EP2531630A1 - Hard metal materials - Google Patents
Hard metal materialsInfo
- Publication number
- EP2531630A1 EP2531630A1 EP11739260A EP11739260A EP2531630A1 EP 2531630 A1 EP2531630 A1 EP 2531630A1 EP 11739260 A EP11739260 A EP 11739260A EP 11739260 A EP11739260 A EP 11739260A EP 2531630 A1 EP2531630 A1 EP 2531630A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- niobium
- hard metal
- titanium
- metal material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007769 metal material Substances 0.000 title claims abstract description 93
- 239000002245 particle Substances 0.000 claims abstract description 154
- 229910052751 metal Inorganic materials 0.000 claims abstract description 84
- 239000002184 metal Substances 0.000 claims abstract description 83
- 238000005266 casting Methods 0.000 claims abstract description 66
- 239000011819 refractory material Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000010955 niobium Substances 0.000 claims description 92
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 claims description 85
- 229910052758 niobium Inorganic materials 0.000 claims description 85
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 70
- 239000010936 titanium Substances 0.000 claims description 70
- 229910052719 titanium Inorganic materials 0.000 claims description 61
- 239000000155 melt Substances 0.000 claims description 55
- -1 titanium carbides Chemical class 0.000 claims description 53
- 229910052804 chromium Inorganic materials 0.000 claims description 39
- 239000011651 chromium Substances 0.000 claims description 39
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 27
- 229910001037 White iron Inorganic materials 0.000 claims description 24
- 239000011159 matrix material Substances 0.000 claims description 24
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 22
- 239000000956 alloy Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- 150000001247 metal acetylides Chemical class 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 229910052723 transition metal Inorganic materials 0.000 claims description 19
- 150000003624 transition metals Chemical class 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 17
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 16
- 229910000617 Mangalloy Inorganic materials 0.000 claims description 12
- 150000004767 nitrides Chemical class 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910001018 Cast iron Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000008602 contraction Effects 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000009257 reactivity Effects 0.000 claims description 3
- 229910000601 superalloy Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 19
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000007792 addition Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 10
- 229910000592 Ferroniobium Inorganic materials 0.000 description 9
- ZFGFKQDDQUAJQP-UHFFFAOYSA-N iron niobium Chemical compound [Fe].[Fe].[Nb] ZFGFKQDDQUAJQP-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005204 segregation Methods 0.000 description 8
- 229910000640 Fe alloy Inorganic materials 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910001275 Niobium-titanium Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 235000000396 iron Nutrition 0.000 description 5
- 238000004663 powder metallurgy Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 238000005552 hardfacing Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000005058 metal casting Methods 0.000 description 3
- 230000031070 response to heat Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 3
- 229910000619 316 stainless steel Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- 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 to components manufactured from the hard metal materials .
- 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.
- powders of metallic binder phase and refractory particles are welded together by pressure and heat. Sintering is
- 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 lOOkgs and typically more than 1 tonne from hard metal materials. This is an issue, particularly in
- 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.
- dispersion typically a dispersion, of 5-50 volume % fine
- particles of a refractory material that is insoluble in the host metal 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.
- 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 comprising 5-50 volume % particles of a refractory material dispersed in a host metal.
- the term "hard metal material” is understood to comprise particles of high melting point carbides and/or nitrides and/or borides of any one or more than one of the nine transition metals titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten 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 and/or borides and/or nitrides of one transition metal, such as bC.
- the particles of the refractory material may be carbides and/or borides and/or nitrides of more than one transition metal where the particles are a chemical mixture (as opposed to a physical mixture) of the carbides and/or borides and/or nitrides of the transition metals .
- the particles of the refractory material may be of the type described as (Mi,M2) C , where "M” is a transition metal.
- the hard metal material may comprise 5-40 volume % particles of the refractory material dispersed in the host metal.
- the hard metal material may comprise greater than 10 volume % particles of the refractory material dispersed in the host metal.
- the hard metal material may comprise greater than 15 volume % particles of the refractory material dispersed in the host metal.
- the hard metal material may comprise less than 30 volume %
- the hard metal material may comprise less than 25 volume %
- 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 .
