GB2248071A - Method and apparatus for production of metal base composite material - Google Patents

Method and apparatus for production of metal base composite material Download PDF

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GB2248071A
GB2248071A GB9119770A GB9119770A GB2248071A GB 2248071 A GB2248071 A GB 2248071A GB 9119770 A GB9119770 A GB 9119770A GB 9119770 A GB9119770 A GB 9119770A GB 2248071 A GB2248071 A GB 2248071A
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particles
crucible
molten metal
metal
gas
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Valery Gavrilovich Borisov
Ljudmila Petrovna Borisenki
Alexandr Ivanchenko
Nikolai Andreevich Kaluzhsky
Alexandr Petrovich Bogdanov
Vladimir Rapoport
Nikolai Nikolaevich Belousov
Svetlana Nikolaevna Pavlova
Tatyana Igorevna Belyaeva
Vladimir Vladimirovich Volkov
Viktor Semenovich Shusterov
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VNI I PI ALUMINIEVOI MAGNIEVOI
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VNI I PI ALUMINIEVOI MAGNIEVOI
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D1/00Treatment of fused masses in the ladle or the supply runners before casting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/06Alloys
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00Charging; Discharging; Manipulation of charge
    • F27D3/18Charging particulate material using a fluid carrier

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Manufacturing & Machinery (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Abstract

A method of making a composite material which includes introducing a stream of ionized inert gas having an additive entrained therein into a molten base metal with agitation. <IMAGE>

Description

1 1 1 METHOD AND APPARATUS FOR PRODUCTION OF METAL BASE COMPOSITE MATERIAL
The present invention relates to the metallurgical field, and more specifically to a method for the production of cast bbase metal material having distributed therein very fine particles which can be particles of ceramics, zietals, alloys, Intermetallics, carbides, nitrides, borides and substances useful in enhancing properties of the base metal.
Development cf the aircraft and ship building, car making and a number of other industries require new materials having improved workability and service properties.
Metallic sltructural naterials (alloys) are nowadays produced by melting the base metal to liquid form with additive components, with the melting process going at the temperature of the entire system which ensures the complete melting and mutual dissolution of the components (Fig. 42a).
With the d.,^cD of temperature oil.' the alloy during cooling and - the alloy components sharply solidification, the solubility c.4 decreases and, at a certain temperature particular for each alloy itate and grow system and co=posizion, solid phases begin to precipi from the homcSeneous melt in the for-m of alloy component crystals, 2 or, more frequently, in the form of the crystals of the =emical compounds of components (intermetallic phases) (Fig. 2, b,c). With, further cooling the rest of the melt is crystallized in the form of a solid solution of the components in the base metal (Fig. 2, d', Intermetallic phases with crystal lattice and properties different from those of the base alloy (matrix) strongly affect the properties of the alloy system as a whole.
The size of the intermetallic phases precipitated in the process of crystallization of the alloy should not exceed fractions of one micron, otherwise quality of the alloy will be sharply impaired due to loss of ductility and strength.
The solubility of metals and metalloids in the metallic matrix is very much limited in the solid state and this factor accounts Lor the narrow selection of commercial alloys and the practically achieved limit of improvement in the properties of the commercial structural alloys by change in composition.
A new class of structural materials have been developed, which contain artificially 'incorporated particles or fibers of oxides, carbides and other compounds enabling the attainment of assured properties of the system as a whole. Such materials are known as composites since the components of the metallic system are not precipitated from the matrix metal, as is the case with the conventional alloys, but are artificially incorporated into the system. All known metallic alloys representing the matrix with incorporated particles, whose properties significantly dif fer frOm the matrix, are basically the composites, although of natural occurrence in the making of the alloy.
by a ccmncsi- The properties of metallic materials represented 1-e system of artificial or natural origin are indicated as follows:
- ductility of the material is determined by ability of the matrix (as a rule the ability of the solid solutions of co=onents in the base alloy) for plastic flow, as well as by size and syngonia (crystalline structure) of intermetalloid and other inclusions in the matrix); - strength, heat resistance, fatig-ue strength, resistance of materials to development of cracks is determined by interaction of the of the inclusions and the matrix, as well as distcr---Jons of the -Jon of inclusions; crystalline lattice of the matrix under act- - hardness, wear resistance, tribotechnical properties c4.
the material are determined by properties of the inclusions; factor, specific modulus of elasIticity, linear expansion.
the rat ined by a set of weight (density) of t I-erial are deternproperties of the matrix and -4.-clusions.
Thus, the development of new metallic materials with a predetermined combination of workabillty and sei:-jice properties should be theoretically achievable on the basis c.E selection of the that is optimum composition c.' the metallic system in each case, 4. selection of the matrix and inclusions whose proper-ties and interaction determine the properties of the c---...mcsite system as a whole.
Selection of the metall---- s.jsten base is determined, by required service properties of the material and level c.E 4-s properties (steel, aluminum, copper, magnesiurm, nickel, etc.).
