WO2018200270A1 - Metal matrix composites and methods of making the same - Google Patents

Metal matrix composites and methods of making the same Download PDF

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Publication number
WO2018200270A1
WO2018200270A1 PCT/US2018/028047 US2018028047W WO2018200270A1 WO 2018200270 A1 WO2018200270 A1 WO 2018200270A1 US 2018028047 W US2018028047 W US 2018028047W WO 2018200270 A1 WO2018200270 A1 WO 2018200270A1
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Prior art keywords
metal
solid particles
metal article
article
continuous phase
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PCT/US2018/028047
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French (fr)
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WO2018200270A8 (en
Inventor
John W. Koenitzer
Andrew Matheson
Diran APELLIAN
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Nanoscale Powders, LLC
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Priority to US201762489515P priority Critical
Priority to US62/489,515 priority
Application filed by Nanoscale Powders, LLC filed Critical Nanoscale Powders, LLC
Publication of WO2018200270A1 publication Critical patent/WO2018200270A1/en
Publication of WO2018200270A8 publication Critical patent/WO2018200270A8/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C49/00Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/02Making alloys by melting
    • C22C1/026Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/02Alloys based on aluminium with silicon as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C47/00Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/08Making alloys containing metallic or non-metallic fibres or filaments by contacting the fibres or filaments with molten metal, e.g. by infiltrating the fibres or filaments placed in a mould
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C49/00Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/04Light metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C49/00Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/04Light metals
    • C22C49/06Aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C49/00Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/10Refractory metals
    • C22C49/11Titanium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F1/00Special treatment of metallic powder, e.g. to facilitate working, to improve properties; Metallic powders per se, e.g. mixtures of particles of different composition
    • B22F1/0003Metallic powders per se; Mixtures of metallic powders; Metallic powders mixed with a lubricating or binding agent
    • B22F1/0007Metallic powder characterised by its shape or structure, e.g. fibre structure
    • B22F1/0011Metallic powder characterised by size or surface area only
    • B22F1/0018Nanometer sized particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F1/00Special treatment of metallic powder, e.g. to facilitate working, to improve properties; Metallic powders per se, e.g. mixtures of particles of different composition
    • B22F1/0003Metallic powders per se; Mixtures of metallic powders; Metallic powders mixed with a lubricating or binding agent
    • B22F1/0007Metallic powder characterised by its shape or structure, e.g. fibre structure
    • B22F1/0048Spherical powder
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F1/00Special treatment of metallic powder, e.g. to facilitate working, to improve properties; Metallic powders per se, e.g. mixtures of particles of different composition
    • B22F1/02Special treatment of metallic powder, e.g. to facilitate working, to improve properties; Metallic powders per se, e.g. mixtures of particles of different composition comprising coating of the powder

Abstract

A metal matrix composite or metal article is described which has a continuous phase of metal or metal alloy and solid particles dispersed in the continuous phase as a non-continuous phase. Methods of making the metal article are further described.

Description

METAL MATRIX COMPOSITES AND METHODS OF MAKING THE SAME
BACKGROUND OF THE INVENTION
[0001] This application claims the benefit under 35 U.S.C. §119(e) of prior U.S. Provisional Patent Application No. 62/489,515, filed April 25, 2017, which is incorporated in its entirety by reference herein.
[0002] The present invention relates to metal matrix composites and methods of making the same. The present invention further relates to metal articles that include the metal matrix composites.
[0003] In the metal and metal alloy industry, there is always a desire to form metal articles that have improved strength or to improve other relevant metal or metal alloy properties. This desire exists especially in the light metal area where such metals have found common uses in the aerospace industry, the airplane industry, the defense industry, and the like. While improvements are sought in one or more properties of a metal or metal alloy, there is an equal desire not to reduce any other property in order to achieve a property improvement.
SUMMARY OF THE PRESENT INVENTION
[0004] A feature of the present invention is to provide metal articles that contain a metal or metal alloy and preferably have one more property improvements compared to conventional metal or metal alloys.
[0005] A further feature of the present invention is to provide light metals or light metal alloys with one or more property improvements. [0006] An additional feature of the present invention is to provide a method of forming a metal article which can avoid the need for flux and/or avoid oxide layered solid particles and/or surface contamination on the solid particles in the process to form the metal articles.
[0007] Additional features and advantages of the present invention will be set forth in part in the description that follows, and in part will be apparent from the description, or may be learned by practice of the present invention. The objectives and other advantages of the present invention will be realized and attained by means of the elements and combinations particularly pointed out in the description and appended claims.
[0008] To achieve these and other advantages, and in accordance with the purposes of the present invention, as embodied and broadly described herein, the present invention relates to a metal article. The metal article has a continuous phase of metal or metal alloy and has solid particles dispersed in the continuous phase. The solid particles are dispersed and present as a non-continuous phase. The solid particles have a melting point that is higher than the melting point of the continuous phase, and are comprised of metal, metal alloy, metal carbide, metal nitride, metal boride, or metal silicide or any combinations thereof. At least a portion of the solid particles have a shape comprising a tight grapelike cluster or dendritic or fibrous configuration or any combination thereof. The solid particles have a property of being substantially insoluble or slightly soluble, for a period of time, in the continuous phase of the metal when the continuous phase is molten.
[0009] The present invention in addition relates to a method of forming the metal article of the present invention. This method includes combining the solid particles which are present as salt- coated solid particles with a molten liquid of the metal or metal alloy that forms the continuous phase. This combination of the solid particles and the molten liquid of the metal or metal alloy forms a liquid matrix. The salt from the salt-coated solid particles then at least in part or entirely separates from the solid particles. The salt can then optionally be substantially removed or entirely removed from the liquid matrix. The method then includes solidifying the liquid matrix (without the salt or substantially without the salt) to obtain the metal article.
[0010] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and intended to provide a further explanation of the present invention, as claimed.
[0011] The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate some of the features of the present invention and together with the description, serve to explain the principles of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a set of figures describing a method according to an example of the present application.
[0013] FIG. 2 is an SEM photograph showing an example of salt-coated particles which are Ti particles coated by NaCl.
[0014] FIG. 3 is an SEM photograph showing an example of salt-coated particles in pellet form which are Ti particles coated by NaCl.
[0015] FIG. 4 is a graph depicting Stress vs Strain curves for an A356 alloy (control) and an A356 alloy with Ti solid particles (present invention).
[0016] FIG. 5 is an SEM photograph showing an image of a solid particle surrounded by a continuous phase of aluminum metal. DETAILED DESCRIPTION OF THE PRESENT INVENTION
[0017] The present invention relates to metal articles that have a continuous phase of metal or metal alloy and have solid particles dispersed in the continuous phase as a non-continuous phase. The present invention further relates to methods of forming the metal article.
