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EP2531630B1 - Matériaux à base de métal dur - Google Patents

Matériaux à base de métal dur Download PDF

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Publication number
EP2531630B1
EP2531630B1 EP11739260.5A EP11739260A EP2531630B1 EP 2531630 B1 EP2531630 B1 EP 2531630B1 EP 11739260 A EP11739260 A EP 11739260A EP 2531630 B1 EP2531630 B1 EP 2531630B1
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EP
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Prior art keywords
particles
metal
niobium
host
refractory material
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EP11739260.5A
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German (de)
English (en)
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EP2531630A1 (fr
EP2531630A4 (fr
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Kevin Dolman
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Weir Minerals Australia Ltd
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Weir Minerals Australia Ltd
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Publication of EP2531630A4 publication Critical patent/EP2531630A4/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1068—Making hard metals based on borides, carbides, nitrides, oxides or silicides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002—Castings of light metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/14—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/06—Cast-iron alloys containing chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/10—Cast-iron alloys containing aluminium or silicon

Definitions

  • the present invention relates in general terms to hard metal materials comprising refractory material particles, as described herein, dispersed in a host metal or metal alloy.
  • the ASM Materials Engineering Dictionary defines the term "hard metal” as a collective term for a sintered material with high hardness, strength and wear resistance.
  • the present invention also provides components manufactured from the hard metal materials.
  • the present invention relates particularly, although by no means exclusively, to large components weighing more than 100kgs and typically more than 1 tonne.
  • the present invention also provides a method of manufacturing the components from the hard metal materials.
  • the present invention relates to hard metal materials that are useful for applications requiring wear resistance.
  • powder metallurgy to manufacture small components from hard metal materials comprising refractory particles dispersed in a host metal (which term is understood herein to include metal alloy).
  • Powder metallurgy processes involve sintering mechanically mixed refractory powders at elevated temperatures under pressure, usually in an inert atmosphere.
  • “Sintering” comprises bonding powdered materials, usually under pressure, by solid-state reactions at temperatures lower than that required for the formation of a liquid phase. During a sintering process, at temperatures below the melting point of the metallic binders, powders of metallic binder phase and refractory particles are welded together by pressure and heat. Sintering is traditionally used for manufacturing ceramic components and has also found uses in such fields as powder metallurgy for the manufacture of products containing very high melting point materials.
  • Powder metallurgy is a useful process for manufacturing relatively small, simple-shaped, wear resistant components such as tungsten carbide tool bits.
  • powder metallurgy is not a practical process for manufacturing larger, complex-shaped, hard metal, wear resistant components such as pump impellers and crusher wear parts weighing more than 100kgs and typically more than 1 tonne from hard metal materials. This is an issue, particularly in applications in the mining and minerals processing industries where large high wear resistant components are often required.
  • wear resistant metal alloys such as high chromium white cast irons
  • hard-facing alloys are formed on the trays of dump trucks that transport mined ore from a mine site to a minerals processing plant.
  • castings of wear resistant alloys are used to form pumps for transporting slurries of ore particles suspended in water through processing stages in flotation circuits in a minerals processing plant.
  • the fracture toughness and corrosion resistance requirements for the wear resistant alloy in each of the above examples are different and, accordingly, the wear resistant alloy compositions are different.
  • the common factor between both, however, is a need to provide wear resistance in addition to other properties.
  • higher wear resistance can be achieved through controlling the alloy composition, but there is a trade-off against other properties.
  • WO 94/11541 A1 there is described a method of making an engineering ferrous metal comprising the steps of adding to liquid engineering ferrous metal solid alloy carbide particles and thereafter permitting the ferrous metal to solidify.
  • the alloy carbide particles are coated with iron or an iron alloy to allow wetting to occur between the powder and the liquid ferrous metal and the particles have a density which matches that of the ferrous metal to provide a uniform distribution of the carbide particles in the ferrous metal.
  • DE 2063181 A1 relates to casting processes wherein a TiC-containing carbide component is incorporated into a Fe, Co or Ni based alloy.
  • the alloy may also contain other carbides of metals which belong to groups IVa, Va and Vla of the periodic table, primarily tungsten carbide, and, for example, carbides of zirconium, vanadium, niobium and tantalum.
  • a casting of a white cast iron alloy comprises the following alloy composition, in weight%: chromium: 12 - 25%; carbon: 1.5 - 6%; manganese: 2 - 7%; silicon: up to 1.5%; molybdenum: up to 2; nickel: up to 4%; microalloying elements selected from the group consisting of titanium, zirconium, niobium, boron, vanadium, and tungsten: up to 2% of each of one or more of the elements; and iron: balance.
  • the microstructure of the casting comprises 15-60 vol% eutectic carbides and primary carbides dispersed in a ferrous matrix that comprises martensite and is at least substantially free of pearlite.
  • JP H07 30429 there is disclosed sintered products having excellent thermal shock resistance and thermal fatigue resistance.
  • the sintered products comprise carbides dispersed in a matrix of a high-alloy steel.
  • the dispersed carbides are selected from 2-20% vanadium carbides, 2-20% of carbides (except vanadium carbide) of the metals of groups Vla, Va, and Vla of the periodic table, and one or more nitrides and carbonitrides of the metals of groups Vla and Va, and one or more solid solutions of two or more thereof.