- the present invention also provides a method of forming a hard metal material comprising:
- the present invention also provides a method of manufacturing a component of a hard metal material comprising:
- 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 microstrueture for the component.
- the production parameters may comprise any one or more of the particle size, reactivity, density, and solubility of the
- 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
- 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 .
- (a) As a fine powder with a selected particle size distribution. For example, 15 wt.% of particles of a refractory material in the form of niobium carbide (NbC) (minus 50 microns in diameter) added to a liquid host metal in the form of a high chromium white cast iron host metal. NbC exhibits a Vickers Hardness of 24 GPa, a melting point of 3600°C, and a very low solubility in the host liquid metal at a casting temperature of about 1500°C.
- the liquid metal slurry comprises a suspension of insoluble NbC particles
- the microstrueture exhibits a dispersion of 15 volume% fine NbC particles (minus 50 microns in diameter) in a high chromium white cast iron matrix containing a negligible amount (less than 0.3 wt.%) of niobium in solution in the matrix.
- the transition metals mentioned above or ferro-alloys of the same transition metals can be added to a wide range of host metals containing all the combinations and permutations of the elements carbon, boron and nitrogen.
- Fe- b 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, nitride or boride 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 CO 2 which can result in severe porosity in the castings.
- reactive elements i.e. the individual metal elements and/or their carbide, nitride or boride 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 CO 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.
- refractory material particles that firmly held the particles in the host metals on solidification. All refractory particles in hard metal material castings produced by the applicant in an inert atmosphere were found to be under compressive loading ensuring intimate contact and good bonding with the host metals. Density of refractory materials
- the density of the refractory material of the particles compared to the density of the host metal in the liquid state, 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
- the nominal density of a host ferrous liquid metal at 1400 °C is 6.9 grams/cc.
- 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
- 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 .
- 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
- 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
- the three hard metal materials produced by the method of the present invention display the known physical and chemical
- 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.
- 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.
- the method comprising adding (a) niobium or (b) niobium and titanium to a melt containing a host metal in a form that produces particles of niobium carbide and/or particles of a chemical mixture of niobium carbide and titanium carbide in a range of 10 to 40 wt% of the total weight of the hard metal material, and allowing the melt to solidify to form the solid hard metal material .
- niobium/titanium carbides 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 microstrueture 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
- 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
- the method may comprise adding the niobium to the melt in the form of ferro-niobium, for example particles of ferro- niobium.
- 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
- 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
- the particles of niobium/titanium carbides may be any suitable chemical mixture of a general formula ( b x ,Ti y )C.
- the niobium/titanium carbides may be ( bo.5,Tio.s) C or ( bo.25,Ti 0 . 75 )C or ( bo. 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 .
- niobium/titanium carbides in the microstrueture 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) .
- the quantity of particles of niobium carbide and/or niobium/titanium carbides in the final microstrueture 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 um in diameter.
- the method may comprise stirring the melt with an inert gas or magnetic induction or any other suitable means in order to
- 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
- 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 microstrueture to achieve desired alloy
- the casting may comprise a uniform dispersion of the
- the casting may be a pump impeller.
- the casting may comprise a non-uniform dispersion of the
- 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) .
- Figure 1 is a micrograph of a high chromium white cast iron alloy including 27 wt% chromium and 15 wt% niobium carbides.
- Figure 2 is a micrograph of martensitic stainless steel (grade 420C) including 15 wt% niobium carbides.
- the applicant carried out an extensive series of laboratory melting trials on the addition of 10 to 30 wt% NbC and Nb/TiC particles to a wide selection of ferrous alloys including high chromium white irons, austenitic-manganese steels (including
- FIG. 1 An example of a microstrueture 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
- the applicant has examined the use of various other particle size ranges of NbC, including ⁇ 45 um in diameter, 45 to 75 um in diameter, 75 to 150 um in diameter and ⁇ 100 um 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.
- microstrueture in Figure 1 exhibits a ferrous matrix
- microstrueture 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
- 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.
- ferro-niobium additions 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. Upon solidification, the casting will have a
- microstrueture that includes niobium carbides dispersed in a ferrous matrix. A similar microstrueture is achieved with
- Hardness of NbC is approx 2500 HV which compares to a hardnes of 1500 HV for M 7 C3 carbides present in high chromium white cast iron alloys.