[0018] In more detail, the metal article, in its final state, is a solid metal article. The metal article has a continuous phase of metal or metal alloy. This metal or metal alloy that forms the continuous phase of the metal article can comprise, consist essentially of, consist of, or include any metal or metal alloy. Examples of the metal and metal alloy include, but are not limited to, aluminum, magnesium, titanium, or any combinations thereof. The metal can be iron, copper, zinc, silver, gold, nickel, manganese, or chromium and alloys thereof or any combinations thereof. The metal of the continuous phase can be iron or steel, and the like. Any alloy of one or more of these metals can be the continuous phase of the metal or metal alloy of the metal article of the present invention. For instance, the continuous phase can be an aluminum alloy such as a Class 300 aluminum alloy. Examples of a Class 300 aluminum alloy include, but are not limited to, A356.0 alloy. Other examples of the metal or metal alloy that can comprise, consist, or consist essentially of the continuous phase include, but are not limited to, lxxx (e.g. 1350), 3xxx (e.g. 5005), 2xxx, 6xxx, 7xxx, and 8xxx type metals based on the Aluminum Association designations, or can be cast aluminum alloys, wrought aluminum alloys, and the like. As another example, the continuous phase can comprise at least 90% by weight aluminum, magnesium, and/or titanium such as from about 90% by weight to about 100% by weight, from about 95% by weight to about 100% by weight, or from about 98% by weight to about 100%) by weight, based on the weight of the continuous phase. [0019] The continuous phase with respect to the overall metal article can comprise f om about 75 wt% to 99.95 wt%, or from 85 wt% to 99.9 wt%, or from 90 wt% to 99.5 wt%, or from 95 wt% to 99.5 wt%, based on the total weight of the metal article.
[0020] With regard to the solid particles dispersed in the continuous phase. The solid particles are present as a non-continuous phase. As an option, the solid particles are dispersed in such a manner that no percolation occurs.
[0021] At least a portion of the solid particles have at least the following four properties:
i) a melting point that is higher than the melting point of the continuous phase. (This melting point can be at least 5°C higher in melting point than the continuous phase's melting point, at least 10°C higher, at least 15°C higher, at least 20°C higher, at least 50°C higher, at least 75°C higher, such as a melting point that is from about 5°C to 200°C higher or more).
ii) comprises, consists essentially of, consists of, or includes metal, metal alloy, metal carbide, metal nitride, metal boride, or metal silicide, or any combinations thereof. (This portion or all solid particles present can comprise at least 25% by weight, at least 50% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, at least 98% by weight, at least 99% by weight, at least 99.5% by weight, or 100% by weight, of the metal, metal alloy, metal carbide, metal nitride, metal boride, or metal silicide, or any combination thereof, based on the weight of the solid particles. The remaining percent of these solid particles can comprise other material, like metals or alloys that are the same as the continuous phase and/or other metal enhancement ingredients).
iii) a shape that comprises, consists essentially of, consists of, or includes tight grapelike clusters, a dendritic shape, or fibrous configurations or any combinations thereof. This shape of the metal particles generally can be for a portion or all of the solid particles. Alternatively, this shape can be from a particle population point of view at least 5% by number, at least 20% by number, at least 50% by number, at least 75% by number, at least 90% by number, at least 95% by number, at least 99% by number, or 100% by number of all solid particles present in the metal article. This can be determined by examining 50 random solid particles in a metal article and using SEM micrographs to confirm their shape. FIGS. 2, 3, and 5 show this shape as an example.
iv) either a) being substantially insoluble in the continuous phase of the metal or metal alloy when said metal or metal alloy is molten. The "substantially insoluble" property is where at least 99.1% by weight of the solid particles are insoluble in the continuous phase of the metal or metal alloy when the metal or metal alloy of the continuous phase is in a molten state. In other words, a substantial amount or all of the solid particles do not dissolve or become soluble in the continuous phase of the metal or metal alloy when the metal or metal alloy of the continuous phase is molten. The solid particles remain as a solid while the continuous phase is molten. Generally, substantially insoluble means that less than 1 wt% of the composition of the solid particles is soluble in the molten continuous phase based on the weight of the continuous phase (such as less than 0.75 wt%, less than 0.5 wt%, less than 0.3 wt%, less tan 0.2 wt%, less than 0.1 wt%). This amount remaining as a solid can be at least 99.2% by weight or at least 99.5% by weight or at least 99.75% by weight or at least 99.9% by weight or 100% by weight of all solid particles originally present that are substantially insoluble. Thus, once the metal article is solidified, these solid particles are dispersed in the continuous phase and can be seen (and differentiated from the continuous phase) or identified in magnified images such as SEM photographs, as for instance shown in FIG. 5.
or b) being slightly soluble in the continuous phase of the metal or metal alloy when said metal or metal alloy is molten. The "slightly soluble" property is where from 1 wt% to 5 wt% of the composition of these solid particles is soluble in the molten continuous phase (such as from about 1.25 wt% to 5 wt% soluble, from about 2 wt% to 4.9 wt%, from about 3 wt% to 4.9 wt% soluble in the molten continuous phase). When the solid particles are or include solid particles that are slightly soluble in the molten continuous phase, generally the amount of slightly soluble solid particles added to the continuous phase is at least greater than the wt% of the composition of the solid particles that is soluble in the molten continuous phase. For instance, if slightly soluble solid particles are used and the solubility of the composition of the solid particles is 4 wt% in the molten continuous phase, then greater than 4 wt% of the slightly soluble solid particles (based on the weight of these solid particles and continuous phase) are at least used and introduced into the continuous phase so as to ensure that at least a portion of the slightly soluble solid particles would not become soluble in the continuous phase due to the solubility saturation point being reached with regard to the solubility of the composition of the slightly soluble solid particles in the molten continuous phase. Generally, the added amount of slightly soluble solid particles would be at least 25 wt% or greater or at least 50 wt% greater than the solubility limit of the composition of the solid particles in the molten continuous phase such as from about 50 wt% to 100 wt% or more. Put another way, by weight, at least 1.5 x SL, at least 2 x SL, at least 3 x SL, at least 4 x SL, or at least 5 x SL of the slightly soluble solid particles are used, where SL (in weight) is the solubility limit of the composition of the solid particles in the molten continuous phase.