  • US 5,030,519 discloses a matrix-bonded carbide-containing material of high hardness prepared using a mixture containing a matrix alloy having a composition in weight percent of from about 15 - 45 percent chromium, from 0 - 3 percent silicon, from about 2 - 6 percent boron, from about 3 - 11 percent titanium (either as metal or as a compound), balance iron and impurities, and a mass of tungsten carbide particles, the tungsten carbide particles preferably being present in an amount of from about 15-60 percent by weight of the total mixture and the matrix alloy preferably being present in an amount of from about 85 - 40 percent by weight of the total mixture.
  • US 3,528,808 discloses a casting of a nickel-base, cobalt-base or chromium-base alloy and a reinforcing phase consisting essentially of a refractory carbide, present predominantly in the form of high strength fibers integrally embedded in the base metal matrix.
  • US 2009/025834 discloses an amorphous steel alloy with up to 10 wt% of NbC.
  • a liquid host metal containing a dispersion, typically a dispersion, of 10-50 volume % fine particles of a refractory material that is insoluble in the host metal, and is described herein as a liquid metal slurry, has very good fluidity during pouring in a foundry and the slurry readily flows to fill sand moulds to produce sound castings of the hard metal material.
  • insoluble is understood herein to mean that for all intents and purposes the refractory material is not soluble in the host metal. There may be limited solubility. However, the refractory particles are essentially distinct from the host metal in that there is negligible partitioning of the transition metals in the refractory material particles to the host metal.
  • mixing and dispersing the insoluble refractory particles in the host metal may be carried out in an effective way in the liquid state in an inert atmosphere, such as in a vacuum furnace, to minimise oxidation of the reactive elements in the refractory material particles.
  • the present invention is a departure from standard foundry practice known to the applicant that involves the complete melting of all alloying additions contained in a casting to form a single phase liquid to ensure maximum fluidity during pouring into a mould.
  • liquid metal slurries when cast within certain production parameters in accordance with the present invention, is sufficient to produce a family of sound hard metal material castings ranging from small to large casings with specific wear resistance, fracture toughness and corrosion resistance that suit a wide range of operating conditions in service.
  • the production parameters may comprise any one or more of the particle size, reactivity, thermal expansion or contraction, density, and solubility of the refractory material, as discussed further below.
  • the present invention provides a hard metal material as set forth in claim 1.
  • hard metal material is understood to comprise particles of high melting point carbides of any of titanium and niobium dispersed in a tough host metal, which acts as a binder phase.
  • the host metal is a ferrous metal alloy.
  • Each of these particles is a particle of a refractory material and is referred to herein as a "refractory material”.
  • the particles of the refractory material may be carbides of one transition metal, such as NbC.
  • the particles of the refractory material may be carbides of more than one transition metal where the particles are a chemical mixture (as opposed to a physical mixture) of the carbides of the transition metals.
  • the particles of the refractory material may be of the type described as (M 1 ,M 2 )C, where "M” is a transition metal.
  • M is a transition metal.
  • the hard metal material may comprise 10-40 volume % particles of the refractory material dispersed in the host metal.
  • the hard metal material may comprise less than 30 volume % particles of the refractory material dispersed in the host metal.
  • the hard metal material may comprise less than 25 volume % particles of the refractory material dispersed in the host metal.
  • the host metal may be a ferrous alloy (such as a steel or a cast iron), a stainless steel, an austenitic-manganese steel such as a Hadfield steel, or a iron-based or nickel-based or cobalt-based superalloy.
  • a ferrous alloy such as a steel or a cast iron
  • a stainless steel such as a stainless steel
  • an austenitic-manganese steel such as a Hadfield steel
  • iron-based or nickel-based or cobalt-based superalloy such as a steel or a cast iron
  • the present invention also provides a method of forming a hard metal material as set forth in claim 8.
  • the present invention also provides a method of manufacturing a component of a hard metal material as set forth in claim 4.
  • the method may comprise forming the slurry and thereafter forming the casting of the component in a chamber under vacuum conditions which remove air from the chamber and supplying an inert gas, such as argon, into the chamber.
  • an inert gas such as argon
  • the method may be carried out in a vacuum melting furnace.
  • the method may comprise selecting the production parameters to form the slurry in step (a) that has a required fluidity for processing in step (b).
  • a skilled person will be able to determine a required fluidity for processing step (b) having regard to standard foundry practice considerations such as the size and shape of the component to be formed and the required dispersion (uniform or segregated) to provide the required microstructure for the component.
  • the production parameters may comprise any one or more of the particle size, reactivity, density, and solubility of the refractory materials, as discussed further below.
  • the refractory material may be a fine particle size.
  • a fine refractory material particle size may be required to ensure a homogeneous dispersion in the host metal.
  • the melting points of the majority of the transition metal refractory materials are in excess of 1800°C and the refractory materials are generally insoluble in host liquid metals.
  • the applicant has found that refractory powders with particle sizes less than 500 microns, typically less than 150 microns, in diameter provide optimum flow characteristics in liquid metal slurries and yield a desirable uniform dispersion of the refractory particulates in the microstructures of the Hard Metal castings.
