EP2527480A1 - Liant NiFe ayant une application universelle - Google Patents

Liant NiFe ayant une application universelle Download PDF

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Publication number
EP2527480A1
EP2527480A1 EP11167901A EP11167901A EP2527480A1 EP 2527480 A1 EP2527480 A1 EP 2527480A1 EP 11167901 A EP11167901 A EP 11167901A EP 11167901 A EP11167901 A EP 11167901A EP 2527480 A1 EP2527480 A1 EP 2527480A1
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Prior art keywords
alloy
weight
base
hardness
powder
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EP11167901A
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German (de)
English (en)
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EP2527480B1 (fr
Inventor
Dr. Benno Gries
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Hoganas Germany GmbH
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HC Starck GmbH
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Application filed by HC Starck GmbH filed Critical HC Starck GmbH
Priority to ES11167901.5T priority Critical patent/ES2628422T3/es
Priority to PL11167901T priority patent/PL2527480T3/pl
Priority to EP11167901.5A priority patent/EP2527480B1/fr
Priority to US14/122,246 priority patent/US9821372B2/en
Priority to KR1020137032074A priority patent/KR102079325B1/ko
Priority to JP2014513132A priority patent/JP6124877B2/ja
Priority to PCT/EP2012/059748 priority patent/WO2012163804A1/fr
Priority to CN201280025581.3A priority patent/CN103562422B/zh
Priority to RU2013158048A priority patent/RU2623545C2/ru
Publication of EP2527480A1 publication Critical patent/EP2527480A1/fr
Priority to IL229654A priority patent/IL229654B/en
Publication of EP2527480B1 publication Critical patent/EP2527480B1/fr
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Priority to US15/730,747 priority patent/US11207730B2/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/105—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing inorganic lubricating or binding agents, e.g. metal salts
    • 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
    • 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
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • 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
    • C22C29/06—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 based on carbides, but not containing other metal compounds
    • 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
    • C22C29/06—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 based on carbides, but not containing other metal compounds
    • C22C29/067—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 based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel

Definitions

  • the invention relates to a process for producing a composite material obtainable by sintering a composition containing a hard carrier and a FeCoNi or FeNi based base binder alloy. Moreover, the invention relates to a sintered composite material, which is obtainable according to the method and its use for tools or components, in particular forming or comminution tools.
  • Cemented carbide is a sintered composite of hardeners, such as carbides and a binder alloy.
  • Carbides are used in many different ways and are used, for example, for processing practically all known materials.
  • Hard metals may also be used, for example, as a structural component, as a forming or comminution tool or for a variety of other purposes, where it depends particularly on wear resistance, mechanical strength or high temperature resistance.
  • a common field of application is the cutting of metallic materials. Due to machining, forming and friction processes locally limited temperatures up to 800 ° C. In other cases, forming operations of metallic workpieces are performed at high temperatures, such as forging, wire drawing or rolling. The tool is under mechanical stress, which can lead to deformation of the carbide tool.
  • high-temperature creep resistance in practice, the hot hardness is usually determined as a substitute
  • the fracture toughness K 1 C
  • the wear resistance, the hot hardness, the fracture toughness and the related strength can be adjusted by the size of the carbide phase and its proportion of the hard metal composition.
  • the present invention relates to novel hard metals having a FeNi or FeCoNibas striving binder alloy, which in hardness (Vickers hardness according to ISO 3878), fracture toughness (K 1 C, calculated according to the formal of Shetty from the crack lengths and the size of Vickershärteeindrucks) and hot hardness the properties of those hitherto conventional hard metals correspond to a Co-based binder alloy.
  • base binder alloying is meant also pure metals with unavoidable impurities, for example, available as commercially available nickel and cobalt metal powders.
  • Ni metal powders are used as a base alloy for the production of corrosion-resistant, oxidation-resistant or non-magnetisable hard metals.
  • the sintering in the liquid phase leads to the formation of a binding alloy based on Ni.
  • This binder alloy contains elements such as W, Co, Cr, Mo, or others added to the cemented carbide base as a metal powder or carbide, for example, and their content in the pure Ni by alloying in the liquid phase sintering to the resulting Ni-base alloy. These elements lead to a better corrosion resistance compared to pure nickel.
  • Hard metals with Ni as a binder-based alloy are not universally used because of their low hardness values compared to those bound with Co-base alloys.
