WO1992003585A1 - Materiau composite contenant du spinelle dans une matrice metallique, et procede de preparation - Google Patents

Materiau composite contenant du spinelle dans une matrice metallique, et procede de preparation Download PDF

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Publication number
WO1992003585A1
WO1992003585A1 PCT/CA1991/000292 CA9100292W WO9203585A1 WO 1992003585 A1 WO1992003585 A1 WO 1992003585A1 CA 9100292 W CA9100292 W CA 9100292W WO 9203585 A1 WO9203585 A1 WO 9203585A1
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WO
WIPO (PCT)
Prior art keywords
spinel
particles
mgo
composite according
metal matrix
Prior art date
Application number
PCT/CA1991/000292
Other languages
English (en)
Inventor
Mukesh Jain
Sadashiv Kashinath Nadkarni
Alan David Mcleod
Original Assignee
Alcan International Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alcan International Limited filed Critical Alcan International Limited
Publication of WO1992003585A1 publication Critical patent/WO1992003585A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/162—Magnesium aluminates
    • 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
    • C22C32/001—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 with only oxides
    • C22C32/0015—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 with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0036—Matrix based on Al, Mg, Be or alloys thereof
    • 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
    • C22C32/0089—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 with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • This invention relates to metal matrix composite materials and, more particularly, to the preparation of aluminum matrix composite materials containing spinel.
  • Metal matrix composites typically are composed of reinforcing particles such as fibres, particulates, powder or the like that are embedded within a metallic matrix.
  • the reinforcement imparts strength, stiffness and other desirable properties to the composite, while the matrix protects the reinforcement and transfers load within the composite.
  • the components, matrix and reinforcement thus cooperate to achieve results improved over what either could provide on its own.
  • the mixing occurs while minimizing the introduction of gas into, and while minimizing the retention of gas within, the mixture of particles and molten metal, and at a temperature at which the particles do not substantially chemically degrade in the molten metal in the time required to complete the step of mixing.
  • the resulting mixture is cast at a casting temperature sufficiently high that substantially no solid metal is present.
  • the metallic material is typically an aluminum alloy and the non-metallic particles are typically metal oxide, metal nitride, metal carbide or metal suicide.
  • the most preferred composite materials are silicon carbide and aluminum oxide particulate reinforcement.
  • Aluminum alloys reinforced with oxides such as aluminum oxide produce a stiffer and stronger alloy.
  • the loss of Mg impairs the age hardening response of the matrix and results in loss of compositional control.
  • the presence of the spinel reaction product also acts to increase the viscosity of a composite melt, and make recycling more difficult.
  • M.E. Fine et al. "Investigation and Synthesis of High Temperature and Increased Stiffness RSP Aluminum Alloys", AFOSR-TR-89-0081, 1989, describes composites having an aluminum-magnesium alloy matrix reinforced by particulate spinel of very small particle size in the order of 30-150 nm.
  • This is concerned with mechanical alloying to produce the ultrafine reinforcement and is not adapted to the production of composites of the characteristics of the present invention.
  • the mechanism of such ultrafine reinforcement is essentially one of dispersion strengthening whereby the main reported effect. is an increase in creep resistance.
  • An object of the present invention is to overcome the problem of the magnesium loss by reaction with reinforcement materials when aluminum oxide particles are used as reinforcement in aluminum alloys.
  • spinel powder of appropriate characteristics is a highly effective reinforcement for magnesium or aluminum alloys and overcomes the problem inherent in the use of aluminum oxide powders.
  • the reinforcement is in the form of particles consisting of fused or sintered material or single crystals of spinel within a size range of 5-20 ⁇ m.
  • the spinel used according to this invention may be either stoichiometric spinel (MgO.Al 2 0 3 ) or non-stoichiometric spinel containing 50 to 95 mole % A1 2 0 3 .