  • the refractory material may be less than 400 microns particle size.
  • the refractory material may be less than 200 microns particle size.
  • the refractory material may be less than 150 microns particle size.
  • the refractory material may be added to the host liquid metal as follows.
  • Fe-Nb readily dissolves in the host liquid metal at 1500°C and niobium immediately combines with carbon in the host liquid metal to form niobium carbides in situ with particle sizes less than 50 microns in diameter.
  • transition metal refractory materials described above are classed as "reactive elements", i.e. the individual metal elements and/or their carbide compound forms react readily with air at metal casting temperatures about 1500°C to form undesirable metal oxides and/or copious quantities of gases such as C0 2 which can result in severe porosity in the castings.
  • reactive elements i.e. the individual metal elements and/or their carbide compound forms react readily with air at metal casting temperatures about 1500°C to form undesirable metal oxides and/or copious quantities of gases such as C0 2 which can result in severe porosity in the castings.
  • the problems of oxidation and porosity in hard metal castings, produced by a liquid metal slurry, and associated with chemical reactions of the reactive refractory materials in air at elevated temperatures are overcome by melting and pouring the liquid metal slurry in an inert atmosphere.
  • the density of the refractory material of the particles is a parameter to consider during the method of the present invention to control the dispersion of refractory particles in the hot host metal. In some situations it may be important to avoid segregation of refractory material particles in the liquid host metal. In other situations, segregation may be desirable.
  • the nominal density of a host ferrous liquid metal at 1400 °C is 6.9 grams/cc. When tungsten carbide particles, with a density of 15.7 grams/cc, are added to a host ferrous metal, the WC particles will sink to the bottom of the mould prior to solidification of the host metal.
  • Niobium carbide When titanium carbide particles, with a density of 4.8 grams/cc, are added to the same host ferrous metal, the TiC particles will float to the top of the ladle or mould.
  • Niobium carbide With a density of 7.7 grams/cc at 1400 C, is fairly close to the density of the host liquid metal at 6.9 grams/cc and is less prone to segregation in the liquid host metal than TiC or WC.
  • NbC particles will segregate to the bottom of large section white iron castings during the process of the present invention when solidification times are in the order of 30 minutes or more.
  • niobium carbide and titanium carbide have similar crystal structures and are isomorphous.
  • refractory material particles that are for all intents and purposes insoluble, i.e. having minimal solid solubility in the host liquid metal, to produce a casting in accordance with the method of the present invention, produces a hard metal material that displays physical and chemical properties that are very similar to the host metal with substantially improved wear resistance due to the presence of a controlled dispersion of a high volume % of hard refractory material particles in the microstructure.
  • the solubility of a refractory material in the form of (Nb,Ti)C in liquid host metals in the form of (a) liquid Hadfield steel and (b) liquid 316 stainless steel and (c) liquid high chromium white cast iron at elevated temperatures is negligible ( ⁇ 0.3 weight%).
  • the addition of 15 weight% (Nb,Ti)C with the required densities to these three metal alloys, followed by standard heat treatment procedure for each host metal produces microstructures consisting of a uniform dispersion of 15 volume% primary niobium-titanium carbides in the host metals which are substantially free of niobium and titanium, i.e. there is negligible partitioning of the transition metals in the refractory material slurry particles to the liquid host metal.
  • the three hard metal materials produced by the method of the present invention display the known physical and chemical properties of (a) Hadfield steel, (b) 316 stainless steel and (c) high chromium white cast iron respectively with an increased wear resistance due to the presence of a dispersion of 15 volume% of primary niobium-titanium carbides in the microstructures.
  • a hard metal material with a microstructure that includes particles of niobium carbide and/or particles of a chemical (as opposed to a physical) mixture of niobium carbide and titanium carbide dispersed in a matrix of a host metal considerably improves wear resistance of the hard metal material without detrimentally affecting the contribution that other alloying elements have on other properties of the hard metal material.
  • the applicant has found that it is possible to adjust the density of particles of a chemical mixture of niobium carbide and titanium carbide to a sufficient extent in relation to the density of a host metal, which forms a matrix of the hard metal material, to make it possible to selectively control the dispersion of the particles in the matrix from a uniform dispersion to a non-uniform dispersion of the particles.
  • This opportunity for density control is an important finding in relation to castings of the hard metal material. In particular, by virtue of this finding it is now possible to produce castings of the hard metal material with controlled segregation of the particles in parts of the castings.
  • forming a hard metal material and castings of the material to include particles of niobium carbide and/or particles of a chemical mixture of niobium carbide and titanium carbide in a range of 10 to 25 wt%, or even up to 33 wt% or higher, dispersed in a host metal, which forms a matrix of the hard metal material, does not have a significant negative impact on corrosion resistance and toughness of ferrous material in the host metal.
  • the present invention makes it possible to achieve high wear resistance of a hard metal material without a loss of other desirable material properties.
  • niobium carbide and titanium carbide and "niobium/titanium carbides” are hereinafter understood to be synonyms.
  • chemical mixture is understood in this context to mean that the niobium carbides and the titanium carbides are not present as separate particles in the mixture but are present as particles of niobium/titanium carbides.