  • hard metals bonded with Ni-base alloys are characterized by comparatively low thermal hardness. Therefore, they are not used in the machining of metallic materials.
  • FeCoNi-based alloys are known as carbide binders.
  • their disadvantage is their low K 1 C values, which is proportional to the strength according to the Griffith equation up to binder contents of about 12% by weight.
  • the K 1 C values of a hard metal made from a tungsten carbide based hard carrier (mean powder diameter: 0.6 ⁇ m) with 7.5% FeCoNi 40/20/40 are between 8.2 and 9.5 MPa m 1/2 while a cemented carbide having the same volume fraction of cobalt (corresponding to 8 wt% due to the higher density of cobalt compared to FeCoNi 40/20/40) reaches a K 1 C of 9.5 MPa m 1/2 .
  • the hot curing of hard metals with FeCoNi base alloys as binders are usually lower at higher temperatures than those bound with cobalt base alloys.
  • FeNi-based alloys are also known as binders.
  • WO-A1-2002 / 0112896 describes FeNi alloys based on 35 to 65% Ni and 65 to 35% Fe.
  • the strength of the described base alloy FeNi 50/50 at room temperature, however, is comparatively low;
  • a carbide with 7.4% FeNi 50/50 volume fraction of the binder corresponding to 8 wt% cobalt due to the lower density of FeNi 50/50
  • FeNi-based alloys with 10 to 50% Ni, Fe 90 to 50% from the dissertation Wittmann (TU Vienna) are known.
  • these have very high K 1 C values (over those achievable with cobalt as the binder-based alloy, see results of Wittmann, evaluated published in: L.Prakash and B.Gries, Proceedings 17th Plansee Seminar 2009, Vol.2, HM 5/1 ).
  • This also applies to a FeNi 75/25 (see above source, there referred to as "A2500").
  • hard metals are with a FeNi 50/50 base alloy having a tungsten solubility in the binder alloy of at most 19.4% equivalent to a cobalt base alloy (maximum 20% W in the binder alloy) in terms of the thermal hardness.
  • tungsten carbides with Ni-base alloys are inferior to both of the above with respect to the hot hardness, and therefore are not used for applications where it comes to high hot hardness such as in metal cutting.
  • EP-B1-1 488 020 FeCoNi base alloys with 10 to 75% Co are known as fcc-structured carbide binders for special machining tasks designed to reduce the adhesive wear that occurs during the machining of special steels.
  • the hot curing of such hard metals with austenitic FeCoNi-based alloys are clearly inferior to those with cobalt-based alloys. It is also believed that, in addition, the strength values of hard metals from these austenitic binder alloys will be lower compared to those hard metals bonded with a cobalt-based alloy.
  • WO-A2-2010 / 046224 describes the use of molybdenum-doped FeCoNi-, Co-, Ni- and Ni-based powdered metal powders alloyed with molybdenum.
  • the hot curing of a WC and 8% Co is not quite reached with 82% of the maximum magnetic saturation ( FIG. 2 of the WO-A2-2010 / 046224 ).
  • the K 1 C is very much dependent on the carbon content of the cemented carbide (Example 4 of the WO-A2-2010 / 046224 ), which tends to fluctuate in industrial sintering practice.
  • the safe achievement of the required properties hardness, K 1 C and hot hardness sensitive depends on the control of the carbon balance, which is not always ensured under industrial conditions.
  • cemented carbide lung In the current production of cemented carbide via powder metallurgical production processes, i. Pressing and sintering of powdered tungsten carbide formulations releases respirable dusts due to the process. If grinding is used in the sintered or pre-sintered state of the hard metal, very fine, breathable dusts (grinding dusts) are also produced.
  • acute inhalation toxicity may additionally occur during the grinding of pre-sintered hard metals or also sintered hard metals.
  • An object of the present invention was therefore to improve the safety of work, hard metals, i. To provide sintered composites that have a reduced acute toxic effect.
  • the base binder alloy has a weight ratio of iron: nickel of from 1: 2 to 1:13, preferably 1: 2.5 to 1:12, more preferably 1: 3 to 1:10, and most preferably 1: 3 to 1: 9, more preferably 1: 4 to 1: 8, for example 1: 4 to 1: 7.
  • base binder alloys comprising 66 to 90% by weight, preferably 70 to 90% by weight of nickel.