-1 ficulty in implementation of The major difA he technology for production of structural metallic materials is the injection o.1 components into the structure in the form of superfine particles of compounds thermodynamically and thermally stable in the matrix, and which measure from a few nanometres to a few microns.
In the production of natural composite metallic materials (i.e. complex alloys) this problem is dealt with by precipitation of particles (intermstalloids) from supersaturated solid solutions of the components of the alloy in the base metal produced by the use of high-rate cooling of homogeneous melts. The recrulred cooling rate can be practically achieved only in case of relatively small quantities of alloy melt. In practice, a high cooling rate is provided by physical dispersion of the nelt followed by cooling f ine drops of the melt in a cooling medium. This requires expensive operations of drying, degassing and compacting particles (granules) to provide pellets. Thus, the technology for production of new hieta1lic alloyis by the pelletizing technique hds not found wide use in the industry.
The difficulty of introducing superfine particles into the metallic melts in attributed to two circumstances. First due to lack of fluidity of superfine particles (thousandths of microns or less in size) the metering of particles when in---ct-ed into the melt is rather difficult or sometimes even impossible. Second, due to presence of adsorbed oxygen on the surface of the partic.Les upon in contact with the melt, oxides of the base metal are formed on the surface, which prohibits wetting of the particles by the melt. This problem especially =anifests itself during injection of the particles into the melts of metals having high oxygen reactivity (aluminum, magnesium, etc.). The above factor also inhibits implementation of such techniques as the direct modification of the alloys by injectlon of particles - crystallization nuclei into the melt, alloying the melts by injection of alloy components in the form of the powder, use c.' powdered waste of alloying materials (eg. silicon) in production -of alloys, in particular those of alu-minum-silicon system.
One of the most important features of the proposed technology and devices for its implementation is the possibility of injection the filler materials (in case c. into the melt of fine particles of production of composites) or structural cc.-,.ponents (in case of production of alloys), with the formaticn of the alloy structure following the scheme shown in Fig. 3.
The matrix free from the atoms c.' the component is injected with particles a.' a desired fi'ller material (Fig. 3a). When ecuilibrium of the system exists between the structural commonent (Ax By) and solution of the alloy component B in the matrix A, particles incorporated -4 nt o the matrix dissolve to the 4 ate temperature wi th the concentration of saturation at k_he approprdecrease in size, this process is highly controllable and enables pr--ducticn of alloys with structure with alloy a predetermined c--.-Donen. C.P 14m., - f - -zed solub-'--y.
Major stages c a process for the proauczicn cf cast composite - 6 materials involved are described in "Solidification, Structures and Properties of Cast Metal-Ceramic Particle Composites11 - Rchatgi P.K., Asthana R., Das S. - Inst. Metal Rev., - 1986 - Vol. 31, N3 pp. 15-139 and include:
production of the basic melt; uniform distribution of solid particles in a mass molten metal; - crystallization of the resultant composite material.
The following methods have been used in the prior art for injection of superfine particles into a melt as described in 11Cast AluMinum-Graphite Particle Composites - a Potential Engineering Material" - Rohatgi P.K., Das S., Dan T. K. - 7. Inst. Eng., -
March, 1989 - Vol. 67, N2 - pp. 77-83:
- mechanical stirring of the melt and added particles; - pressing pellets nixed powered matrix metals and reinforcing particles followed by plunging the particles to the nelt and mechanical stirring of the melt; by ult dispersion of particles in nell. -rasound irradiation.
Problems encountered in the production of cast metal composites relate to lack of or low wetabillty of the reinforcing filler particles with the matrix n.eltL-, as well as non-un-4.,fcr,.n-Jty of the cast material due to large differences An densities between the matrix and the filler material.
increase in the strength of the bond between the reinforcing filler particles and the base metal matrix is achieved by a number of techniques as described in "Wetability of Graphite to Liquid Aluminum and the Effect of alloying Elements on It", Choh Takao, Kemmel Roland, Oki Takeo - Z. Metallklundell - 1987 - Vol. 78, N4 - pp. 286-290, i.e.: application of metal-philic coatings on the surface of the reinforcing filler particles; introduction of surfactants into the base metal melt, f the nelt temperature.
- increase of There is also known a method for production of composites (Application No. 556-141960, Yapan, dated 08.04.80 (No. 55-45955), published 05.11.81) in which is suggested the use as a filler of natural hollow microspheres 150 micron in diameter sufficiently compatible with various metallic materials, as well as graphite powders, TiB aluninum nitride and oxide, flaky and chipped 2 graphite and calcium metal is added to the melt in quantity of 0.05-5.0 wt.% to ensure uniform.,ity of materials.
The major disadvantage of this method is the necessity for introduction into the melt of an elenent (calcium) which is soluble ,cally insoluble in the case -,t pract.- in the liquid base metal, solid matrix and which forms a brittle eutectic corponent with the matrix. This results in lowered mechanical properties of the matrix and of the composite itself. Besides, the use, as a filler, of hollow microspheres of the recited sizes (!50 nicron) does not 8 - -ies and can help to improve absolute values of mechanical propert result only in some improvement in their relative values per unit of mass.