  • Niobium carbides and titanium carbides each have a Vickers hardness (HV) around 2500, which is about 1000 HV above the hardness of chromium carbides. Accordingly, hard metal materials having a microstructure containing 10 to 40 wt% particles of niobium carbide and/or niobium/titanium carbides have excellent wear resistance properties.
  • HV Vickers hardness
  • niobium carbides and titanium carbides and niobium/titanium carbides are substantially inert chemically with respect to other constituents in the hard metal material so those constituents provide the hard metal material with the properties for which they were selected. For example, chromium added to cast iron alloys still produces chromium carbides and provides corrosion resistance.
  • the melt may be in the form of a weld pool in a hard-facing process.
  • the niobium and/or the titanium may be added to the weld pool in a wire alloy in order to meter the addition of niobium and/or titanium.
  • the melt may be in the form of a melt for forming a casting.
  • niobium and the titanium may be added to the melt in any suitable form, bearing in mind the requirement of forming particles of niobium carbides and/or niobium/titanium carbides in the solid hard metal material.
  • the method may comprise adding the niobium to the melt in the form of ferro-niobium, for example particles of ferro-niobium.
  • the ferro-niobium dissolves in the melt and the resultant free niobium and carbon in the melt form niobium carbides in the melt.
  • the method may also comprise adding the niobium to the melt as elemental niobium.
  • the method may also comprise adding the niobium and the titanium to the melt as ferro-niobium-titanium.
  • the method may also comprise adding the niobium to the melt in the form of particles of niobium carbide.
  • the method may also comprise adding the niobium and the titanium to the melt in the form of particles of niobium/titanium carbides.
  • the solidified metal alloy may be formed from a slurry of particles of niobium carbide and/or niobium/titanium carbides suspended in the melt. It is anticipated that if the weight fraction of these carbides in the melt slurry is too high, the flow properties of the slurry may be adversely affected with the result that unsound castings of the melt may be produced. Nevertheless, casting a slurry contrasts with the standard operating procedure in foundries which involves casting clear (single phase) liquid melts, i.e. where the melt is above the liquidus temperature of the highest melting point constituent of the melt.
  • the particles of niobium/titanium carbides may be any suitable chemical mixture of a general formula (Nb x ,Ti y )C.
  • the niobium/titanium carbides may be (Nb 0.5 ,Ti 0.5 )C or (Nb 0.25 ,Ti 0.75 )C or (Nb 0.75 ,Ti 0.25 )C.
  • the niobium and/or the titanium may be added to the melt to produce particles of niobium carbide and/or niobium/titanium carbides in a range of 12 wt% to 33 wt% niobium carbides and niobium/titanium carbides of the total weight of the solidified hard metal material.
  • the niobium and/or the titanium may be added to the melt to produce particles of niobium carbide and/or niobium/titanium carbides in a range of 12 wt% to 25 wt% niobium carbides and niobium/titanium carbides of the total weight of the solidified hard metal material.
  • the quantity of particles of niobium carbide and/or niobium/titanium carbides in the microstructure of the solidified hard metal material may depend on the system.
  • the applicant is concerned particularly with solid hard metal materials that include host metals in the form of ferrous alloys, such as ferrous alloys described as high chromium white cast irons, stainless steels, and austenitic manganese steels (such as Hadfield steels).
  • ferrous alloys such as ferrous alloys described as high chromium white cast irons, stainless steels, and austenitic manganese steels (such as Hadfield steels).
  • the quantity of particles of niobium carbide and/or niobium/titanium carbides in the final microstructure may be in a range of 10 to 33 wt% or in a range of 12 to 25 wt% of the total weight of the solidified hard metal material.
  • the particle size of niobium carbide and/or niobium/titanium carbide may be in a range of 1 to 150 ⁇ m in diameter.
  • the method may comprise stirring the melt with an inert gas or magnetic induction or any other suitable means in order to disperse particles of niobium carbide and/or niobium/titanium carbides in the melt.
  • the method may comprise adding particles of niobium carbide and/or particles of niobium/titanium carbides to the melt under inert conditions, such as an argon blanket, to reduce the extent to which niobium carbide and/or titanium carbide oxidize while being added to the melt.
  • inert conditions such as an argon blanket
  • the method may comprise adding particles of ferro-niobium and/or ferro-titanium and/or ferro- niobium-titanium to the melt under inert conditions, such as an argon blanket, to reduce the extent to which niobium and/or titanium oxidize while being added to the melt.
  • inert conditions such as an argon blanket
  • the method may comprise pre-melting ferro-niobium and ferro-titanium and/or ferro-niobium-titanium under inert conditions and forming a liquid phase that is a homogeneous chemical mixture of iron, niobium and titanium and solidifying this chemical mixture.
  • the chemical mixture can then be processed as required, for example by crushing to a required particle size, and then added to the melt (containing carbon) under inert conditions.
  • the iron, niobium and titanium dissolve in the melt and the niobium and titanium and carbon in the melt form niobium/titanium carbides in the melt.
  • the method may comprise forming the solidified hard metal material by casting the melt into a cast product, such as a pump impeller or a pump throatbush.