  • Base binder alloys having 10 to 34 wt% iron are preferred. Particularly preferred is an iron content in the base binder alloy of 10 to 30 wt .-%.
  • the base binder alloy contains the Basisbindeleg ist therefore less than 8 wt .-%, preferably less than 5 wt .-%, in particular less than 1 wt .-% of cobalt.
  • the base binder alloy is substantially free of cobalt.
  • the base binder alloy is substantially free of other elements, in particular substantially free of metals other than nickel and iron.
  • Nonmetals such as carbon, oxygen and nitrogen may be present in the base binder alloys and are acceptable because their contents in the sintered composite may be desirable and may volatilize in whole or in part during sintering.
  • Essentially free in the sense of the present invention means that the element in an amount of less than 0.5 wt .-%, preferably less than 0.1 wt .-%, more preferably less than 0.08 wt .-% and in particular less than 0.02 wt .-% and in particular less than 0.001 wt .-%, for example less than 0.005 wt .-%, each based on the total weight of the base binder alloy, is present.
  • the base binder alloy contains less than 0.1% by weight, preferably less than 0.08% by weight, in particular less than 0.02% by weight, in particular less than 0.01 Wt .-% molybdenum.
  • the hardness carrier is selected from the group consisting of carbides, nitrides, borides and carbonitrides. These particularly preferably contain one or more elements of the 4th, 5th or 6th subgroup of the periodic table. It may be both binary hardness carrier, in particular tungsten carbide, as well as to ternary hardness carrier, such as tantalum-niobium mixed carbide, titanium carbonitride or tungsten-titanium carbide or even quaternary, such as tungsten-titanium-carbonitride or tungsten-titanium-niobium -Tantalcarbid.
  • the hardness carrier is selected from the group consisting of titanium carbide, chromium carbide, tantalum carbide, niocarbide, vanadium carbide, molybdenum carbide, tantalum-niobium mixed carbide, titanium carbonitride, tungsten-titanium carbide, tungsten-titanium carbonitride, and in particular tungsten carbide.
  • the hardness carrier comprises at least 50 wt.% Tungsten carbide, based on the total weight of the hardness carriers.
  • the hardness carriers are preferably in powder form.
  • the powders have an average particle diameter of 0.01 to 150, preferably 0.1 to 100 microns.
  • the average particle diameter is determined according to ASTM B330.
  • the hardness carriers preferably have a hardness above 800 kg / mm 2 , in particular above 1000 kg / mm 2 (measured in accordance with ISO 6507, Part 2).
  • the composition used in the process of the invention may preferably contain various powdery components.
  • the FeNi or FeCoNi based binder base alloy can be provided by prealloyed or melt-derived powders, but also by metal powder, i. for example, by iron, nickel and optionally cobalt powder.
  • the hardness carrier and / or the base binder alloy is present in powder form.
  • the base binder alloy is present as alloy powder.
  • compositions used in the process according to the invention may optionally also contain other components as additives, such as metals, for example selected from the group consisting of rhenium, molybdenum, chromium and aluminum.
  • additives such as metals, for example selected from the group consisting of rhenium, molybdenum, chromium and aluminum.
  • elemental tungsten or elemental carbon can be preferably used because it is used to correct the carbon content of the composite after sintering suitable is.
  • intermetallic compounds such as Ni 3 Al or chromium nitride decomposing during sintering can also be added to the compositions to be sintered.
  • additives may constitute up to 20% by weight, preferably up to 10% by weight, the weight data being based on the total weight of the composition.
  • the composition to be used in the process according to the invention comprises from 50% by weight to 97% by weight of hard carrier, more preferably from 60% by weight to 96% by weight, in particular from 70% by weight to 96% by weight. % Hardness carrier, in each case based on the total weight of the composition.
  • the composition contains from 3 to 50% by weight of the base binder alloy, preferably from 4 to 40% by weight, in particular from 4 to 30% by weight, of the base binder alloy, based in each case on the total weight of the composition.
  • the total weight of base binder alloy, hardness carrier and optionally present additives is supplemented to 100 wt .-%.
  • the sintering is preferably carried out at temperatures above 1000 ° C, more preferably above 1100 ° C and in particular at temperatures between 1150 ° C and 1600 ° C.
  • the sintering is in the presence of liquid phase.
  • the base binder alloy is completely or partially present in liquid form during the sintering process.