  • the spinels of this invention may be broadly defined as MgO:Al 2 0 3 containing 50 to 95 mole % A1 2 0 3 and 50 to 5 mole % MgO.
  • the spinel powder can be purchased from commercial sources, or a highly pure form of spinel may be produced from aluminum industry wastes containing alumina or an alumina precursor, such as aluminum dross residue.
  • Particles of the waste material are mixed with particles of magnesium oxide and the mixture is then calcined to form spinel.
  • the spinel particles are collected in the desired size range.
  • the spinel reinforcement particles of this invention by electrofusion of an aluminum dross residue, e.g. the product available from Alcan Chemicals North America under the trade mark NOVAL.
  • the NOVAL may be subjected to electrofusion as is or it may be calcined prior to electrofusion. Pre- calcination is preferred to minimize gas evolution during fusion. During calcination A1N present oxidizes to form alumina.
  • a typical NOVAL product when subjected to electrofusion results in non-stoichiometric spinel, e.g. Mg0.2Al 2 0 3 . If stoichio etric spinel (MgO.Al 2 0 3 ) is desired, then MgO may be added to the NOVAL prior to the electrofusion.
  • aluminum matrix a wide range of standard wrought, cast, or other aluminum alloys may be used, such as those having the Aluminum Association designations 6061, 2024, 7075, 7079, etc. Such alloys typically contain a substantial amount, e.g 1-4%, magnesium, as well as other alloying elements.
  • the preferred procedure for producing the composite material of the invention reinforced with particles of spinel comprises melting the metallic material; adding particles of spinel to the molten material; mixing together the molten metal and the particles of spinel to wet the molten metal to the particles, under conditions that the particles are distributed throughout the volume of the melt and the particles and metallic melt are sheared past each other to promote wetting of the particles by the melt, this mixing to occur while minimizing the introduction of gas into, and while minimizing the retention of gas within, the mixture of particles and molten metal, and casting the resulting mixture at a casting temperature sufficiently high that substantially no solid metal is present.
  • the composite material made by the method of the invention comprises a cast microstructure of the metallic matrix, with particulate distributed generally evenly throughout the cast volume.
  • the particulate is well bonded to the matrix, since the matrix is made to wet the particulate during fabrication.
  • the cast composite is particularly suitable for processing by known primary forming operations such as rolling and extruding to useful shapes.
  • the properties of the cast or cast and formed composites are excellent, with high stiffness and strength, and acceptable ductility and toughness.
  • Composite materials have been prepared with volume 5 factions of particulate ranging from about 5 to about 40 percent, so that a range of strength, stiffness and physical properties of the composite are available upon request. The absence of any reaction of the reinforcement with magnesium enables the composition range of preferred 10 and useful products to be widened.
  • Fig. 1 is a photomicrograph of stoichiometric spinel powder according to the invention
  • 15 Fig. 2 is a plot of UTS as a function of aging time for composites containing 15 vol% of respectively alumina and spinel reinforcement
  • Fig. 3 is a plot of YS as a function of aging time for composites containing 15 vol% of respectively alumina 20 and spinel reinforcement
  • Fig. 4 is a plot of modulus as a function of aging time for composites containing 15 vol% of respectively alumina and spinel reinforcement
  • Fig. 5 is a plot of elongation as a function of aging 25 time for composites containing 15 vol% of respectively alumina and spinel reinforcement
  • Fig. 6 is a photomicrograph of an extruded rod of AA- 6061/15% spinel composite of the present invention
  • Fig. 7 is a plot of yield stress, UTS and elongation 30 as a function of age time for an AA-6061 aluminum - 15% spinel composite
  • Fig. 8 is a photomicrograph of non-stoichiometric spinel.
  • Fig. 9 is a photomicrograph of an extruded rod of AA- 35 6061/15% non-stoichiometric spinel composite of the present invention. Best Modes for Carrying Out the Invention The following examples serve to illustrate aspects of the invention, which should not be taken as limiting the scope of the invention in any respect.
  • Example 1