  • the cast product may be subject to subsequent thermal treatment for adjusting the microstructure to achieve desired alloy properties.
  • the casting may comprise a uniform dispersion of the niobium/titanium carbide particles in the matrix.
  • the casting may be a pump impeller.
  • the casting may comprise a non-uniform dispersion of the niobium/titanium carbide particles in the matrix.
  • the casting may be a pump throatbush.
  • the host metal may be a ferrous alloy, such as a high chromium white cast iron, a stainless steel, or an austenite manganese steel (such as a Hadfield steel).
  • a ferrous alloy such as a high chromium white cast iron, a stainless steel, or an austenite manganese steel (such as a Hadfield steel).
  • the applicant carried out an extensive series of laboratory melting trials on the addition of 10 (comparative) to 30 wt% NbC and Nb/TiC particles to a wide selection of ferrous alloys including high chromium white irons, austenitic-manganese steels (including Hadfield steels), superalloys, stainless steels (including duplex, ferritic, austenitic and martensitic) and hard-facing weld deposits.
  • ferrous alloys including high chromium white irons, austenitic-manganese steels (including Hadfield steels), superalloys, stainless steels (including duplex, ferritic, austenitic and martensitic) and hard-facing weld deposits.
  • FIG. 1 An example of a microstructure of a high chromium white cast iron alloy including 15 wt% NbC is shown in Figure 1 .
  • the alloy was produced by casting a 50g ingot from a melt produced in an electric arc melting furnace under a partial pressure of argon in a water cooled copper hearth, i.e. the ingot was chill cast.
  • the NbC was added to the furnace melt as discrete particles which had a particle size range of 2 to 20 ⁇ m in diameter.
  • the applicant has examined the use of various other particle size ranges of NbC, including ⁇ 45 ⁇ m in diameter, 45 to 75 ⁇ m in diameter, 75 to 150 ⁇ m in diameter and ⁇ 100 ⁇ m in diameter.
  • High chromium white cast iron alloys conventionally rely on the high chromium content to produce a significant volume of hard chromium carbides that provide castings with high wear resistance.
  • high chromium white cast iron alloys conventionally rely on some chromium remaining in the ferrous matrix and provides alloys with corrosion resistance.
  • the microstructure in Figure 1 exhibits a ferrous matrix containing a fine dispersion of eutectic M 7 C 3 carbides (approximating 30 volume%) and a dispersion of 15 wt% NbC particles which appear as a phase of white coloured spheroids in the Figure.
  • the microstructure shown in Figure 2 is a form of 420C grade martensitic stainless steel that was produced by the same process described above for the high chromium white cast iron shown in Figure 1 .
  • NbC particles (white coloured in Figure 2 ) are not regular spheroids as in the high chromium white cast iron, but rather an irregular NbC carbide shape that appears to be typical for various stainless steel grades that have been alloyed with NbC.
  • microstructures of the test castings in Figure 1 and other test castings produced by the applicant show that all the NbC particles added to the ferrous alloys are primary carbides in suspension in the liquid metal.
  • the analogy is that all conventional castings above the liquidus temperature (approximately 1300-1400°C) are "clear liquids", i.e. single phase liquids.
  • niobium carbide particles were added, for example 20 wt%, the particles remained in suspension so the liquid metal and NbC particles approximate a "slurry" (2 phases) with good fluidity, which is a mandatory requirement for producing sound castings.
  • the experimental work found a similar outcome when niobium/titanium carbide particles were added to a liquid melt.
  • niobium carbides can form as solid particles in a melt, rather than added to the melt, by adding ferro-niobium to the melt.
  • the melt contains carbon, and the weight% carbon is greater than one eighth of the weight% of niobium.
  • the iron and niobium separate in the melt.
  • the niobium which has a high affinity for carbon, chemically combines with carbon from the liquid melt to form solid niobium carbide particles dispersed in the liquid melt.
  • the melt is cast as a "slurry" consisting of solid niobium carbide particles suspended in the liquid melt.
  • the casting will have a microstructure that includes niobium carbides dispersed in a ferrous matrix. A similar microstructure is achieved with niobium/titanium carbide particles.
  • Niobium carbide can be added to ferrous alloys, such as high chromium white cast irons in two distinct ways, as follows.
  • the density of NbC is 7.8 grams/cc at room temperature and this is close to the density of high chromium white cast iron (7.5 grams/cc).
  • the presence of phases with similar densities assists in achieving a uniform dispersion of NbC particles in the liquid metal during a casting process.
  • high chromium white cast iron increases with temperature.
  • the coefficient of thermal expansion of high chromium white cast iron is double that of NbC.
  • high chromium white cast iron undergoes a step increase in volume at the solid to liquid phase change at approximately 1260°C.
  • the density of high chromium white cast iron in the liquid state at 1400°C is 6.9 grams/cc whereas the density of NbC at 1400°C is about 7.7 grams/cc.
  • This density difference is sufficient to cause segregation of NbC particles in liquid high chromium white cast iron at foundry casting temperatures of 1300°C or greater.
  • Titanium carbide is similar in many characteristics to NbC.
  • the crystal structures are the same, with group number 225.
  • the lattice parameter of NbC is 4.47 Angstroms and the lattice parameter of TiC is 4.32 Angstroms.