  • the duration of sintering may vary. Usually sintering takes place over a period of at least 5 minutes, preferably at least 10 minutes. Sintering time and sintering temperature are related because at higher sintering temperatures the time required for complete compaction can be shortened. The necessary Sinterzeit- and in particular temperature also depends heavily on the content of binder base alloy. For example, while the base biting alloy content of 20 wt% could reduce the sintering temperature to as high as 1250 ° C, 5 wt% base binder alloying would have temperatures from above 1400 ° C desirable.
  • the realizable sintering times depend on the heat capacity of the sintering furnaces, since they can not be heated and cooled arbitrarily fast to sintering temperature. However, very short sintering times of a few minutes can be achieved by microwave sintering or so-called SPS sintering.
  • step a) The provision of the dispersion described in step a) is carried out in a preferred embodiment by adding a solvent to a pulverulent composition containing a hardness carrier and base binder alloy powder.
  • Preferred solvents are those which have a boiling point of ⁇ 250 ° C at 1 bar.
  • alcohols in particular aliphatic alcohols, for example ethanol, and water or mixtures thereof, for example mixtures of water and organic solvents, in particular water and alcohols.
  • organic solvents in particular selected from the group consisting of ketones and hydrocarbons, for example acetone and aliphatic hydrocarbons, such as heptane and hexane.
  • the milling of the dispersion prepared in step a) can be carried out using milling tools familiar to the person skilled in the art.
  • the milling of the dispersion is carried out in a ball mill or a gate, which are particularly preferably equipped with hard metal balls.
  • the dispersion may optionally additionally contain organic auxiliaries, such as waxes, dispersion aids, inhibitors, adhesives or emulsifiers, before the drying step.
  • organic auxiliaries such as waxes, dispersion aids, inhibitors, adhesives or emulsifiers
  • step b) is followed by preparing a powder by drying the dispersion.
  • the dispersion may, for example, be spray-dried or dried under reduced pressure.
  • the solvent low-boiling solvent which can be easily distilled off under reduced pressure.
  • the dried powder from step c) is used to produce compacts or extrudates.
  • the pressing of the dried powder is preferably carried out in suitable tools, or isostatically.
  • step e) the compact or the extrudate is sintered.
  • the sintering is carried out in the presence of a protective gas atmosphere or under reduced pressure.
  • the sintered composites are further densified at elevated pressure in a separate or integrated post-densification step.
  • the pressing and the sintering are carried out simultaneously and preferably by additional application of electric fields or currents. These can provide an elevated temperature during sintering and compression.
  • the composite materials obtained according to the method according to the invention are optionally subsequently ground to the required shape, with tools for metal cutting usually by means of chemical vapor deposition techniques (CVD) or physical vapor deposition (PVD) or combined methods can be further coated.
  • CVD chemical vapor deposition techniques
  • PVD physical vapor deposition
  • a further subject of the present invention is a sintered composite material obtainable according to the method according to the invention.
  • the composite materials according to the invention include as binder alloy one or more elements of the group Fe, Ni and optionally Co.
  • binder alloy elements whose content in the binder alloy in contrast to the above is not arbitrary, but the result of solubilities and Balance settings during sintering are. These are in particular W, Mo and Cr, but in smaller amounts, other carbide-forming metals (for example, V, Ti, Zr, Hf, Ta, Nb) and in particular carbon, but also non-carbide-forming metals such as rhenium and ruthenium.
  • the binder alloy present in the sintered hard metal therefore only forms during sintering from the base alloy and the equilibrium settings with the other components that are still contained in the hard metal.
  • the base alloy may already contain such elements. However, the final composition of the binder alloy does not become established until sintering and subsequent cooling of the cemented carbide.
  • the binder alloy may also contain one or more elements selected from the group consisting of W, Mo, Cr, V, Ta, Nb, Ti, Zr, Hf, Re, Ru, Al, Mn, C.
  • These elements have limited solubility in FeNi base alloy as well as in other base alloys, and their contents on sintering and cooling due to their temperature-dependent solubility in addition to the carbon content according to the principle of the solubility product of the carbides depending on their thermodynamic stability.
  • the sum of these elements in the binder alloy according to the invention is therefore generally less than 30 wt .-%, based on the total weight of the binder alloy of the sintered composite material.
  • the binder alloy of the sintered composite of the invention comprises up to 30% by weight of one or more elements selected from the group consisting of W, Mo, Cr, V, Ta, Nb, Ti, Zr, Hf, Re, Ru , Al, Mn, B, N and C.