  • Fine spinel powder (-325 mesh) was obtained from Muscle Shoal Minerals, Tuscumbia, Alabama and was classified using a Nisshin 15 M air classifier.
  • Figure 1 is a photomicrograph of the classified powder and other details are given below.
  • That furnace includes a crucible which is resistively heated to melt the aluminum alloy, with the crucible positioned within a chamber which may function as a vacuum chamber.
  • a connector provides for the ingress and egress of argon.
  • the mixer comprises a dispersion impeller positioned vertically along the centerline of the crucible and adapted to operate so as to induce high shears within the melt but a small vortex at the surface of the melt.
  • a typical impeller for the purpose is a vertical rotor shaft with a plurality of flat blades. The blades are not pitched with respect to the direction of rotation, but are angled from about 15° to about 45° from a line perpendicular to the rotor shaft.
  • the furnace was set at a temperature of about 850- 870°C and 6061 aluminum alloy stock was charged to the furnace with an argon cover gas. As the aluminum began to melt, the temperature was reduced to about 680°C and argon was blown into the melt to displace any absorbed hydrogen, and bringing oxide particles to the surface, which were 5 then skimmed off.
  • the above described spinel powder was then added to the melt in an amount of 15% by volume and a mixing assembly was put in place and a vacuum was pulled on the furnace.
  • the mixer impeller was rotated at 750 rpm for a 10 total of about 45 minutes under vacuum, after which the mixing chamber was slowly brought back to atmospheric pressure and after a total mixing time of about 55 minutes, the mixer was stopped.
  • the composite material thus obtained was cast into billets, which were then 15 extruded to an extrusion ratio of 16:1.
  • the bars obtained were solution treated, followed by aging at 175°C. Mechanical properties of samples aged for 0, 2, 4, 6 and 16 hours were measured using standard techniques.
  • Figures 2 to 5 show the ultimate tensile strength, 20 yield strength, modulus and elongations obtained. Data for A1 2 0 3 are included for comparison.
  • Elongation for spinel is somewhat lower than A1 2 0 3 but the difference disappears at high aging times.
  • Example 2 Following the same procedure as in Example 1, an AA 35 6061 aluminum/15% by volume spinel composite was produced. This composite was cast into 57 mm diameter extrusion billets and then extruded to 9.5 mm diameter rod using a 550'C billet temperature.
  • the microstructure of the extruded rod is shown in Figures 6a and 6b.
  • the rod was sound with good distribution of spinel particles.
  • the high magnification micrographs reveal that many of the particles have an interaction layer at the interface, resulting from the presence of a small amount of excess A1 2 0 3 which has reacted to spinel.
  • the extruded material was solution treated for 1 hour at 550"C, then water quenched, naturally aged for two days and then artificially aged at 175°C. Data for the aged samples are shown in Figure 7.
  • the four hour aging (T4) and six hour aging (T6) properties compare very favourably to equivalently processed AA6061-Al 2 O 3 composites.
  • the Young's modulus for the T4 and T6 conditions are given in Table 1 below, where A and B indicate duplicate tests:
  • Test samples of spinels were produced from NOVAL in a small electric arc furnace with a 19 litre size cast iron crucible.
  • the furnace included graphite electrodes 3.2 cm in diameter and about 1.2 m in length. These were mounted in the center of the crucible about 5 cm apart and were equipped with a mechanism to lower or lift while the fusion was in progress.
  • the power source was two 500 Ampere transformers similar to those employed in welding.
  • a typical chemical analysis for NOVAL is shown in Table II below:
  • NOVAL product After being calcined at 900°C for about 4 hours, the NOVAL product had the chemical analysis shown in Table III below:
  • FIG. 8 is a photomicrograph of the classified non-stoichoimetric spinel of Ingot #1.
  • Samples of classified powder for Ingot #1 and Ingot #2 were respectively combined in an amount of 15% by volume with AA-6061 in the same manner as described in Example 1.
  • the samples of composite material which were obtained were cast into billets, which billets were then extruded to form 9.5 mm diameter rods.
  • the rods obtained were solution treated followed by aging at 175"C.
  • Mechanical properties for samples aged four hours under natural conditions or six hours under artificial conditions are given in Table V below:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