[0022] The portion of all solid particles present that can have these four properties can be from 50 wt% to 100 wt%, from 75 wt% to 100 wt%, from 85 wt% to 100 w%, from 90 wt% to 100 wt%, from 90 wt% to 99 wt%, from 95 wt% to 99.9 wt% based on the total weight of solid particles. The balance of solid particles, if any, can have one, two, or three of these properties. [0023] The solid particles, as indicated, can comprise, consist of, include, or be any metal, metal alloy, metal carbide, metal nitride, metal boride, or metal silicide or any combination thereof. At least a portion of the solid particle is substantially insoluble or slightly soluble in the continuous phase of the metal or metal alloy when the metal or metal alloy is molten. Examples of the solid particles include, but are not limited, titanium, or titanium alloys such as titanium diboride. Other examples of the particles include, but are not limited to, tantalum, niobium, tungsten, molybdenum, zirconium, platinum, or carbides or borides of any one of these metals.
[0024] The solid particles are preferably uniformly dispersed in the continuous phase. For purposes of the present invention, uniformly dispersed solid particles in the continuous phase would appear to be uniformly dispersed upon visual SEM micrograph inspection of a cross sectional area of the metal article. As an example, uniformly dispersed solid particles in the continuous phase can be considered to have an interparticle spacing in the range of from about 5 nanometers to about 1000 nanometers, preferably from about 5 nanometers to about 500 nanometers or from about 10 nanometers to about 225 nanometers or an interparticle spacing of less than 500 nanometers, less than 300 nanometers, less than 125 nanometers, or less than 75 nanometers, and the like.
[0025] For purposes of the present invention, "at least a portion" in general, when referring to any of the solid particles means from 50 wt% to 100 wt%, from 75 wt% to 100 wt%, from 85 wt% to 100 w%, from 90 wt% to 100 wt%, from 90 wt% to 99 wt%, from 95 wt% to 99.9 wt% based on the total weight of solid particles.
[0026] The solid particles that are present in the metal article can be present in an amount of from about 0.5 wt% to about 25 wt% percent based on the total weight of the metal article. Other ranges include, but are not limited to, from about 1 wt% to about 20 wt%, from about 2.5 wt% to about 15 wt%, from about 5 wt% to about 25 wt%, all based on the total weight of the metal article. Other amounts can be present such as over 25 wt% or less than 0.5 wt% based on the total weight of the metal article.
[0027] The solid particles can have an average particle size. For instance, at least a portion or all of the solid particles can have an average particle size and have a BET surface area that is at least 100% higher compared to comparative solid particles (i.e., baseline solid particles that are the same as the solid particles used in the present invention with the four properties including having the same average particle size, except baseline solid particles have a spherical shape and do not have tight grapelike cluster, dendritic, or fibrous configurations). At least a portion or all of the solid particles of the present invention for instance can have a BET surface area that is at least 500% higher or at least 1000%) higher, such as from about 100% to about 1000%) higher compared to the baseline solid particles that are the same as the solid particles including having the same average particle size except are of spherical shape.
[0028] With regard to at least a portion of the solid particles having a tight grapelike cluster, dendritic, or fibrous configuration or any combination thereof, for purposes of the present invention, these are branch-like structures, as can be seen for instance in FIGS. 2, 3, and 5 which are SEM photographs of the solid particles prior to their introduction into the continuous phase (FIGS. 2 and 3) when the continuous phase is in a molten stage and after formation of the metal article (FIG. 5). For purposes of the present invention, the shape of at least a portion of the solid particles used in the present invention and present in the metal article can have a similar shape to shapes that are seen for carbon blacks. These shapes of these type solid particles are not spherical, are not flake, are not platelet, are not rods, and do not have standard geometrical shapes such as triangles, rectangles, or multi-sided geometrical shapes. For purposes of the present invention, the shape of at least a portion of the solid particles present in the metal article are as stated above, and comprise, consist essentially of, consist of, or include the tight grapelike cluster, dendritic, or fibrous configurations or any combinations thereof. For example, at least 25%, at least 50%, at least 70%, or at least 90% of the solid particles and preferably at least 99% or 100% have this shape, based on the total population of solid particles present.
[0029] At least a portion of the solid particles of the present invention can comprise, consist essentially of, consist of, or include or be primary particles, aggregates, or agglomerates or both. Aggregates are a collection of primary particles connected or fused together and agglomerates are multiple aggregates fused or connected together.
[0030] The solid particles of the present invention can have an average particle size for instance from about 10 nm to about 50 microns. This average particle size is for "particles" where it is understood for purposes of the present invention that the term "particles" includes primary particles, aggregates, and/or agglomerates. This average particle size can especially apply to the solid particles having the tight grapelike cluster, dendritic, and/or fibrous configurations.
[0031] The average particle size can be from about 10 nanometers to about 50 nanometers, from about 10 nanometers to about 100 nanometers, from about 10 nanometers to about 1 micron, from about 10 nanometers to about 10 microns, from about 1 nanometer to about 25 microns, from about 100 nanometers to about 50 microns, from about 500 nanometers to about 50 microns, from about 1 micron to about 50 microns, from about 5 microns to about 50 microns, from about 10 microns to about 50 microns, or any other particle ranges.
[0032] At least a portion or all of the solid particles of the present invention can be substantially void or entirely void of an oxide layer on the solid particles. "Substantially void" would mean that there would be less than 25% surface area, less than 10% surface area, less than 5% surface area, less than 1% surface area or 0% surface area of the solid particles having any oxide layer on the outer surface (exposed surface) of the solid particles.
[0033] In the present invention, the solid particles that are not solubilized and that have a shape that comprises, consists essentially of, consists of, or includes tight grapelike clusters, a dendritic shape, or fibrous configurations or any combination thereof retain this shape since they did not melt or solubilize in the molten continuous phase and these shapes are maintained once the metal article is casted or hardened such that it becomes a solid. When a portion of the metal particles solubilize especially in a case where the metal particles are slightly soluble in the molten continuous phase, upon casting or hardening of the molten continuous phase, the metal article can contain solid particles that have the tight grapelike clusters, dendritic shape, or fibrous configurations and other solid particles (or additional solid particles) can be present which do not have this structure since these other solid particles partially or fully solubilized in the continuous phase while molten and upon casting or solidifying of the continuous phase, at least a portion of these other solid particles precipitate (e.g., precipitated hardening) and this can form shapes other than the grapelike clusters, dendritic shape, or fibrous configurations in the continuous phase. For instance, these shapes can be spherical or have needle like shapes or rod like shapes or platelet like shapes. Further, when this precipitation occurs, at least a portion of these solid particles can become a reactive product wherein the solubilized particles reacted with the molten continuous phase to form a composition that contains both. For instance, when the molten continuous phase is aluminum and titanium solid particles are introduced, some of the titanium can solubilize in the molten aluminum phase and upon hardening or solidifying of the continuous phase, the solid particles that solubilize can form needle and/or rod shaped particles and be for instance Al3Ti. Thus, these solid particles that have been solubilized and then precipitated can be seen for instance in an SEM photograph as solid particles that are also dispersed in the continuous phase as a non-continuous phase.