  • the selection and contents of the above elements have an influence on the properties of the binder alloy.
  • W, Cr and Mo increase the hot hardness due to their solubilities on the order of a maximum of 5 to 25% by weight. Therefore, it is desirable in industrial practice to set the carbon of the cemented carbide so low that the contents of these elements in the binder alloy are as high as possible without causing harmful carbon deficiency phases (so-called eta phases).
  • the actual dissolved tungsten content in hard metals with Co base alloys is determined by the magnetic saturation. If the magnetic saturation of the Co content of pure WCCo hard metals is less than 70% that of pure cobalt, eta phases are formed. For industrial reasons, however, a safety margin is kept to this limit for reasons of process safety.
  • the sintered composite materials according to the invention can be ground and coated, depending on the requirement of the intended application. They can also be used in tool holders, joined, soldered or diffusion welded.
  • cemented carbides according to the invention can be used for all applications where cemented carbides with a cobalt, nickel, CoNi, FeNi or FeCoNi-based cemented carbide are used today.
  • the hard metal part present after sintering and optionally after the grinding or electroerodizing finishing advantageously has a defined geometry.
  • This may particularly preferably be elongated (for example, ground out of a sintered round rod), but particularly preferably also plate-shaped for the rotary or milling machining of materials such as metals, stones and composite materials.
  • the cemented carbide tools may preferably have one or more coatings from the classes of nitrides, borides, oxides or superhard layers (eg, diamond, cubic boron nitride). These can be applied by PVD or CVD methods or their combinations or variations and still be changed after application in their residual stress state.
  • carbide parts of further and arbitrary geometry and application such as forging tools, Forming tools, countersinks, components, knives, peeling plates, rollers, punching tools, pentagonal drill bits for soldering, mining chisels, milling tools for milling concrete and asphalt, mechanical seals as well as any other geometry and application.
  • the carbide may also have the surface resulting from sintering, and optionally subsequently coated or uncoated used.
  • the sintered composite material according to the invention can be used for forming or comminution tools.
  • the tool is a tool for cutting metallic tools or for forming metallic workpieces at high temperatures, for example a tool for forging, wire drawing or rolling.
  • the ethanol was separated by distillation in vacuo, and pressed the obtained hard metal powder axially at 150 MPa and sintered at 1420 ° C.
  • the plate-shaped hard metal pieces were ground, polished and examined for their properties. Both batches showed no eta phases or carbon precipitates as sinters.
  • the different carbon content after sintering and the consequent different tungsten content in the binder metal alloy is the result of mass transfer during sintering.
  • the binder metal alloy in the base is cobalt, with proportions of tungsten and possibly carbon.
  • both hard metal batches were sintered again and the pieces obtained had a density of 14.79 g / cm 3 and a magnetic saturation of 127 (+/- 1) Gcm 3 / g, corresponding to 78.5% of the theoretically possible magnetic saturation, im Case of the "low carbon” variant.
  • the "high carbon” variant had on average a density of 14.75 (+/- 0.01) g / cm 3 and a magnetic Saturation of 133 (+/- 1) Gcm 3 / g, corresponding to 82% of theoretical saturation.
  • Example 1 was repeated, but the two batches consisted of 461.5 g tungsten carbide with 0.6 ⁇ m grain size and the binder metal base of 38.5 g of an alloy powder with 15% by weight Fe and 85% by weight Ni.
  • the carbon content of these hard metal batches was adjusted by soot addition (5.55% for the "low carbon” variant or 5.65% for the "high carbon” variant), that after sintering at 1440 ° C. for 60 minutes neither eta-phases are still obtained carbon precipitates.
  • the different carbon content after sintering and the consequent different tungsten content in the binder metal alloy is the result of mass transfer during sintering.
  • the binder metal alloy in the base consists of iron and nickel in a weight ratio of 1: 5.7, alloyed with proportions of tungsten and possibly carbon.
  • the room temperature hardnesses are slightly lower than those of Example 1, which is due to the low hardness and higher plasticity of the austenitic base alloy.
  • the fracture toughness even taking into account the somewhat lower hardnesses, is at least at the same level as in example 1. Increasing carbon values in the sintered material correlate with increasing magnetic saturation and - due to the low density of graphite - with decreasing density.
  • the hot hardnesses were determined as before (see results FIG. 1 ).
