EP2527480B1 - NiFe binder with universal application - Google Patents

Description

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. Carbides 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. Therefore, high-temperature creep resistance (in practice, the hot hardness is usually determined as a substitute) is an important property of the carbide tool. But the fracture toughness (K ₁ C) is an important factor in all applications, since otherwise the tool or component mechanical peak loads is not up to it and can break. The wear resistance, the hot hardness, the fracture toughness and the related strength (the latter most often expressed as flexural strength) can be adjusted by the size of the carbide phase and its proportion of the hard metal composition.

In addition, the properties of the hard metals depend strongly on the binding alloy used. Crack resistance, corrosion and hot hardness are mainly determined by the nature of the binder alloy and its basis. The The present invention relates to novel hard metals having a FeNi or FeCoNibasierten 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 the Vickershärteeindrucks) and hot hardness the properties of those hitherto conventional hard metals correspond to a Co-based binder alloy.

For various reasons, instead of cobalt as the base alloy, other base alloys are used in special hard metals. By "base binder alloying" is meant also pure metals with inevitable impurities, e.g. available as commercially available nickel and cobalt metal powders.

For example, 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 hard metal batch as a metal powder or carbide, for example, and their contents 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. Furthermore, 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.

Furthermore, FeCoNi-based alloys are known as carbide binders. However, their disadvantages are 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. Thus, the K ₁ C values of a hard metal are based on tungsten carbide (average powder diameter: 0.6 μm) with 7.5% FeCoNi 40/20/40 at values 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; Thus, 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) has a K ₁ C of only 8.5 MPa m ^1/2 .

Furthermore, FeNi-based alloys with 10 to 50% _Ni, Fe 90 to 50% from the dissertation Wittmann (= TU Wien =) are known. For example, at 15% Ni and 85% Fe, 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" =). However, the hot hardness of hard metals with Fe-rich FeNi-base binder alloys above 400 ° C are significantly lower than those bound with Co-base alloys, this is exemplified by a base alloy of FeNi 82/18 (Proceedings International Conference on Tungsten , Refractory and Hard Metals, Washington, 2008, there referred to as "M1800" =).

An attempt to explain the dependence of the hard hardness of hard metals on the composition of the FeCoNi base alloys used, the maximum solubility of tungsten in the binder metal alloy, which can be adjusted after carbide sintering (= B._Gries, Proceedings EUROPE 2009 Copenhagen, October 10-12, 2009 ). Thereafter, however, the maximum hot hardness of hard metals with FeNi-based alloy would have to be at a binding alloy with pure Ni, since here with about 25 wt .-%, the maximum solubility of tungsten in the binder alloy occurs. In practice, however, 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. Despite the even higher solubility to 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.

They are also out 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 when machining special steels. The hot curing of such hard metals with austenitic FeCoNi base 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. However, above 400 ° C, 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 ). In addition, 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. Thus, 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.

In summary, it can be said that neither Ni, FeNi nor FeCoNi base alloys as hard metal binders lead to universally and industrially usable hard metals, which are comparable at the same time in the points K ₁ C, hardness and hot hardness with those bonded cobalt-based binders. For reasons of the health risk by cobalt as well as for the sake of the preservation of resources, it would be desirable, if possible complete replacement of cobalt as a binder alloy base by FeNi or FeNi with low cobalt contents, if possible less than 10%. In particular, levels of iron in the binder alloy and in the binder-based alloy result in a reduction or avoidance in the generation of hyperoxide radicals such as are encountered in the contact corrosion of WC with cobalt in the presence of water and oxygen.

In addition, a statistically significant increase in the incidence of pulmonary fibrosis has been observed in the cemented carbide industry, which is observed in association with the handling of dust-like cemented carbide. The disease is also referred to as "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. In particular, in the case of mainly cobalt-containing hard metals, an 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.

Furthermore, it is an object of the present invention to provide a method for producing a composite material, which leads to hard metals, which are at least equivalent to those composite materials, both in terms of hot hardness and in terms of hardness and fracture toughness, one of the prior Technique conventional cobalt-based alloy.

