 Terves, Llc Fluid activated disintegrating metal system
US12031400B2 (en) 2014-02-21 2024-07-09 Terves, Llc Fluid activated disintegrating metal system
US12018356B2 (en) 2014-04-18 2024-06-25 Terves Inc. Galvanically-active in situ formed particles for controlled rate dissolving tools
US10378303B2 (en) 2015-03-05 2019-08-13 Baker Hughes, A Ge Company, Llc Downhole tool and method of forming the same
US10221637B2 (en) 2015-08-11 2019-03-05 Baker Hughes, A Ge Company, Llc Methods of manufacturing dissolvable tools via liquid-solid state molding
US10016810B2 (en) 2015-12-14 2018-07-10 Baker Hughes, A Ge Company, Llc Methods of manufacturing degradable tools using a galvanic carrier and tools manufactured thereof
US11649526B2 (en) 2017-07-27 2023-05-16 Terves, Llc Degradable metal matrix composite
US11898223B2 (en) 2017-07-27 2024-02-13 Terves, Llc Degradable metal matrix composite

Also Published As

Publication number Publication date
DE1758569A1 (de) 1971-02-18
CH520204A (fr) 1972-03-15
NL6811571A (zh) 1969-09-29
BE717884A (zh) 1969-01-10
FR95986E (fr) 1972-05-19
GB1237111A (en) 1971-06-30
ES356027A2 (es) 1969-12-16

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