[0034] Accordingly, in aspects of the present invention, the metal article can comprise a) solid particles that have a shape comprising tight grapelike clusters, dendritic shapes, or fibrous configurations and also b) comprise other solid particles having shapes other than these shapes and which can comprise the metal, metal alloy, metal carbide, metal nitride, metal boride, or metal silicide of the solid particle and also optionally comprise the metal or metal alloy from the continuous phase. For purposes of the present invention, generally when two types of solid particles are present in the continuous phase of the metal or metal alloy, the solid particles having the grapelike cluster, dendritic, and/or fibrous configurations can be present in an amount of from 1 wt% to 100 wt%, such as from about 1 wt% to 95 wt%, 10 wt% to 50 wt%, 10 wt% to 90 wt%, 10 wt% to 80 wt%, 10 wt% to 70 wt%, 30 wt% to 90 wt%, 50 wt% to 90 wt %, 70 wt% to 90 wt%, 85 wt% to 99.9 wt%, 75 wt% to 99.5 wt%, 70 wt% to 99 wt%, 85 wt% to 100 wt%, 90 wt% to 100 wt%, 95 wt% to 100 wt%, where the wt% is based on the total wt% of all solid particles present in the metal article as a solid.
[0035] In the present invention, when slightly soluble solid particles are used in the formation of the metal article, the time that the slightly soluble solid particles are present in the molten continuous phase can have an effect on the amount of slightly soluble solid particles that become soluble in the continuous phase. Thus, shorter duration times of the slightly soluble solid particles in the molten continuous phase can ensure that a greater portion of these solid particles that are present in the metal article, upon solidification, are more of the shape that is tight grapelike clusters, dendritic, or fibrous configurations. If the slightly soluble solid particles are present in the molten continuous phase for longer periods of time, a larger weight percentage of these solid particles solubilize in the molten continuous phase and upon hardening of the continuous phase to form the metal article, at least a greater portion of these particles, due in part at least to precipitation hardening, precipitate back as solid particles but in a shape that is not of grapelike clusters, dendritic, or fibrous configurations. Thus, when especially dealing with slightly soluble solid particles in forming metal articles, short residence and/or mixing times can be used if it is desired to have solid particles, of a higher percent, having the grapelike cluster, dendritic, or fibrous configurations. For instance, contact times or residence time or mixing times of the slightly soluble solid particles or even the substantially insoluble solid particles can be less than 30 minutes, or less than 15 minutes, for instance from one minute to 29 minutes prior to solidifying (e.g. casting) the continuous phase to form the solid article with dispersed solid particles.
[0036] The metal article of the present invention, as an example, can comprise, consist essentially of, consist of, or include from about 75 wt% to about 95.5 wt% of the continuous phase of metal or metal alloy and from about 0.5 wt% to about 25 wt% of the solid particles dispersed therein, based on the total weight of the metal article.
[0037] The metal article upon solidifying can be an ingot or block or any other shape of metal. The metal article can be a wrought metal article. The metal article can be a cast metal article. The metal article can have the shape of the component being cast or be considered a bar, plate, rod, or other shape.
[0038] The metal article can be part of or be an engine block, part of an engine, a turbine, or part of a turbine, or can be a chassis or be a high integrity component of a land, air, or sea or space vehicle. The dimensions of the metal article can be of any dimensions. The metal article can find use in any area using metal articles, and can be shaped into any metal article using the same metal forming techniques known in the industry. Thus, the metal article of the present invention can, for instance, be forged, rolled, hammered, molded, stamped, extruded, cold worked, hot worked, annealed, or any combination thereof to achieve any desirable shape or use of the metal article.
[0039] One significant advantage of the present invention, in at least a preferred embodiment, is that the metal article can have a modulus of elasticity as measured per ASTM El 11 that is at least 20% higher compared to a baseline or comparative metal article that is otherwise the same as the metal article of the present invention except that the solid particles are not present. In other words, with the present invention, the modulus of elasticity can be at least 20% higher when compared to a metal article that has only the continuous phase of the same metal or same metal alloy and no solid particles dispersed therein. This modulus of elasticity can be at least 25% higher, at least 30% higher, at least 35% higher, at least 40% higher, at least 45% higher, at least 50% higher, at least 55% higher, at least 60% higher, at least 65% higher, at least 70% higher, at least 75%) higher, at least 80% higher, at least 85% higher, at least 90% higher, at least 95% higher, at least 100% higher, as compared to the same metal article that does not have solid particles dispersed therein. This modulus of elasticity can be therefore from 20% to 100% higher or over 100% higher compared to the same metal article that has no solid particles dispersed therein.
[0040] With the solid particles of the present invention that have the four properties (i, ii, iii, and iv as mentioned herein), the use of this particles provides the ability to use less of these solid particles and yet achieve comparable or better properties compared to metal articles that have solid particles that do not have these four properties. For instance, with the present invention, at least 10%) less by weight, at least 20% less by weight, or at least 30% less by weight of the solid particles with the four properties can be used compared to solid particles that do not have the four properties and achieve the same or better results in the metal article. By using less solid particles, this permits a lower cost product, a product that maintains the properties of the continuous matrix more so, and yet achieves better properties regarding modulus and/or tensile strength, or in general the strength of the metal.
[0041] The following specific combinations of metals and/or metal alloys for the continuous phase and solid particles would especially benefit from the present invention:
Continuous Phase of Metal/Metal Alloy Solid Particles
1. Al (99.9 wt%, or 99.99 wt%, or 99.999 Ti, TiC, TiB2, SiC, BC, BN, W, Mo, Zr, Hf, wt% pure) Ta, Nb, or borides thereof, carbides thereof, nitrides thereof, phosphides thereof
2. Al cast alloy 356 Ti, TiC, TiB2, SiC, BC, BN, W, Mo, Zr, Hf,
Ta, Nb, or borides thereof, carbides thereof, nitrides thereof, phosphides thereof
3. Al alloys Ti, TiC, TiB2, SiC, BC, BN, W, Mo, Zr, Hf,
Ta, Nb, or borides thereof, carbides thereof, nitrides thereof, phosphides thereof
4. Mg (99.9 wt%, 99.99 wt% pure) Ti, TiC, TiB2, SiC, BC, BN
5. Mg alloys Ti, TiC, TiB2, SiC, BC, BN
6. Ti (99 wt%, 99.9 wt%, 99.99 wt% pure) ZrC, HfC, TiB2, ZrB, HfB
7. Ti alloys ZrC, HfC, TiB2, ZrB, HfB
8. Titanium aluminides ZrC, HfC, TiB2, ZrB, HfB
9. 48-48-2-2 ZrC, HfC, TiB2, ZrB, HfB
[0042] The present invention in addition, can find benefits in additive manufacturing such as 3D printing in the formation of any type of printed metal object or article.