  • TiC and NbC are isomorphorous, i.e. Ti atoms will readily substitute for Nb atoms in NbC.
  • the hardness of TiC is similar to NbC.
  • the melting point of TiC is 3160°C, which is similar to the melting point of NbC (3600°C).
  • the density of TiC is 4.9 grams/cc at room temperature, and this is much less than the density of NbC. Since TiC and NbC are isomorphous, it is possible to achieve any density value for the mixed carbide in a range 4.9-7.8 grams/cc by selecting the corresponding chemical composition with the general formula (Nb x ,Ti y )C.
  • the niobium/titanium carbides may be (Nb 0.5 ,Ti 0.5 )C or (Nb 0.25 ,Ti 0.75 )C or (Nb 0.75 ,Ti 0.25 )C.
  • This density difference is the basis of a cost effective method of reducing the segregation of hard, solid carbides in liquid metal at usual foundry casting temperatures.
  • This selection may be desirable for some castings where uniform wear resistance through the castings is desirable and for other castings where it is desirable to have a concentration of wear resistant particles in one section, such as a surface, of the castings.
  • the specification refers to the microstructures of hard metal materials of the present invention by volume % rather than the usual bulk chemical weight %.
  • the table set out below is provided to explain the reason for this selection of nomenclature.
  • the third and fourth cases in the table, the exercise is repeated for 10 and 20 volume % NbC in Hadfield steel.
  • the chemistry of the host metal is identical and is essentially Fe-12Mn-1.2C-2 Mn-0.5Si. Again, the bulk chemistries of these two hard metal materials are widely different and are not descriptive of the microstructures.
  • the final bulk chemistry of each of the hard metal materials is a complex function of the selected microstructure and the actual bulk chemistry is not a useful means of describing the required features of the hard metal materials.
  • the required features of the hard metal material of the present invention are (a) host metal chemistry and (b) volume% of the selected refractory particles.
  • the hard metal material of the present invention may be cast as a final product shape and may be formed as a solid material that is subsequently hot worked in a downstream processing operation to form a final product shape.
  • the hard metal material of the present invention may be formed as an ingot and subsequently hot worked by rolling or forging as required into a final product such as a bar or a plate.

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Claims (10)

  1. Matériau de métal dur sous la forme d'une coulée comprenant plus de 15 et jusqu'à 50 % en volume de particules d'un matériau réfractaire dispersées dans un métal hôte, dans lequel les particules du matériau réfractaire sont sélectionnées parmi : (a) des particules de carbure de niobium contenant des particules réfractaires ; et (b) des particules d'un mélange chimique de carbure de niobium et de carbure de titane, et dans lequel les particules sont insolubles dans le métal hôte à sa température de coulée et le métal hôte comprend un alliage ferreux (tel qu'un acier, une fonte, un acier inoxydable, un acier austénitique au manganèse).
  2. Matériau de métal dur selon la revendication 1 comprenant moins de 30 % en volume de particules du matériau réfractaire dispersées dans le métal hôte, et de préférence moins de 25 % en volume de particules du matériau réfractaire dispersées dans le métal hôte.
  3. Matériau de métal dur selon l'une quelconque des revendications précédentes dans lequel les particules du matériau réfractaire ont une granulométrie inférieure à 500 microns.
  4. Procédé de fabrication d'un composant d'un matériau de métal dur comprenant :
    (a) la formation d'une suspension épaisse d'un matériau de métal dur comprenant plus de 15 et jusqu'à 50 % en volume de particules d'un matériau réfractaire dispersées dans un métal hôte liquide dans une atmosphère inerte, les particules du matériau réfractaire étant sélectionnées parmi : des particules de carbure de niobium ; et des particules d'un mélange chimique de carbure de niobium et de carbure de titane, et le métal hôte comprenant un alliage ferreux (tel qu'un acier, une fonte, un acier inoxydable, un acier austénitique au manganèse), dans lequel les particules sont insolubles dans le métal hôte à sa température de coulée, et
    (b) le versement de la suspension épaisse dans un moule et la formation d'une coulée du composant, telle que dans une atmosphère inerte.
  5. Procédé selon la revendication 4 comprenant la formation de la suspension épaisse et par la suite la formation de la coulée du composant dans une chambre dans des conditions de vide qui éliminent l'air de la chambre et l'introduction d'un gaz inerte, tel que l'argon, dans la chambre.
  6. Procédé selon la revendication 4 ou la revendication 5 dans lequel le matériau réfractaire a une granulométrie inférieure à 400 microns, et de préférence inférieure à 150 microns.
  7. Procédé selon l'une quelconque des revendications 4 à 6 comprenant la sélection d'un ou de plusieurs parmi (a) le fait pour le matériau réfractaire d'avoir une contraction thermique inférieure au métal hôte, (b) le fait pour la densité du matériau réfractaire, comparée à la densité du métal hôte à l'état liquide, de réguler la dispersion des particules du matériau réfractaire dans le métal hôte, et (c) le fait pour le matériau réfractaire pour d'une solubilité à l'état solide minimale dans le métal hôte liquide.