Prior art relevant to the present invention is the method for production of composite materials (Met. Trans., 1978, v. 9 N 3, pp. 383-388) using the base molten metals - Mg. Al, Fe, Ni, Cr, Co doped with insoluble oxide particles (A'203, BeO,CaO, Ce02, T'021 MgO, Th02, V02, Zro,), carbides, borides, nitrides of Nb, Ta, Hf, Ti, Zr sized 0.01-10 micron. The particles are injected as powder or thin fibers. To ensure uniform distribution of the particles in the melt they are injected in a stream of preheated inert cas (Ar, "olume percentage of He) while vigorously stirring the base metal. particles may range from 0.5 to 20%. Also one of the elements which improve the surface activity at the interface the particlemelt is injected into the molten metal. injection of such surface ac,z:ive metals (Mg, Si, Ti, Zr, V, Nb) ensures fonnation of a metalphilic casing on the oxides which significantly improves wetability in the system ane- there is no segregation in the melt over a period of 30 min.
-ages:
The foregoing method has the following disadvant 1) the chemical composition of the matrix melt is li-mited by need to inject surface active metals which in a nu.-.,Lber of cases may lead to impairment of technological and nechanical properties of the resulting cc-.-,-.tposi4%--e material; 2) the absence 0 -P st-Jr-r-ing in solidification promotes, especially -J n case t 1-1 e course 0 p 0 4 a long - 9 solidification tine, the formation of segregated and laminated -Jng composite mater-al areas, and consequently quallty of the resultis lowered; 3) insolubility of the reinforcing particles excludes the possibility of using this method for production of materials hose with the matrix reinforced with superfine particles of 't.
elements or their compounds which are traditional strengtheners in production of materials by joint crystallization of the base metal with alloying additives and subsequent thermo-nechanical working.
-y An object of the present invention is improvement in auali4 of composite materials by increasing the uniformity of dispersion of reinforcing filler particles and the strength of t.heir adhesion with the base metal matrix and the ability to provide an expanded : ceramic group of composite materials by the use of a wide range o4 particles, metals and intermetallics including carbides, nit,-r-icies, borides, oxides, graphite and glasses.
The foregoing object and other objects are achieved by a method of making composite materials which includes the stems of entraining finely divided solid additive particles, e.a. of a ceramic, metal, intermetallic including oxides, borides, carbides, nitrides, graphite, glasses in an inert cas and ionizing the entraining inert gas to heat the solid particles to a high. temperature which is less than the temperature at which the particles become non-solid due zo melting, sublimation, er dissociation, but mere than about 1/2 of such, temperature, and injecting a stream of the ionized entraining gas and entrained heated solid particles into a molten ruetal mass while maintaining a stirring movement in the mass of molten metal sufficient to promote and to maintain dispersion of the added particles to solidify in a composite mass while maintaining a stirring movement in the solid particle- containing nolten metal until solidification thereof is complete.
BRIEF DESCRIPTION OF THE DRAWINGS
Figures 1, 4 and 5 show apparatus for the practice of various embodiments of the invention; and Figures 2 and 3 are representations of metallurgical conditions which occur in the course of alloy formation.
f the present invention, t In the practice o.1 %-he base metal nmelt ran be aluminum, iron, copper, magnesium, nickel, cobalt, chromium.
Suitable base metals are alloys of the above-mentioned metals in which they are the predominant constituent, -such as alurminum.
- J ron containing up to 40% by weight -zianganese, and steels, and casi. and ductile iron materials. Also suitable as base metals are magnesium, copper, nickel, titanium and alloys thereof.
The reinforcing filler addition particles are very fine and average from 1-100 micron in size. The particles can be metals which do not form chemical compounds with the matrix elements, such as Si in Al; intermetallics such as: TiAl ZrAl FeAl,, Fe Alc I 3, 3, 2 1 71 ides such as:SiC, T14C, WC, CrAl CrAl,, NiAl 2A19, ScAl c a rb I 31 Co 3; NbC, Fe3C; nitrides such as TiN, S',N4, ZrN; borides such as TiB,, AlB; oxides such as: Zro,,, -1 - TiO B 0; and also other ceramic 2 A 2"31 21 2 3 materials such as sapphire, glasses, graphite and carbo-nitrides. Other particle materials used in the dispersion strengthening of metals can be used, provided they satisfactorily retain thermodynamic stability th- roughout the steps of the present process.
The entraining inert gases used in the present invention are preferably argon or helium although other inert gases are usable.
-rained particles are preheated The inert gas is ionized and the ent in the ionized gas prior to being in3ected into the melt to a high temperature below that at which the particles melt or sublime or dissociate; i.e. about 0.9 of the melting point, sublimation temperature, or dissociation temperature as the case may be. At a higher temperature, the particles either agglomerate produce undesirably large particles in the melt, or result in particles of a composition other than that, intended, or there occurs substantial depletion of the desired amount of particles in the melt. At particle temperatures below about 0.5 of the nelting point (sublimation temperature or dissociation temperature) the resulting composite product does not exhibit the increase - strength, hardness and structural uniformity, unifor-mity of dispersed particles and homogeneity.