[0043] With regard to methods of forming the metal articles of the present invention, various methods can be used such as follows.
[0044] In one method, the solid particles are present as salt-coated solid particles. These salt- coated solid particles are added to a molten liquid of metal or metal alloy that forms a liquid matrix. This molten liquid of said metal or metal alloy becomes the continuous phase of metal or metal alloy upon solidifying. The salt-coated solid particles can be obtained following the various methods described in previously filed U.S. Patent Application No. 15/051,267 filed February 23, 2016, U.S. Patent No. 8,673,051, U.S. Patent Application Publication No. 2010/0154475, U.S. Patent Application Publication No. 2012/0167716, U.S. Patent Application Publication No. 2014/0061549, U.S. Patent Application Publication No. 2014/0072498, U.S. Patent Application Publication No. 2014/0199202, WO 2009/018425, WO 2011/009014, and WO 2012/158592, all incorporated in their entireties by reference herein.
[0045] After the salt-coated solid particles have been introduced into the molten liquid of metal or metal alloy, the salt coating separates from the solid particles and salt can form a top layer on the molten liquid of metal or metal alloy and/or form on one or more sides of the container. This salt layer can optionally then be skimmed off or removed by any other technique such as, but not limited to, decanting, siphoning, pouring, and the like. Alternatively, the liquid matrix can be partly or completely removed from the salt using the same techniques. The substantial separation or removal of the salt from the liquid matrix can be at least 90% by weight of all salt being separated or removed from the liquid matrix, at least 95% by weight, at least 98% by weight, at least 99% by weight, or 100 wt% of all salt from the salt-coated solid particles being separated or removed from the liquid matrix. Afterwards, the liquid matrix can then be solidified to form a solid metal article. The solidifying can be achieved through a number of solidifying techniques such as, but not limited to, permitting solidification to occur simply at room temperature, cooling the liquid matrix, and the like.
[0046] For purposes of the present invention, the salt that forms the salt-coated solid particles can be any metal halide such as a sodium halide, potassium halide, and the like. The salt can be a metal chloride salt. Specific examples of salts include, but are not limited to, sodium chloride or other alkali, or alkaline earth chloride or halide salts. With regard to the salt-coated solid particles, generally, the salt is present in the salt-coated solid particles in a wt% of from about 1 wt% to about 99 wt%, such as from about 20 wt% to about 90 wt% or from about 50 wt% to about 75 wt% based on the total weight of the salt-coated solid particles. For purposes of the present invention, the salt- coated solid particles can be in the form of powder, chunks, or blocks and can be introduced in this manner to the molten liquid of metal or metal alloy. The powder, chunks, or blocks can have a size, for instance, of from about 1 cm by about 1 cm to about 100 cm by about 100 cm or other dimensions. When a powder, the salt-coated particles can be from about 1 mm to about 10 mm. The salt-coated solid particles can be introduced into the molten liquid of metal or metal alloy by any technique such as using an injection tube, chute, using gravity, or encapsulating it in an envelope made of the same material as the molten metal or metal alloy. The salt-coated solid particles can be introduced as a single addition, multiple additions, or the like. When using multiple additions, these several or multiple additions can be done over time such as over a span of minutes or hours to the molten liquid. The dispersing of the salt-coated solid particles in the molten liquid can be done simply by letting time expire so that the solid particles disperse amongst the molten liquid or can be agitated or stirred or vibrated in order to improve dispersing of the solid particles.
[0047] In one example, the molten liquid can be in a molten state for at least 5 minutes or at least 10 minutes, such as for at least 20 minutes, at least 30 minutes, at least 1 hour, at least 1.5 hours, at least 2 hours, or more prior to any of the salt-coated solid particles being introduced into the molten liquid. Furthermore, once salt-coated solid particles are introduced into the molten liquid and optionally after the salt has been substantially separated or removed from the liquid matrix, the molten liquid can be kept in a molten state for at least 5 minutes, at least 30 minutes, at least 1 hour, at least 5 hours, at least 10 hours, at least 1 day, or more prior to solidifying the liquid matrix. [0048] For purposes of the present invention, the solid particle can have a phase stability or be thermodynamically stable in the continuous phase indefinitely or for minutes (for instance from 1 minute to 60 minutes) or for hours (e.g., 1 hour to 24 hours) or for days (e.g., 1 day to 30 days). Depending upon the phase stability or the thermodynamic stability of the solid particles, this will control or influence the manner in which the continuous phase should be kept as a liquid matrix. For instance, if the thermodynamic stability of the solid particles is for minutes or hours, the process should be conducted in a time that is shorter than the thermodynamic stability of the solid particles and therefore the solidifying of the liquid matrix should occur before that time so as to achieve the solid particles being present in the continuous phase.
[0049] The method of the present invention can further comprise, consist essentially of, consist of, or include one or more of the following steps:
a) annealing the metal article,
b) cold working of the metal article, and/or
c) hot working of the metal article, or any other working or heat treatment step.
[0050] FIG. 1 is a series of figures showing an example of forming the metal article of the present invention using a process of the present invention. Specifically, metal or metal alloy can be heated in a crucible or other container 9 to form molten metal or metal alloy 7. Salt-coated solid particles 15 can be introduced into the molten metal or metal alloy by various transfer techniques 23 such as a chute, injection tube, conveyor belt, or other gravity feeding techniques. The molten metal or metal alloy 7 can be agitated, vibrated or otherwise stirred or mixed prior to, during, and/or after the introduction of the salt-coated solid particles 15. This optional agitation/stirring 25 can assist in obtaining better dispersion of the solid particles in the molten metal or metal alloy. Then as shown in 2, the solid particles 15 are dispersed in a continuous phase of molten metal or metal alloy 11. The salt 35 from the salt-coated particles 15 can migrate or collect on the sides of the container 9 or be at the surface of the molten metal or metal alloy 7. Then as shown in part 3, the salt 35 can be separated or otherwise removed from the container 9 or vice versa, molten metal or metal alloy with solid particles dispersed therein can be transferred to another container or holding tank and or some of the continuous phase of metal or metal alloy in the molten state along with solid particles dispersed therein can be transferred using any technique such as a siphon or transfer tube 21 to one or more molds 19 to form a metal article 23.