  8. Procédé de formation d'un matériau de métal dur selon l'une quelconque des revendications 1 à 3, comprenant :
    (a) la formation d'une suspension épaisse d'un matériau de métal dur comprenant plus de 15 et jusqu'à 50 % en volume de particules d'un matériau réfractaire dispersées dans un métal hôte liquide, les particules du matériau réfractaire étant sélectionnées parmi : (a) des particules de carbure de niobium contenant des particules réfractaires ; et (b) des particules d'un mélange chimique de carbure de niobium et de carbure de titane, et le métal hôte comprenant un alliage ferreux (tel qu'un acier, une fonte, un acier inoxydable, un acier austénitique au manganèse), dans lequel les particules sont insolubles dans le métal hôte à sa température de coulée, et
    (b) le fait de laisser la suspension épaisse se solidifier pour former un matériau de métal dur solide.
  9. Procédé de formation d'un matériau de métal dur résistant à l'usure défini dans l'une quelconque des revendications 1 à 3, le procédé comprenant l'ajout de titane, et de niobium à une masse fondue d'un métal hôte sous une forme qui produit : (a) des particules de carbure de niobium contenant des particules réfractaires ; et (b) des particules d'un mélange chimique de carbure de niobium et de carbure de titane, dans une plage de plus de 15 et jusqu'à 50 % en volume du volume total du matériau de métal dur, le métal hôte comprenant un alliage ferreux (tel qu'un acier, une fonte, un acier inoxydable, un acier austénitique au manganèse), dans lequel les particules sont insolubles dans le métal hôte à sa température de coulée, et le fait de laisser la masse fondue se solidifier pour former le matériau de métal dur solide.
  10. Procédé de coulée d'un matériau de métal dur ayant une dispersion de matériau réfractaire de : (a) particules de carbure de niobium contenant des particules réfractaires ; et/ou (b) particules d'un mélange chimique de carbure de niobium et de carbure de titane, dans un métal hôte comprenant un alliage ferreux (tel qu'un acier, une fonte, un acier inoxydable, un acier austénitique au manganèse) qui forme une matrice du matériau de métal dur dans une coulée solide, dans lequel les particules représentent plus de 15 et jusqu'à 50 % en volume et sont insolubles dans le métal hôte à sa température de coulée, le procédé comprenant la sélection de la densité des particules de matériau réfractaire par rapport à la densité du métal hôte et par conséquent la régulation sélective de la dispersion des particules de matériau réfractaire dans la matrice d'une coulée solide allant d'une dispersion uniforme à une dispersion non uniforme.
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Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013101561A1 (fr) 2011-12-30 2013-07-04 Scoperta, Inc. Compositions de revêtement
US20140263194A1 (en) * 2013-03-15 2014-09-18 Lincoln Global, Inc. Cored non-arc consumable for joining or overlaying and systems and methods for using cored non-arc consumables
AT514133B1 (de) * 2013-04-12 2017-06-15 Feistritzer Bernhard Ringförmiges Werkzeug
AU2014374832B2 (en) * 2013-12-30 2018-07-26 Weir Minerals Australia Ltd Composite metal product
US10173290B2 (en) 2014-06-09 2019-01-08 Scoperta, Inc. Crack resistant hardfacing alloys
CN104043812A (zh) * 2014-06-11 2014-09-17 张家港市华尊宝特种材料科技有限公司 一种含碳金属部件的制作方法
CN104018042A (zh) * 2014-06-13 2014-09-03 苏州汉力新材料有限公司 一种易导热金属材料
CN104070723A (zh) * 2014-06-17 2014-10-01 张家港市橡燊达机械有限公司 一种复合高塑性金属材料
CN104073672A (zh) * 2014-06-17 2014-10-01 张家港市橡燊达机械有限公司 耐热金属部件的制作方法
CN104073705A (zh) * 2014-06-17 2014-10-01 张家港市橡燊达机械有限公司 一种热双金属材料
DE102014112374A1 (de) * 2014-08-28 2016-03-03 Deutsche Edelstahlwerke Gmbh Stahl mit hoher Verschleißbeständigkeit, Härte und Korrosionsbeständigkeit sowie niedriger Wärmeleitfähigkeit und Verwendung eines solchen Stahls
CN106704718B (zh) * 2015-07-24 2021-02-05 徐工集团工程机械股份有限公司 复合管道、扫路车和复合管道的制造方法
AU2016317860B2 (en) 2015-09-04 2021-09-30 Scoperta, Inc. Chromium free and low-chromium wear resistant alloys
EP3507388A4 (fr) * 2016-08-04 2020-09-23 Weir Minerals Australia Ltd Pièce coulée en matériau composite à matrice métallique
CN106626600A (zh) * 2016-11-08 2017-05-10 西安科技大学 一种硬金属材料
CN107904475A (zh) * 2017-12-11 2018-04-13 四川才阁机械有限公司 一种稳定性高的高性能金属材料