The temperature interval for particle preheating was determined exper-4-entally based on the recruiremen-: of p-roviding a necessary and suf ficient dearee o4- activation for inter-chase action I - 12 ensuring a strong bond between the particles and base metal by removal of adsorbed oxygen from the surface of the particles in the course of ion etching and breaking by the particles in the base stream of the molten metal surface.
Determination of the appropriate temperature range applicable to a particular particle material can be determined from published temperature data in hand books or the like and the use of pyrometry devices such as from Agema with precision of + IOC. However, it is frequently more convenient, particularly when particles such as intermetallics or others are involved and the published data is not conveniently available, to establish base-line conditions. For example, prior to the making of composites, a test run is performed with the gas ionization apparatus to be used for the preheating step, for a particular particle loading and the gas flow and the residence time of the particles in the ionized cas is increased to that just required to melt (volatilize or dissociate) the particle is observed and then slightly reduced to avoid melting, etc. '. hese process conditions then represent the 0.9 melting point temDerature. A residence time of about 1/2 the residence time at which particle melting occurs will correspond to 0.5 melting point. The empirical intervals can similarly be dete=ined by adjusting -he gas flow and particle loading of t gas following fundamental concepts well known to the art.
-ive particle materials for A selection of particularly effect t use in the present. invention is listed in Table A hereinhelow with temperature ranges and suitable, exemplary base metal ccnpositions - 1 '> also indicated.
TABLE A
Additive Particle Particle Temperature Base (Composition) size Range CO Melt micron sic 5-50 1100 - 2 00 Al, Al alloys, A1-4%Cu-1.5% M - 0.5%Mn, Fe Ti A13 1-10 670 1200 Al, Al alloys, A1-4%Cu-1.5% M Ti B2 5-10 1400-2500 Al,Al base alloys S i 3 N4 i-S 950-1710 Cu,Ni Graphite 5-50 1800-3240 AI-12% Si In the present invention, fr-cm about 0.5% by weight up to about 25% by weight of filler material can be incorporated in a base metal bath of nolten rietal and the particular material and amount added is determined on the basis of concepts known art to achieve a particular enhancement or mechanical properties, e.g. elasticity.
in the combination cf hardness, strength, ductilithy, Table B hereinbelow shows exemplary particle contents and base materials and an indication of the enhanced mechanical properties TABLE B
Particle Quantity (Composition) Wt. % ------------------------------ 1. sic 10 Base Metal Enhanced (Composition) Property ------------------------------------ A1 Rm=20OMPa,E=120 KN MM2, 2. ZrA13 +Cr A13 1 -- 1 Al -Rn2 0'99 Rm TiA13 15 Al S, = 300 S, Where: Rn temporary tensile strength P.3 2 proof st- ress E Modulus of Elasticity K ---rateof linear wear S - specific density of particles in the matrix 1,2,3 indices applicable to aluminum base composite material, aluninum and Al-10% Ti ce of the present invention, it is important that In the pract.
the molten base metal be -physically agitated e.g. by being subjected to a stirring force continuously from the commencement of the introduction of solid particles until casting and solidification of the cast metal is complete. Initially, the base melt is in physical agitation, i.e. in a crucible type vessel and a stirring force is suitably and preferably applied to the base metal bath by non-interfering contact magnetic means as know to the art. At this stage of the process mechanical stirring using : stirring impellers of known type can also be used. The degree of should vigorous enough e.g. a continuous obser-vable rolling of the bath, to ensure uniform dispersion of the additive particles and test samzles can he taken at intervals to so determine. When the particle containing base metal melt is ready for casting the ferred directly to a suitable mold and physical material is trans. agitation is maintained in the molten material in the mold, suitably by vibration, e.q. ultrasound energy coupled to the outside of the mold and causing vibrations in the molten metal until all of the metal in the mold has solidified. The application of ultrasound to provide physical agitation should be of sufficient strength to maintain the uniformity achieved in the crucible but should not result in any significant visible motion of the mass of the molten metal.
In the practice of the present invention the stream of ionized inert gas with entrained solid particles is inDected into the base metal bath so that the solid particles enter the bath to a depth of - 16 at least 5 cm, e.g. about 10% of the bath depth. continuous stirring in the course of change of the volume of the liquid phase from 100% to 0%, i.e. complete solidification, is a prerequisite of the present invention for ensuring uniform -F the matrix distribution of reinforcing material in the volume o. enabled by the previous steps of the process and enhancement of wetability at the "particle-melt" interface. Lack of stirring at any stage of liquid-solid state of the composite material can result in weakening the surface contact between the base metal matrix and particles, and the undesirable formation of laminations, segregations and non-uniformities of chemical and structural composition.