[0051] The present invention, in addition, relates to a method to improve the modulus of elasticity of a metal article. The method comprises, consists essentially of, consists of, or includes the step of adding solid particles to a continuous phase of a metal or metal alloy, wherein at least a portion of the solid particles have a shape comprising tight grapelike cluster, dendritic or fibrous configurations, or any combinations thereof. The solid particles are introduced to the continuous phase of a metal or metal alloy while the metal or metal alloy is in a molten state and thereafter the continuous phase along with the solid particles dispersed therein can be solidified to form a metal article. The continuous phase of metal or metal alloy as well as the solid particles dispersed therein can have any one or more of the various properties and/or characteristics and/or features as described above in the description for the metal article, the solid particles, and the continuous phase, and the methods of making the same. This method of improving the modulus of elasticity can achieve at least a 20% increase in modulus of elasticity or an increase of from about 20% to about 100% increase in modulus of elasticity compared to a baseline metal article that is the same as the baseline metal article except no solid particles are present in the baseline metal article.
[0052] The present invention will be further clarified by the following examples, which are intended to be exemplary of the present invention. EXAMPLES
Example 1
[0053] In this example, tensile bars were made using aluminum as the continuous phase and titanium nanoparticles or nanopowders as the solid particle dispersed in the continuous phase.
[0054] Specifically, 4 kg of 99.95% pure aluminum was put in a clay crucible and heated to 900°C using an induction furnace. Once the temperature reached 900°C which melted the pure aluminum and formed a molten liquid of aluminum, this temperature was essentially kept for about 30 minutes (plus or minus 10°C). After 30 minutes, salt-coated titanium powders such as shown in FIG. 1 and FIG. 2 were introduced into the molten aluminum. In this example, two runs were done. In run no. 1, salt-coated titanium powder in loose form as shown in FIG. 1 was introduced into the molten aluminum. In run no. 2, the salt-coated titanium powders in compressed pellet form as shown in FIG. 2 were introduced in a separate run to molten aluminum. Except for the salt-coated titanium powder being in loose form or compressed pellet form, the two experiments (run no. 1 and 2) were otherwise identical. In either run, 5 wt% of the salt-coated titanium was introduced into the molten aluminum based on the total weight of aluminum and salt-coated titanium. The salt-coated titanium was introduced into the melt. All of the salt-coated titanium was introduced within about 2 minutes or less. After introduction of the salt-coated titanium powders, the molten aluminum with the salt-coated titanium present was stirred for approximately 5 minutes using a graphite mixer. Afterwards, the salt from the salt- coated titanium was skimmed off using a skimmer. Then, one inch diameter tensile bars were cast. Various samples of one inch tensile bars were casted over a period of time after at least 5 minutes of stirring was completed. Particularly, three samples were cast, one immediately after the 5 minutes of stirring, another after 7 minutes of stirring, and the last sample after 10 minutes of stirring.
[0055] As a comparison for control, a one inch tensile bar was also formed following this example except no titanium was introduced as solid particles.
[0056] In addition, a further experiment was conducted wherein 10 wt% of salt-coated titanium was used in loose powder form to form one inch tensile bars and otherwise the same procedures and experiments were followed as above. The summary of properties achieved for these four samples are set forth in Table 1 below where "Pure Al" is the control sample where no titanium is present. Exp. -1 is where 5 wt% of titanium was used in loose powder form, Exp. -2 is where 5 wt% of titanium was used in pellet form, and Exp. -3 is where 10 wt% of titanium was used in loose powder form. The tensile properties shown in Table 1 were calculated pursuant to ASTM E111.
Table 1
Figure imgf000023_0001
[0057] As can be seen by the data, the strength of the aluminum (metal article) as shown in the measuring of tensile properties in the bars increase by about 140% with the addition of titanium solid nanoparticles.
Example 2
[0058] In this example, Example 1 was followed except instead of molten aluminum, an aluminum alloy was used, namely A356.0 which is commercially available. Salt-coated titanium powder was again used as the solid particles and instead of 900°C the molten temperature used was 850°C and instead of stirring for 5 minutes, the stirring time was 2 minutes. One inch tensile bars were casted in a copper mold and a cooling rate of approximately 100°C/second was used. The analysis of the tensile bars is shown below in Table 2.
[0059] Table 2 shows the measured alloy compositions of A356.0 and Α356.0+Ή alloys in wt% based on total weight of composition. It shows that about 0.35 wt% of Ti remains in molten aluminum when 5 wt% of Ti (NaCl) powders were added into the melt.
Table 2
Figure imgf000024_0001
[0060] The tensile properties of A356.0 and A356+Ti alloys were tested, and each alloy was tested for seven specimens. Tables 3 and 4 show the measurement details as averages of 7 samples. Table 5 summarizes the mechanical property differences between the two alloys. As can be seen, yield strength (YS), tensile strength (UTS), elongation (%), and modulus of elasticity (ME) are improved when Ti solid particles were added in the A356 alloy. FIG. 4 shows the typical strain- stress curves of A356.0 and Α356.0+Ή alloys. This indicates that the overall mechanical properties were improved by the addition of the Ti solid particles.
Table 3
Tensile Property Measurement - A356 without Ti (A356.0
Figure imgf000025_0001
Table 4
Tensile Property Measurement - A356 added 5% Ti+NaCl
Figure imgf000025_0002
Table 5
Comparison: - (A356-5 - A356-0VA356-0
Figure imgf000025_0003
[0061] The present invention includes the following aspects/embodiments/features in any order and/or in any combination:
1. A metal article comprising a) a continuous phase of metal or metal alloy, and b) solid particles dispersed in said continuous phase as a non-continuous phase, wherein at least a portion of said solid particles i) have a melting point that is higher than melting point of said continuous phase, ii) comprise metal, metal alloy, metal carbide, metal nitride, metal boride, or metal silicide or any combinations thereof, iii) have a shape comprising tight grapelike cluster, dendritic, or fibrous configurations or any combinations thereof; and iv) have a property of being substantially insoluble or slightly soluble in said continuous phase of metal or metal alloy when said metal or metal alloy is molten.
2. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal article has a modulus of elasticity as measured per ASTM El 11 that is at least 20% higher as compared to a baseline metal article that is the same as said metal article except for said solid particles not being present.
3. The metal article of any preceding or following embodimeni feature/aspect, wherein said modulus of elasticity is from 20% to 100% higher.
4. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal article is a wrought metal article.
5. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal article is a cast metal article.
6. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal article is a bar, plate, rod, or has a near-net-shaped configuration.
7. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal article is an engine block or part of an engine block.
8. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal article is a turbine or part of a turbine.
9. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal article is a component of an engine or transmission.
10. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal article constitutes the chassis or structural high integrity part of a land, air, sea, or space vehicle. 11. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles are uniformly dispersed in said continuous phase.
12. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles are dispersed in said continuous phase such that no percolation occurs.
13. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal of the continuous phase comprises aluminum, magnesium, titanium, or any combinations thereof.
14. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal of the continuous phase comprises at least 90% by weight aluminum, magnesium, and titanium.
15. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles are present in said metal article in an amount of from about 0.5 wt% to about 25 wt% based on total weight of metal article.
16. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles are present in said metal article in an amount of from about 1 wt% to about 20 wt% based on total weight of metal article.
17. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles are present in said metal article in an amount of from about 5 wt% to about 20 wt% based on total weight of metal article.
18. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles comprise titanium.
19. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles comprise titanium and said metal of the continuous phase comprises aluminum. 20. The metal article of any preceding or following embodiment/feature/aspect, wherein at least a portion of said solid particles having an average particle size and having a BET surface area that is at least 100% higher compared to base solid particles that are the same as the solid particles including said average particle size except having a spherical shape.
21. The metal article of any preceding or following embodiment/feature/aspect, wherein at least a portion of said solid particles having an average particle size and having a BET surface area that is at least 500% higher compared to base solid particles that are the same as the solid particles including said average particle size except having a spherical shape.
22. The metal article of any preceding or following embodiment/feature/aspect, wherein at least a portion of said solid particles having an average particle size and having a BET surface area that is at least 1000%) higher compared to base solid particles that are the same as the solid particles including said average particle size except having a spherical shape.
23. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles comprise aggregates or agglomerates or both.
24. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles have an average particle size of from about 10 nm to about 50 microns.
25. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles are at least substantially void of an oxide layer.
26. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal article is an ingot or block.
27. The metal article of any preceding or following embodiment/feature/aspect, wherein said continuous phase comprises an A356.0 alloy. 28. The metal article of any preceding or following embodiment/feature/aspect, wherein said continuous phase comprises an aluminum alloy.
29. The metal article of any preceding or following embodiment/feature/aspect, wherein said continuous phase is a Class 300 aluminum alloy.
30. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles consist of substantially insoluble solid particles.
31. A method of forming the metal article of any preceding or following embodiment/feature/aspect, said method comprising:
a. combining said solid particles as salt-coated solid particles to a molten liquid of said metal or metal alloy to form a liquid matrix, wherein salt from said salt- coated solid particles separates from said solid particles;
b. substantially separating salt and said liquid matrix from each other;
c. solidifying said liquid matrix from step b to obtain said metal article.
32. The method of any preceding or following embodiment/feature/aspect, further comprising one or more of the following steps:
a. annealing said metal article;
b. cold working of said metal article;
c. hot working of said metal article; or
d. hot isostatic pressing (HIP).
33. The method of any preceding or following embodiment/feature/aspect, wherein said salt is a sodium halide or potassium halide.
34. The method of any preceding or following embodiment/feature/aspect, wherein said salt- coated solid particles are in the form of a chunks or blocks. 35. The method of any preceding or following embodiment/feature/aspect, wherein said chunks or blocks have a size of from about 1 cm by about 1 cm to about 100 cm by about 100 cm.
36. The method of any preceding or following embodiment/feature/aspect, wherein said combining comprising introducing said salt-coated solid particles by techniques, but not limited to the following: immersion, injection, chuting, and any other methods of introducing the particles into the molten continuous phase.
37. The method of any preceding or following embodiment/feature/aspect, said method further comprising mixing or agitating said salt-covered solid particles and molten liquid to disperse said solid particles in molten metal.
38. The method of any preceding or following embodiment/feature/aspect, wherein said salt- coated solid particles are introduced in several additions over time to said molten liquid.
39. The method of any preceding or following embodiment/feature/aspect, wherein said molten liquid is in a molten state for at least 10 minutes prior to any of said salt-coated solid particles being introduced to said molten liquid.
40. The method of any preceding or following embodiment/feature/aspect, wherein after step b, and prior to step c, the molten liquid is kept in a molten state for at least 10 minutes.
41. The method of any preceding or following embodiment/feature/aspect, wherein after step b, and prior to step c, the molten liquid is kept in a molten state for at least 30 minutes.
42. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles consist of slightly soluble solid particles.
43. The metal article of any preceding or following embodiment/feature/aspect, wherein said metal article further comprises as a non-continuous phase additional solid particles that
i) have a melting point that is higher than melting point of said continuous phase ii) comprise metal, metal alloy, metal carbide, metal nitride, metal boride, or metal silicide or any combinations thereof,
iii) having a shape other than a tight grapelike cluster, dendritic, or fibrous configuration or combination thereof, and
iv) have a property of being slightly soluble in said continuous phase of metal or metal alloy when said metal or metal alloy is molten.
44. The metal article of any preceding or following embodiment/feature/aspect, wherein said additional solid particles have a shape comprising needles, rods, or both.
45. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles are present in an amount of at least 50 wt% based on the total weight of all solid particles present in said metal article.
46. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles are present in an amount of at least 75 wt% to 100 wt% based on the total weight of all solid particles present in said metal article.
47. The metal article of any preceding or following embodiment/feature/aspect, wherein said solid particles are present in an amount of at least 95 wt% to 99.9 wt% based on the total weight of all solid particles present in said metal article.
48. The metal article of any preceding or following embodiment/feature/aspect, wherein said additional solid particles comprise said metal, metal alloy, metal carbide, metal nitride, metal boride, or metal silicide of the additional solid particles and includes in part the metal or metal alloy from said continuous phase.
[0062] The present invention can include any combination of these various features or embodiments above and/or below as set forth in sentences and/or paragraphs. Any combination of disclosed features herein is considered part of the present invention and no limitation is intended with respect to combinable features.
[0063] Applicant specifically incorporates the entire contents of all cited references in this disclosure. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.
[0064] Other embodiments of the present invention will be apparent to those skilled in the art from consideration of the present specification and practice of the present invention disclosed herein. It is intended that the present specification and examples be considered as exemplary only with a true scope and spirit of the invention being indicated by the following claims and equivalents thereof.