CA3095046A1 (fr) 2018-03-29 2019-10-03 Oerlikon Metco (Us) Inc. Alliages ferreux a teneur reduite en carbures
JP7641218B2 (ja) 2018-10-26 2025-03-06 エリコン メテコ（ユーエス）インコーポレイテッド 耐食性かつ耐摩耗性のニッケル系合金
CN113631750A (zh) 2019-03-28 2021-11-09 欧瑞康美科（美国）公司 用于涂布发动机气缸孔的热喷涂铁基合金
CA3136967A1 (fr) 2019-05-03 2020-11-12 Oerlikon Metco (Us) Inc. Charge d'alimentation pulverulente destinee au soudage en vrac resistant a l'usure, concue pour optimiser la facilite de production
PL448834A1 (pl) * 2024-06-14 2025-12-15 Akademia Górniczo-Hutnicza im. Stanisława Staszica w Krakowie Staliwo chromowe o podwyższonej odporności na ścieranie

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3528808A (en) * 1967-10-11 1970-09-15 United Aircraft Corp Monocarbide reinforced eutectic alloys and articles
US20090025834A1 (en) * 2005-02-24 2009-01-29 University Of Virginia Patent Foundation Amorphous Steel Composites with Enhanced Strengths, Elastic Properties and Ductilities

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1222685B (de) * 1962-11-17 1966-08-11 Kurt Dies Dr Ing Verwendung eines Eisennitrid in eutektoider feiner Verteilung enthaltenden Werkstoffes auf Eisenbasis fuer Gegenstaende, die auf Abnutzung durch Reibung, Gleitung und Verschleiss beansprucht sind
SE369937B (fr) 1970-01-07 1974-09-23 Uddeholms Ab
SE399911C (sv) * 1976-02-05 1980-02-18 Sandvik Ab Slitdetalj med hog slitstyrka och god hallfasthet, sammansatt av hardmetall och gjutjern
JPS60169515A (ja) * 1984-02-10 1985-09-03 Kubota Ltd 耐摩耗鋳物の製造法
US5030519A (en) * 1990-04-24 1991-07-09 Amorphous Metals Technologies, Inc. Tungsten carbide-containing hard alloy that may be processed by melting
US5184389A (en) * 1990-09-11 1993-02-09 Newmont Gold Company Gyratory mantle liner assembly
RU2017578C1 (ru) * 1991-05-05 1994-08-15 Омский политехнический институт Способ изготовления отливок из высокохромистых чугунов
CN1079996A (zh) * 1992-06-08 1993-12-29 东北机器制造总厂 热加工用的轻质硬质合金
US5720830A (en) * 1992-11-19 1998-02-24 Sheffield Forgemasters Limited Engineering ferrous metals and method of making thereof
JPH08506143A (ja) * 1992-11-19 1996-07-02 シェフィールド フォゲマスターズ リミテッド エンジニアリング・フェラス・メタル類
DE4419996C2 (de) * 1993-10-18 1996-10-17 Gfe Ges Fuer Fertigungstechnik Werkzeugschneiden, insbesondere von technischen Messern, mit einer verschleißfesten Verbundschicht und ein Verfahren zur Herstellung der Werkzeugschneiden
US6013141A (en) * 1995-06-06 2000-01-11 Akers International Ab Cast iron indefinite chill roll produced by the addition of niobium
CN1068067C (zh) * 1995-08-25 2001-07-04 东芝图格莱株式会社 含片晶碳化钨的硬质合金及其制备方法
CN1091171C (zh) * 1997-01-13 2002-09-18 中国科学院金属研究所 一种非连续陶瓷增强剂增强的金属基复合材料的制备方法
SE522667C2 (sv) * 2000-05-16 2004-02-24 Proengco Tooling Ab Förfarande för framställning av en legering baserad på järn innehållande kromkarbid med inlöst volfram och en sådan legering
US6332903B1 (en) * 2000-08-04 2001-12-25 Tony U. Otani Materials processing cylinder containing titanium carbide
US7250069B2 (en) * 2002-09-27 2007-07-31 Smith International, Inc. High-strength, high-toughness matrix bit bodies
AU2003902535A0 (en) 2003-05-22 2003-06-05 Weir Warman Ltd Wear resistant cast iron
JP2005068479A (ja) * 2003-08-22 2005-03-17 Tungaloy Corp ホウ素含有超硬合金
US8088232B2 (en) * 2004-08-31 2012-01-03 H.C. Starck Inc. Molybdenum tubular sputtering targets with uniform grain size and texture
WO2006030795A1 (fr) * 2004-09-13 2006-03-23 Hitachi Metals, Ltd. Couche externe obtenue par coulage centrifuge pour cylindre de laminage et procede de fabrication de celle-ci
US8221517B2 (en) * 2008-06-02 2012-07-17 TDY Industries, LLC Cemented carbide—metallic alloy composites
MX350021B (es) * 2008-06-13 2017-08-18 Weir Minerals Australia Ltd Pasador de acople de recubrimiento.
PE20130484A1 (es) * 2010-02-01 2013-04-17 Weir Minerals Australia Ltd Aleaciones de metal para aplicaciones de alto impacto

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3528808A (en) * 1967-10-11 1970-09-15 United Aircraft Corp Monocarbide reinforced eutectic alloys and articles
US20090025834A1 (en) * 2005-02-24 2009-01-29 University Of Virginia Patent Foundation Amorphous Steel Composites with Enhanced Strengths, Elastic Properties and Ductilities

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