The thermodynamic stability of particles in the matrix melt inhibits their chemical action with the base metal and the formation of undesirable comDounds of uncontrolled sizes and shapes, thus ensuring, in contrast to the prior art technology, the formation of superfine part icle-re inf orced alloys by melting the base metal, followed by combined crystallization and heat treatment, and the production of composite materials 0. "-4etalintermetallide (metal)" type with preset values of quantity, sizes and shapes of reinforcing phases.
With reference to Figure 1, a crucible (10) suitably made of graphite contains a molten metal bath (1) of matrix metal e.g. aluminum which is stirred by way of a conventional nagnetic inductor 4 to physically agitate the metal bath (1), preferably in the vigorous rotating motion shown in Figure 1. The crucible (10) is provided with a protective cover (1-5) in which is installed an ionization chamber (2) of extended length. Inert gas, e.g. argon is controllably introduced from lines (8) into ionization chamber (2) and the gas is ionized to produce a plas=a arc in accordance with known techniques, and very high temperatures are developed in the ionization chamber (2) ranging from 8000 deg. C to 20000 deg.C. Finely divided filler material is held in hopper (3) with metering means (not shown) for measuring the weight of finely divided filler material which is introduced via conduit (16) into the ionization chamber (2). The filler particles entering ionization chamber (2) are rapidly heated to a high temperature below that at which melting of the particles occurs, e.g. between 0.5 and 0.9 of the melting point temperature of the particles. The thus heated and activated particles entrained in a stream of the ionized inert gas (25) are introduced into the nolten bath (1) by injection of the inert gas and penetration thereof below the surface of the metal bath. The continuous physical agitation of the metal bath (1) by magnetic inductor 4 establishes a uniform d--spersion of the solid heated activated filler particles. The temperature of the metal bath is measured, e.g. by thermocouples (not shown) to ensure that the temperature is below that at which undesirable melting or decomposition of the filler particles occurs. Uniformity of dispersion of the filler particles in the bath is established by analyzing samples taken from bath at convenient intervals. When the pre-determined desired amount of solid filler particles have r been introduced into the molten metal bath, plug (5) at the base of - 18 crucible (10) is opened and molten metal containing the solid additive particles (0) is introduced into mold (6) e.g. suitably made of steel. The molten metal is caused to solidify in the mold and surrounds the uniformly dispersed solid filler particles. To ensure that the solid filler particles remain uniformly dispersed in the molten metal phase as solidification progresses, an ultrasound transducer (7) is coupled to mold (5) so that molten metal in the mold is physically agitated by ultrasonic energy vibrations until all of the molten phase has passed into the solid state.
Figure 4(A) shows the crucible of Figure 1 provided with a conduit (20) for introducing reactant into ionization chamber (21) with an increased velocity of the ionized gas being indicated at (25) resulting in deeper penetration of the additive into the metal bath. Figure 4(B) shows the crucible of Figure 4(A) with ionized gas and additive being introduced at the bottom of the ladle. The inert gas forms bubbles (30) which are broken iip and dispersed by ultrasonic transducer (12) in contact with the upper portion of the metal bath at its surface.
Figure 5 shows the crucible of Figure 4(B) with the ultrasonic transducer (12) and the injection of ionized gas (25) being offset from the central alignment of Figure 4(B) to achieve the illustrated upwardly spiralling movement of the particle containing bubbles (30).
19 EXAMPLE
For testing the method of the invention use was made of unalloyed metalsaluminum and iron, as well as an aluminum base alloy 4%Cu, 1.5%Mg, 0.5% Mn also known as D16. These materials were separately used as the base melt for production of various composite materials. The starting reinforcing materials used were powdered silicon carbide, 5 - 50 micron in size, titanium aluminide TiAl 3 with particle size of 1-10 micron, and also titanium powder 10-100 micron in size.
Tests to produce composite materials were run in the pilot unit, shown schematically in Fig. 1. The crucible was made of graphite and contained a matrix melt (1) which was injected with a stream of ionized argon gas with entrained reinforcing particles preheated to predete=ined tenperature by means of a conventional plasmatron type ionization device (2) fitted with the metering device (3) to establish a predetermined rate of powder flow through the ionization device. The temperature of the particles, T P was varied and was monitored by detecting the change in neat content of the base melt before and after injection of particles of powder. TP was calculated by the formula:
CP m_ - 20 where: 0 - melt temperature after inject of additives, OC; Tm matrix temperature before injection of additives, IC;.
Cm - specific heat of matrix metal, MM - metal mass, K 9 CP - specific heat of particles, M P - particles' mas, Kg Kn - dimensionless factor taking into account heat effects upon air cooling of melt surface during preheating in treatment by stream of ionized gas without injection of particles, K, = 0.05-0-06 for 5 Kg of molten metal and an f low Of 0. 1 M3/M metal and an ionized argon gas in.
Stirring the mix in the course of injection of additives casting was accomplished by means of the magnetic inductor (4). After injection of predetermined quantities of solid additives the plug (5) was removed from the crucible and a lic-,iids-solid mixture flowed through the hole in the crucible bottom to fill a casting mold made of steel. The steel mold (6), 50 mm diameter, was used and the molten metal-solid particle mix was stirred by ultrasound generator (7) until the mold contents solidified. The resulting solid casting of 2.5 kg. was hot extruded. Quality assessment of resulting composite material was determining the following parameters: -chemical and structural uniformity, -size of reinforcing particles, -strength of composite naterial.