  • new sintered bodies were made from the existing hard metal approaches.
  • a density of 14.81 g / cm 3 and a magnetic saturation of 54 to 55 Gcm 3 / g was achieved with the "low carbon” variant.
  • Densities between 14.77 and 14.79 g / m 3 and magnetic saturations between 70.5 and 72.5 Gcm 3 / g were achieved with the "high carbon” variant.
  • the limit for the eta phase is below 51 Gcm 3 / g, the limit for carbon excretion at about 75 Gcm 3 / g.
  • the sintered pieces were thus free from eta-phase and carbon precipitations.
  • the two sinter batches were in the middle and in the high, but not in the low range for the carbon content, which would have been beneficial for a high hot hardness.
  • FIG. 1 with the course of the hot curing shows that the hard metals according to the invention are based on FeNi base despite the average and high carbon content in the range of thermal hardness of hard metals such as cobalt-based, have the same volume fraction of base binder alloy and in the lower half of the carbon window, and thus have favorable heat curing.
  • the results obtained for the hot hardness are thus determined by the nature of the base binder alloy. It should be noted that this effect occurs although the initial level of hardness is lower compared to Example 1.
  • the room-temperature hardnesses in the hot-cure curve are not consistent with those in the above Tables of Examples 1 and 2 since they were determined using another hardness tester, the hot-hardness tester.
  • Example 2 HC Starck GmbH, D, composition: Analogously to Example 2, different approaches (from a WC (0.6 micron grain size and 7.5% of a FeCoNi alloy powder AMPERSINT ® MAP A6050, manufacturers were Fe 40%, Co 20%, Ni40%) The volume fraction of the base binder alloy corresponds to that of Example 1.
  • the resulting cemented carbides containing neither eta phase nor carbon precipitates had an HV30 between 1626 and 1648.
  • the K 1 C values were for the most part between 8.5 and 8.9 MPa m 1/2 . Only in a very narrow range with high carbon contents at the boundary to the area of carbon precipitation, values of 9.3 to 9.5 for the K 1 C were found.
  • cemented carbides having a FeCoNi 40/20/40 base bond in terms of K 1 C and hot hardness are inferior to those bonded with cobalt as the base for the binder alloy.
  • Example 2 Hard metals with 7.4 wt% of a FeNi 50/50 alloy powder (AMPERSINT MAP ® A5000, manufacturer HC Starck GmbH, D) were prepared as the base binder alloy.
  • the volume fraction of the base binder alloy corresponds to that of Example 1.
  • the K 1 C values were between 8.3 and 8.6 MPa m 1/2 .
  • FIG. 2 shows that the hot hardnesses correspond to those of a corresponding carbide with cobalt as the binder alloy base.
  • carbides with a FeNi 50/50 based alloy have at least equal hot hardness, but show comparatively low K 1 C values, which means carbides bonded in this way can not be used universally ( Fig. 3 ).
  • carbides with this binder-based alloy can be used for turning metal, but not for milling because of their low K 1 C value, since the mechanical shock resistance is insufficient.
  • Hard metals with different Fe / Ni ratios between 35/65 and 0/100 were prepared analogously to Example 1.
  • the volume fraction of the binder base alloy was that of Example 1.
  • the Fe: Ni ratio variation in the binder base alloy was adjusted by FeNi 50/50 as in Example 4 (Fe: Ni ratio 1: 1) and Ni. Powders (manufacturer: Vale-Inco, GB, type 255) were used in amounts such that the desired Fe: Ni ratio was obtained, and the volume fraction of Example 1 was achieved.
  • By additionally varying the carbon content in the batches it was ensured that all cemented carbides were free of carbon deposits and of eta phases after sintering. All hard metals were sintered together at 1420 ° C for 60 minutes.
  • Table 3 Fe / Ni HV30 K1C density magnetic relationship (kg / mm 2) (MPa m 1/2 ) (g / cm 3 ) saturation (G cm 3 / g) 35/65 * 1618 9.2 14.75 102 25/75 * 1626 9.3 14.67 94.7 15/85 * 1608 9.4 14,74 98.4 10/90 * 1618 11.3 14.84 42.3 5/95 1541 10.7 14.79 38.2 0/100 1478 12.4 14.81 42.7
  • FIGS 2 and 3 illustrate the results of Example 4 and Examples 1 and 4 in comparison.
  • the hardness barely drops from 50% Ni to unexpectedly high Ni contents of 90%.