Claims

WHAT IS CLAIMED IS:
1. A metal article comprising a) a continuous phase of metal or metal alloy, and b) solid particles dispersed in said continuous phase as a non-continuous phase, wherein at least a portion of said solid particles i) have a melting point that is higher than melting point of said continuous phase, ii) comprise metal, metal alloy, metal carbide, metal nitride, metal boride, or metal silicide or any combinations thereof, iii) have a shape comprising tight grapelike cluster, dendritic, or fibrous configurations or any combinations thereof; and iv) have a property of being substantially insoluble or slightly soluble in said continuous phase of metal or metal alloy when said metal or metal alloy is molten.
2. The metal article of claim 1, wherein said metal article has a modulus of elasticity as measured per ASTM El 11 that is at least 20% higher as compared to a baseline metal article that is the same as said metal article except for said solid particles not being present.
3. The metal article of claim 2, wherein said modulus of elasticity is from 20% to 100% higher.
4. The metal article of claim 1, wherein said metal article is a wrought metal article.
5. The metal article of claim 1 , wherein said metal article is a cast metal article.
6. The metal article of claim 1, wherein said metal article is a bar, plate, rod, or has a near- net-shaped configuration.
7. The metal article of claim 1, wherein said metal article is an engine block or part of an engine block.
8. The metal article of claim 1, wherein said metal article is a turbine or part of a turbine.
9. The metal article of claim 1, wherein said metal article is a component of an engine or transmission.
10. The metal article of claim 1, wherein said metal article constitutes the chassis or structural high integrity part of a land, air, sea, or space vehicle.
11. The metal article of claim 1, wherein said solid particles are uniformly dispersed in said continuous phase.
12. The metal article of claim 1, wherein said solid particles are dispersed in said continuous phase such that no percolation occurs.
13. The metal article of claim 1, wherein said metal of the continuous phase comprises aluminum, magnesium, titanium, or any combinations thereof.
14. The metal article of claim 1, wherein said metal of the continuous phase comprises at least 90% by weight aluminum, magnesium, and titanium.
15. The metal article of claim 1, wherein said solid particles are present in said metal article in an amount of from about 0.5 wt% to about 25 wt% based on total weight of metal article.
16. The metal article of claim 1, wherein said solid particles are present in said metal article in an amount of from about 1 wt% to about 20 wt% based on total weight of metal article.
17. The metal article of claim 1, wherein said solid particles are present in said metal article in an amount of from about 5 wt% to about 20 wt% based on total weight of metal article.
18. The metal article of claim 1, wherein said solid particles comprise titanium.
19. The metal article of claim 1, wherein said solid particles comprise titanium and said metal of the continuous phase comprises aluminum.
20. The metal article of claim 1, wherein at least a portion of said solid particles having an average particle size and having a BET surface area that is at least 100% higher compared to base solid particles that are the same as the solid particles including said average particle size except having a spherical shape.
21. The metal article of claim 1, wherein at least a portion of said solid particles having an average particle size and having a BET surface area that is at least 500% higher compared to base solid particles that are the same as the solid particles including said average particle size except having a spherical shape.
22. The metal article of claim 1, wherein at least a portion of said solid particles having an average particle size and having a BET surface area that is at least 1000% higher compared to base solid particles that are the same as the solid particles including said average particle size except having a spherical shape.
23. The metal article of claim 1, wherein said solid particles comprise aggregates or agglomerates or both.
24. The metal article of claim 1, wherein said solid particles have an average particle size of from about 10 nm to about 50 microns.
25. The metal article of claim 1, wherein said solid particles are at least substantially void of an oxide layer.
26. The metal article of claim 1, wherein said metal article is an ingot or block.
27. The metal article of claim 1, wherein said continuous phase comprises an A356.0 alloy.
28. The metal article of claim 1, wherein said continuous phase comprises an aluminum alloy.
29. The metal article of claim 1, wherein said continuous phase is a Class 300 aluminum alloy.
30. The metal article of claim 1 wherein said solid particles consist of substantially insoluble solid particles.
31. A method of forming the metal article of claim 1 , said method comprising:
a. combining said solid particles as salt-coated solid particles to a molten liquid of said metal or metal alloy to form a liquid matrix, wherein salt from said salt- coated solid particles separates from said solid particles;
b. substantially separating salt and said liquid matrix from each other;
c. solidifying said liquid matrix from step b to obtain said metal article.
32. The method of claim 31, further comprising one or more of the following steps:
a. annealing said metal article;
b. cold working of said metal article;
hot working of said metal article; d. hot isostatic pressing (HIP).
33. The method of claim 31 , wherein said salt is a sodium halide or potassium halide.
34. The method of claim 31, wherein said salt-coated solid particles are in the form of a chunks or blocks.
35. The method of claim 31, wherein said chunks or blocks have a size of from about 1 cm by about 1 cm to about 100 cm by about 100 cm.
36. The method of claim 31, wherein said combining comprising introducing said salt-coated solid particles by immersion, injection, or chuting.
37. The method of claim 31, said method further comprising mixing or agitating said salt- covered solid particles and molten liquid to disperse said solid particles in molten metal.
38. The method of claim 31, wherein said salt-coated solid particles are introduced in several additions over time to said molten liquid.
39. The method of claim 31, wherein said molten liquid is in a molten state for at least 10 minutes prior to any of said salt-coated solid particles being introduced to said molten liquid.
40. The method of claim 31, wherein after step b, and prior to step c, the molten liquid is kept in a molten state for at least 10 minutes.
41. The metal article of claim 1, wherein said solid particles consist of slightly soluble solid particles.
42. The metal article of claim 1, wherein said metal article further comprises as a non- continuous phase additional solid particles that
i) have a melting point that is higher than melting point of said continuous phase ii) comprise metal, metal alloy, metal carbide, metal nitride, metal boride, or metal silicide or any combinations thereof,
iii) having a shape other than a tight grapelike cluster, dendritic, or fibrous configuration or combination thereof, and
iv) have a property of being slightly soluble in said continuous phase of metal or metal alloy when said metal or metal alloy is molten.
43. The metal article of claim 42, wherein said additional solid particles have a shape comprising needles, rods, or both.
44. The metal article of claim 42, wherein said solid particles are present in an amount of at least 50 wt% based on the total weight of all solid particles present in said metal article.
45. The metal article of claim 42, wherein said solid particles are present in an amount of at least 75 wt% to 100 wt% based on the total weight of all solid particles present in said metal article.
46. The metal article of claim 42, wherein said solid particles are present in an amount of at least 95 wt% to 99.9 wt% based on the total weight of all solid particles present in said metal article.
47. The metal article of claim 42, wherein said additional solid particles comprise said metal, metal alloy, metal carbide, metal nitride, metal boride, or metal silicide of the additional solid particles and includes in part the metal or metal alloy from said continuous phase.
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