Chemical non-unif orm ity of composite material was evaluated by change incontent of conponents of reinforcing particles in various cross- sections of the casting across the casting direction by determining the chemical non-uniformity factor K:
Kc - cl," Ivi C v, Where: C, - content of components of reinforcing particles in cross- section of the casting, wt. %; n - number of cross sections analyzed; Cmax Cmin - maximum and m inimum content of components of reinforcing particles in cross-sect ions, wt.
Structural non-unifor-nity of the composite material was assessed by change of average sizes of reinforcing particles by the f actor Kave: the f actor Kave v (nve = -G m C")( - JM! ti _L M I 1 -7 0 L L= I Where di average size of ii-th particle, micron; dmax dmin - maximum and minimum sizes of analyzed particles n - number of analyzed particles.
-he ultimate tensile Strength was assessed by neasurIng It h --Ion was determined by tl,e strength R,, MPa (UTS). Chemical compositcra, antimeter A-RL 7ZOOO, with a p-recisicn of = 0.01%; structural characteristics were determined by the metallographic optic - 22 microscope MeF-3A at magnifications up to 300OX and the structural analyzer Omnimet 2 for quantitative determination of elements in the structure. Determination of strength was by the tensile machine UTS-100 with maximum applied force of 100 KN. All of the foregoing equipment is state-of-the-art. Table I shows the results of the tests.
The resulting data proves that the best characteristics are ensured by the samples of composite materials produced in the experiments No. 6, 9, 12, 36, 42, 51, 57, 66, 69, 72 in accordance with the method of the present invention for production of metal base composite materials.
In a further embodiment of the present invention, filler material for the making of a composite material is synthesized in the environment of an ionized entraining gas and the thus produced nascent materials, shielded by the cleaning ionized gas, are introduced into the base metal melt which is physically agitated, e.g. by magnetic and ultrasound techniques to uniformly distribute the synthesized material in the base metal matrix. The f illei: materials are synthesized by introducing substantially stoichiometric amounts of the reactants for producing the filler material. For example, in making titanium nitride filler material titanium powder suitable sized 20-50 micron is entrained in nitrogen gas in proportions corresponding to the equation:
2 Ti + N 2 ---- 2 N The titanium./nitrogen mixture is passed into a s--ream of ionized inert gas and exposed to the ionized gas at a temperature - 23 in the range of 2200-3000 degrees C for a time sufficient to complete reaction between the titanium and nitrogen to forr, titanium nitride in vapor form which is carried by the ionized inert gas onto the surface of the base metal melt, e.g. aluminum, which is physically agitated to uniformly disperse the titanium nitride in small discrete volumes which, on solidification in the base metal, provide ultrafine strengthening filler particles.
Other filler materials can be similarly synthesized as follows:
3Si (powder) +2N, - - - - S'3 N 4 Ti (powder) + 3A1 (powder) ---- TiAl 3 The temperature of the base metal melt is naintained at a temperature which will quench the additive materials so that the synthesized additive material is not undesirably dissolved in the melt.
in another embodiment of the invention, a carbon bearing gas, such as the hydrocarbons, propane, butane natural gas, nethane, Cr. carbon monoxide, carbon dioxide are ionized in mixture with a stream of ionized inert gas and dissociated. The carbon dissociation product is monatomic elemental carbon which is injected into the base melt as a filler addition. For the oxygen bearing gases, the liberated monatomic oxygen is an ionized gas stream which reacts with the melt, e.g. al=inu..i., to form ultrafine filler particles of aluminum oxide, A12,03 in the melt.
Following the practice of the present invention under the condition of Table 2 and using the materials of Table 2, the - 21t - indicated additives were introduced into the indicated molten base metal matrix to produce co-mposite materials having inproved mechanical properties.