On produit un matériau composite à matrice d'aluminium contenant du spinelle à titre de matériau de renforcement. Le spinelle utilisé présente une granulométrie comprise entre 5 et 20 νm et peut avoir une composition variable de MgO:Al2O3 contenant de 50 à 95 % en mol de Al2O3 et de 50 à 5 % en mol de MgO. Ces composites présentent des propriétés supérieures à celles du même alliage renforcé par des particules d'alumine.
PCT/CA1991/000292 1990-08-17 1991-08-19 Materiau composite contenant du spinelle dans une matrice metallique, et procede de preparation WO1992003585A1 (fr)

Applications Claiming Priority (2)

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US56898790A 1990-08-17 1990-08-17
US568,987 1990-08-17

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WO1992003585A1 true WO1992003585A1 (fr) 1992-03-05

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AU (1) AU8331891A (fr)
WO (1) WO1992003585A1 (fr)
ZA (1) ZA916428B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2519655A1 (fr) * 2009-12-29 2012-11-07 Nokia Corp. Composite métallique coloré et procédé permettant sa fabrication

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2286119A1 (fr) * 1974-09-26 1976-04-23 Quigley Co Procede de production de spinelle d'aluminate de magnesium
US4743299A (en) * 1986-03-12 1988-05-10 Olin Corporation Cermet substrate with spinel adhesion component
DE3807541C1 (fr) * 1988-03-08 1989-07-27 Daimler-Benz Aktiengesellschaft, 7000 Stuttgart, De

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2286119A1 (fr) * 1974-09-26 1976-04-23 Quigley Co Procede de production de spinelle d'aluminate de magnesium
US4743299A (en) * 1986-03-12 1988-05-10 Olin Corporation Cermet substrate with spinel adhesion component
DE3807541C1 (fr) * 1988-03-08 1989-07-27 Daimler-Benz Aktiengesellschaft, 7000 Stuttgart, De

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
& J. Mater. Sci., vol 26 no 10, 15-5-1991 p.2750-2758 *
CHEMICAL ABSTRACTS, vol. 100, no. 10, 5 March 1984, Columbus, Ohio, US; abstract no. 72586B, IZZAT, N ET AL: 'SEM study of fracture in an aluminum-alumina-magnesia cast particle composite.' see abstra& J. Mater. Sci. Lett., vol. 2 no.12, 1983. p.750-752 SA 50175 030 *
CHEMICAL ABSTRACTS, vol. 103, no. 2, 15 July 1985, Columbus, Ohio, US; abstract no. 9912B, ABDUL-LATTEF, NAWAL IZZET ET AL: 'Preparation of aluminum-alumina-magnesia cast particulate composites using magnesia coating technique.' see abstract & J. Mater. Sci. Lett., vol.4 no.4, 1985. p. 385-388 *
CHEMICAL ABSTRACTS, vol. 115, no. 10, 9 September 1991, Columbus, Ohio, US; abstract no. 97016P, SINGH, J. ET AL: 'Elevated temperature tensile properties of squeeze-cast aluminum-alumina-magnesia particulate MMCs up to 573 K.' see abstract *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2519655A1 (fr) * 2009-12-29 2012-11-07 Nokia Corp. Composite métallique coloré et procédé permettant sa fabrication
EP2519655A4 (fr) * 2009-12-29 2014-06-11 Composite métallique coloré et procédé permettant sa fabrication
US8790438B2 (en) 2009-12-29 2014-07-29 Nokia Corporation Colored metal

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AU8331891A (en) 1992-03-17
ZA916428B (en) 1992-05-27

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