  • the course of the hardness is surprisingly almost constant up to values of 90% Ni, then drop off abruptly. It can be interpolated that the required hardness level, which results from the lower hardness value of Comparative Example 1, is achieved at Ni contents of up to 93%.
  • the combination of properties of the WCCo cemented carbides of Example 1 are achieved with a Fe / Ni ratio of between about 34/66 (corresponding to about 1: 2) and 7/93 (corresponding to about 1:13), below which the K 1 C falls off, on top of that, the hardness drops off sharply and sharply.

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EP11167901.5A 2011-05-27 2011-05-27 Liant NiFe ayant une application universelle Active EP2527480B1 (fr)

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ES11167901.5T ES2628422T3 (es) 2011-05-27 2011-05-27 Aglutinante de FeNi con aplicabilidad universal
PL11167901T PL2527480T3 (pl) 2011-05-27 2011-05-27 Spoiwo NiFe o uniwersalnym zastosowaniu
EP11167901.5A EP2527480B1 (fr) 2011-05-27 2011-05-27 Liant NiFe ayant une application universelle
PCT/EP2012/059748 WO2012163804A1 (fr) 2011-05-27 2012-05-24 Liants feni ayant une aptitude à la mise en oeuvre universelle
KR1020137032074A KR102079325B1 (ko) 2011-05-27 2012-05-24 보편적 유용성을 갖는 FeNi 결합제
JP2014513132A JP6124877B2 (ja) 2011-05-27 2012-05-24 汎用性を有するＦｅＮｉバインダー
US14/122,246 US9821372B2 (en) 2011-05-27 2012-05-24 FeNi binder having universal usability
CN201280025581.3A CN103562422B (zh) 2011-05-27 2012-05-24 通用型FeNi-粘结剂
RU2013158048A RU2623545C2 (ru) 2011-05-27 2012-05-24 FeNi - СВЯЗУЮЩИЙ АГЕНТ С УНИВЕРСАЛЬНЫМИ ВОЗМОЖНОСТЯМИ ИСПОЛЬЗОВАНИЯ
IL229654A IL229654B (en) 2011-05-27 2013-11-27 A universally useful iron-nickel binder
US15/730,747 US11207730B2 (en) 2011-05-27 2017-10-12 FeNi binder having universal usability

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CN108350528B (zh) 2015-09-04 2020-07-10 思高博塔公司 无铬和低铬耐磨合金
US10287824B2 (en) 2016-03-04 2019-05-14 Baker Hughes Incorporated Methods of forming polycrystalline diamond
CN109072347A (zh) 2016-04-20 2018-12-21 奥科宁克有限公司 铝、钴、铁和镍的fcc材料及由其制成的产物
US11434549B2 (en) * 2016-11-10 2022-09-06 The United States Of America As Represented By The Secretary Of The Army Cemented carbide containing tungsten carbide and finegrained iron alloy binder
US11396688B2 (en) 2017-05-12 2022-07-26 Baker Hughes Holdings Llc Cutting elements, and related structures and earth-boring tools
US11292750B2 (en) 2017-05-12 2022-04-05 Baker Hughes Holdings Llc Cutting elements and structures
US11536091B2 (en) 2018-05-30 2022-12-27 Baker Hughes Holding LLC Cutting elements, and related earth-boring tools and methods
CN112313354B (zh) * 2018-06-29 2022-05-10 山特维克科洛曼特公司 具有替代性粘结剂的硬质合金
CN109136610A (zh) * 2018-09-11 2019-01-04 张家港市六福新材料科技有限公司 一种氮化铝基金属陶瓷材料的制备方法
JP2022505878A (ja) 2018-10-26 2022-01-14 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
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BR112021023538A2 (pt) * 2019-05-27 2022-01-18 Sandvik Coromant Ab Uma ferramenta de corte revestida
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IL229654A0 (en) 2014-01-30
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US9821372B2 (en) 2017-11-21
PL2527480T3 (pl) 2017-12-29
IL229654B (en) 2018-12-31
JP6124877B2 (ja) 2017-05-10
CN103562422B (zh) 2016-02-10
KR20140032414A (ko) 2014-03-14
RU2623545C2 (ru) 2017-06-27
US11207730B2 (en) 2021-12-28
KR102079325B1 (ko) 2020-02-19
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RU2013158048A (ru) 2015-07-10

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