TEST RESULTS L TABLE 1 rlow rate now Rate matrix Matrix Reinforcing Power Change in Composition Average Of particles of Inert Temperature Material material preheating quanitity of of composite size of Kg/min Gag C temperature liquid phase material rVirzCing K X P, M HVmin C W/stirring pwticles c ave % micron MPa 1 1 0.14 0.12 670 2 3 4 0.11 0.11 6 7 0.09 0.10 a 0.05 0.09 11 13 O.D2 0.09 14 is 20% sic Sao 200-80 Al-Sic 20 0.5 2.2 160 80-0 20 0.6 2.2 150 200-0 20 0.4 2.2 180 1100 100-80 8 0.4 0.8 215 80-0 8 0 5 0.8 205 100-0 0:1 0.6 250 2540 200-80 7 0. 4 0.7 220 80-0 7 0.5 0.7 210 100-0 7 0.013 0.7 255 2000 100-80 6 0.4 0.5 225 80-0 6 0,5 0.5 220 100-0 6 0.07 0.5 260 2200 2 00-80 25 0.3 3 195 80-0 15 0.4 4 190 0-0 15 0.18 2 200 16 0.15 0.12 AI 670 % Ti 720 100-95 AI-Ti-TiAl 50 0.4 6 170 17 R1 11 to 1 95-0 1 3 60 0.5 a 160 is If cc h:1 100-0 If 45 0.3 5 200 19 0.12 0.11 cc 01 900 100-95 to 40 0.4 6 195 W 01 cc 95-0 of ?1 91 45 0.5 7 185 It 100-0 to 30 0.3 5 250 12 0.9 0.10 1250 100-95 91 40 0.4 6 195 ?3 go #1 95-0 to 14 cc 11 45 0.5 6 190 cc 11 100-0 91 25 0.3 5 260 0.9 ff 1600 100-95 to 30 0.3 5 250 16 95-0 90 35 0.4 6 220 !7 on 100-0 Al-TA13 20 0.2 4 280 ?8 0.3 0.8 1800 100-95 30 0.2 4 250 !9 n 95-0 40 0.3 5 210 30.1 100-0 20 0.15 3 300 31 0.18 0.12 15% T'A13 540 100-85 7 0.3 2 290 32 of 11 90 85-0 01 7 0.6 2 280 13 to 91 cc 11 100-0 It 7 0.4 2 300 34.15 0.11 11 91 670 100-85 of 4 0.4 0-8 320 Re te 91 85-0 If 4 0.6 0.6 310 36 t, 1$ 91 100-0 4 0.6 0.5 400 3 4 5 6 7 8 9 10 37 0 ' 12 0.10 AI 670 151 TiAl 940 100-85 AI-TiAl 3 0.3 0.6 310 38 10 0 11 85-OT to 3 0.4 0.6 300 39 01 to to 11 1. to 100-0 3 0.05 0.6 420 0.09 0.09 1 1200 100-85 2 0 2 0.4 340 41 H of 0 to 10 85-0 2 0:3 0.4 320 42X 99 m 0 of to 1 100-0 0 2 0 05 0.4 440 43 0.06 0.08 U 11 11 1340 100-85 is 0:2 3 270 44 #1 91 c to to 85-0 0 20 0.3 4 250 45. - W H to of to M 100-0 10 0.1 2 300 46 0.14 0. 12 D 16 660 20% SiC 880 100-80 D16-SiC 20 0.4 2 400 47 g h 10 c 80-0 20 0 5 2 390 48 91 10 91 100-0 20 0:3 2 420 49 0.11 0.11 1100 100-80 8 0.3 0.7 480 so 91 91 80-0 8 0.4 0.7 470 51 100-0 8 0.09 0.7 620 52 0.08 0.10 91 1540 100-80 7 0.3 0.6 490 53 11 It 11 11 80-0 7 0.4 0.6 54 of of 480 100-0 7 0.07 0.6 640 0.05 0.09 2000 100-80 it 6 0.3 0.5 520 56 99 11 01 It 80-0 o' 6 0.4 0.5 500 57 q, 11 1. 11 100-0.1 6 0.05 0.5 660 1 z 3 4 5 6 7 8 9 10 0.02 0.08 R16 660 20% SiC 2200 100-80 D16-SiC 15 0.2 2.5 410 59 10 80-0 of 15 0.3 3 400 cc 100-0 19 15 0.09 1.5 420 61 0.14 0.12 Fe 1540 20% SiC 880 100-80 Fe-SiC 20 0.6 2.5 620 62 c 0 of I@ I to 80-2 0 20 0.7 2.5 600 63 10 cc 11 it go 100-0 09 20 0.5 2.5 650 64 0.11 0.11 0 go 1100 100-80 01 8 0.5 0.9 690 to 05 0 go g 80-0 $g 8 0.6 0.9 680 66 of of fl 01 of 100-0 a 0.12 0.9 790 67 0.08 0.10 01 10 of 1540 100-80 7 0.4 0.8 710 68 or 00 ll of to 80-0 7 0.6 0.8 700 69 to 51 to it cc 1,00-0 xt 7 0.10 0.08 800 7d 0.05 0.09 09 99 11 2000 100-80 6 0.3 0.7 720 71 90 ke If 10 to g$ 80-0 6 0.5 0.7 700 72 if 00 #P if 19 to 100-0 11 6 0.8 0.7 810 73 0.02 0.08 It go to 2200 100-80 to 15. 0.4 3.5 610 74 lf U 80 S# P, 11 80-0 99 is 0.5 4 600 100-0 91 15 0.1 2.5 640 TABLE 2
Matrix Matrix Reactant Reactant Ionized Apparatus #2 Gas Flow Addition Amount Fict. ---- 5 Metal Temp C (SCFM) of Kg c & Addition Temp. C wt. % AI AI Ti 14000 TiAI3 is + + 4.22kCJ 670 5-50 5-50 micron micron 0.02kg/min 0.04kg/min Cu 980 Si N2 14000 Si3 N4 2 + + 4. gkg 5-50 micron 0.02kg/Inin 0.008M3/Min Fe 1540 Ti CO? 14000 TiC 5 + + 4.75 5-50 micron 0.04kg/min 0.013M3/min AI 660 Ti N2 14000 TiN 2 + + 12tSi 4.9 5-50min 0.005 0.04kg/min M3/min - 30

Claims (1)

1. A method of making a composite material which includes introducing a stream of ionized inert gas having an additive entrained therein into a molten base metal with agitation.