- Niobium is a very strong carbide former and can be added as ferro niobium or NbC powder to the ferrous melt.
- the melting point of NbC is 3600°C, i.e. about 2000°C above the temperature of the ferrous melt of steels, cast irons and hard-facing weld deposits. Additionally, fine NbC particles (e.g. 2 to 20 um in diameter) do not grow in size or coalesce in the melt during the casting process. This is important in terms of the castability of the melt and the resultant wear resistance of the cast product.
- the wear resistance of the cast product is optimised when a dispersion of fine NbC particles is evenly distributed throughout the microstrueture .
- NbC particles high melting point NbC particles. Accordingly, the chemical composition of the NbC particles is not altered and they will retain their physical properties during preparation of the melt and after casting. (e) The solubility of NbC in the ferrous matrix is negligible
- NbC The density of NbC is 7.82 grams/cc at room temperature. This is very close to the densities of ferrous materials which are approximately 7.5 grams/cc. This means that NbC particles will not segregate in the liquid melt by sinking (compared with tungsten carbide, for example, which has a density of 15.8 grams/cc) or by floating (compared with titanium carbide, for example, which has a density of 4.93 grams/cc).
- 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
- high chromium white cast iron undergoes a step increase in volume at the solid to liquid phase change at
- 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
- 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
- the niobium/titanium carbides may be (Nbo.5,Ti 0 .5) C or (Nb 0 .25,Ti 0 . 7 5) C or (Nb 0 . 7 5,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.
- the density of the niobium/titanium carbides within the range of 4.9-7.8 grams/cc and control whether the particles will form a uniform dispersion in or segregate in a casting of a metal alloy, such as a high chromium white iron, which includes the particles .
- 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-l .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 .
- Microstructure 90 volume% white cast iron + 10 volume% NbC
- 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 . It is noted that the bulk chemistry is even more complicated when carbides and/or nitrides and/or borides of two or more transition metals are included in the hard metal materials .
- 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
- 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.
Abstract
Description
Claims
Applications Claiming Priority (3)
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AU2010900457A AU2010900457A0 (en) | 2010-02-05 | Wear resistant metal alloys | |
AU2010904416A AU2010904416A0 (en) | 2010-10-01 | Wear Resistant Metal Alloys | |
PCT/AU2011/000092 WO2011094800A1 (en) | 2010-02-05 | 2011-02-01 | Hard metal materials |
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EP2531630A1 true EP2531630A1 (en) | 2012-12-12 |
EP2531630A4 EP2531630A4 (en) | 2014-04-02 |
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EP (1) | EP2531630B1 (en) |
KR (3) | KR20190107188A (en) |
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CN106626600A (en) * | 2016-11-08 | 2017-05-10 | 西安科技大学 | Hard metal material |
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AP2012006430A0 (en) | 2012-08-31 |
CN104805346A (en) | 2015-07-29 |
MX345311B (en) | 2017-01-25 |
CN102822367A (en) | 2012-12-12 |
MY178072A (en) | 2020-10-01 |
WO2011094800A1 (en) | 2011-08-11 |
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CA2788673A1 (en) | 2011-08-11 |
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PL2531630T3 (en) | 2023-09-18 |
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KR20190107188A (en) | 2019-09-18 |
US20130039800A1 (en) | 2013-02-14 |
AU2016203320A1 (en) | 2016-06-09 |
AU2011213543A1 (en) | 2012-08-30 |
IL221232B (en) | 2019-03-31 |
PE20130483A1 (en) | 2013-04-17 |
ES2950985T3 (en) | 2023-10-17 |
KR20120123693A (en) | 2012-11-09 |
AP3219A (en) | 2015-04-30 |
EA033535B1 (en) | 2019-10-31 |
KR20180045067A (en) | 2018-05-03 |
US20190003014A1 (en) | 2019-01-03 |
CA2788673C (en) | 2019-04-09 |
EP2531630B1 (en) | 2023-05-24 |
ZA201206300B (en) | 2013-04-24 |
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AU2018201084A1 (en) | 2018-03-08 |
AU2018201084B2 (en) | 2020-03-05 |
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