2. A method in accordance with Claim 1 comprising entraining finely divided solid additive particles, in a stream of ionized inert gas and ionizing the inert gas and utilizing heat generated by the ionized gas to heat the solid particles to a high temperature which is less than the temperature in at which the solid particles become non-solid due to melting, sublimation or dissociation, but more than about 1/2 of such temperature of melting, sublimation or dissociation, and injecting said stream of gas and entrained heated solid particles into a molten metal mass to provide a mixture of finely divided solid particles and molten metal and thereafter causing physical agitation of the mixture of molten metal and solid particles to establish a substantially uniform distribution of solid particles in the molten metal and continuing physical agitation of molten metal until the mixture of finely divided particles and metal is completely solidified.
3. A method in accordance with claim 2 wherein the mixture of molten metal and solid particles is initially contained in a crucible and agitation is provided by magnetic means external to the crucible and subsequently a portion of said mixture is transferred to a mold and agitation of the mixture is provided by ultrasound means external to the mold.
4. A method in accordance with claim 1 comprising entraining in a stream of ionized inert gas finely divided solid and/or gaseous reactant in proportions to provide upon reaction a predetermined composition, causing reaction between said reactants while entrained in said ionized inert gas to provide 1 a reaction product t-- -penetrate into a molten =etal bath, and causing physical agitation of said netal bath to uniformly disperse said 1 reaction product "..,.erein.
S. A method according to any ene of claims 1, 2 or 3, wherein the base metal is selected from aluminium, iron, magnesium, copper.
nickel, chromium, titanium and said additive is selected from twoor =ulticc.nponent chemical compounds of one of the base metals with other metals as well as from carbides, nitrides, cartonitrides, oxides and borides of metals.
A composite material or alloy wit.h. uniformly distributed comyjcnents fcrmed by injecting additive par-4cles which have been heated by an ionized gas into a physically agitated molten base metal, the resultina material being continuously removed from the zone of injection, with subsequent cooling while physical agitation is c=tinuously maintained.
Compcsite material or alloy in accordance with Clai= 6 wherein said base metal is selected from aluminun, iron, magnesium, ccpper, nickel, chromium, titanium and said additive material is selected from two- or multil-component compounds of the base metals with ccher metals as well as fr-cm carbides, nitrides, cartcnitrides, oxides and bborides of metals.
:Z.
Apparatus for =aking a composite material comprising:
i) cr.,.cible means for containing a molten base =er-al; (ii) plasma generar-4ng means posit4cneci adjacent the Z - - -- crucible means for receiving a stream of inert - 32 gas and entrained filler particles and ionizing said gas and thereby heating said particles; (iii) Means for injecting said ionized gas and heated marticles into said crucible means to penetrate into molten metal when present in said crucible; (iv) means for continuously agitating molten metal when present in said crucible; (v) mold means for receiving molten metal containing filler particles from said crucible; and (vi) means for continuously agitating molten metal when present in said mold means.
9. Apparatus in accordance with Claim 8 wherein said crucible is covered and the means for injecting ionized gas and heated part4cles passes through said cover.
10. Apparatus in accordance with Claim 8 or 9 wherein the means for agitating molten metal in the crucible are magnetic stirring means.
Apparatus in accordance with Claim 8 or 9 wherein the means for aaitatina molten metal in the mold means is ultrasonic transducer means.
12. Apparatus!.n accordance with Claim 8 wherein the means for injecting ionized gas and heated particles passes through 4- k-he hottom. of said crucible.
1 33 - Amparatus in accordance with claim 11 wherein ultrasonic transducer:leans are provided adjacent 1k---he upper portion J of 41A.e crjc-.dle means 14. Apparatus in accordance with Claim 13. wherein the ultrasonic transducer and means for injecting ionized gas and heated particles are horizontally displaced so that -,.,olten metal in the crucible is subjected to rotaticnal movement.
S. Ylerhod or composite or apparatus substantially as here.inbe-J--e described with reference to the accompanying ExamiDles.
Published 1992 at The Patent OffIce. Concept House, Cardiff Road. Newport. Gwent NP9 1RH. Further copies may be obtained from Sales Brunch. Unit 6. Nine Mile Point, Cwmfelinfach, Cross Keys. Newport. NP I 7HZ. Printed by Multiplex techniques lid. St Mary Cray, Kent.
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ITMI912431A1 (en) 1993-03-13
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DE4131239A1 (en) 1992-03-26
CN1062769A (en) 1992-07-15
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IT1258217B (en) 1996-02-21
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JPH0673469A (en) 1994-03-15
FR2666819A1 (en) 1992-03-20

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