Unexpectedly, it has now been found that certain hard metals with Ni-rich FeNi base binder alloys are comparable in hardness, thermal hardness and fracture toughness (K ₁ C) to those bonded to cobalt base binder alloys. This is completely unexpected in that these results are not based on the behavior of pure nickel as a base On the other hand, and the behavior of FeNi 50/50 on the other hand, can be linearly interpolated. Perhaps this is the reason why so far no such bound hard metals have become known. Occasionally, the use of NiCrFe-based binder alloys was described for cubic hardeners - for example in GB 1 330 218 or in DE 19 38 074 These systems exhibit significantly lower hardness values than hard metals with tungsten carbide and cobalt-based binder alloys. DE 10 2007 04937 and WO 02 052 054 disclose hard materials with binding metals, which include nickel and iron.

It has now surprisingly been found that the problems arising from the prior art can be solved by the composite materials produced according to the invention.

1. a) mindestens einen Härteträger und
2. b) einer Basisbindelegierung, umfassend
   • α) 66 bis 93 Gew.-% Nickel,
   • β) 7 bis 34 Gew.-% Eisen und
   • γ) 0 bis 9 Gew.-% Kobalt,

wobei sich die Gewichtsanteile der Basisbindelegierung zu 100 Gew.-% ergänzen.The present invention is a process for the preparation of a composite material comprising sintering a composition having the features of claim 1, in particular containing

1. a) at least one hardness carrier and
2. b) a basic binding alloy comprising
   • α) from 66 to 93% by weight of nickel,
   • β) 7 to 34 wt .-% iron and
   • γ) 0 to 9% by weight of cobalt,

wherein the weight proportions of the base binder alloy supplement to 100 wt .-%.

In the context of the present invention, the term "hard metal" and "sintered composite material" is used synonymously.

According to the present invention, the base binder alloy has a weight ratio of iron: 1: 2 to 1: 1, preferably 1: 2.5 to 1: 12, more preferably 1: 3 to 1: 10, and more preferably 1: 3 to 1: _9, more preferably 1 _: _ 4 to 1 _: _ 8, for example 1_: 4 to 1 _: _ 7 on.

In particular, good results can be obtained with 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 .-%.

Due to the toxic properties of the cobalt, it is preferred to keep this content as low as possible in the base binder alloy. The base binder alloy therefore preferably contains less than 8% by weight, preferably less than 5% by weight, in particular less than 1% by weight, of cobalt.

In a particularly preferred embodiment, the base binder alloy is substantially free of cobalt. In a further preferred embodiment, the base binder alloy is substantially free of other elements, in particular substantially free of metals other than nickel and iron. Non-metals 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 as they sinter or partially.

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.

In a further preferred embodiment of the method according to the invention, 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.

Another essential component of the composition is the hardness carrier. In a preferred embodiment of the present invention, 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. He comprises at least 50% by weight of the binary hardener tungsten carbide, based on the total weight of the hardness carriers, and may also contain further hardeners, such as ternary hardeners, such as tantalum-niobium mixed carbide, titanium carbonitride or tungsten-titanium carbide or even quaternary, such as tungsten-titanium-carbonitride or tungsten-titanium-niobium-tantalum carbide.

In a particularly preferred embodiment, the hardness carrier is selected from the group consisting of titanium carbide, chromium carbide, tantalum carbide, niobium carbide, vanadium carbide, molybdenum carbide, tantalum-niobium mixed carbide, titanium carbonitride, wolfram titanium carbide, tungsten titanium carbonitride and in any case contains at least 50 wt % Tungsten carbide.

The hardness carriers are preferably in powder form. In an advantageous embodiment, 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 powders, ie, for example, iron, nickel, and optionally cobalt powders.

In a preferred embodiment, the hardness carrier and / or the base binder alloy is present in powder form. In a particularly preferred embodiment, the base binder alloy is present as alloy powder.

The 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. In particular, elemental tungsten or elemental carbon may be preferably used since it is suitable for correcting the carbon content of the composite after sintering. However, intermetallic compounds such as Ni ₃ Al or chromium nitride decomposing during sintering can also be added to the compositions to be sintered. These 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 contains 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 of hard carrier, in each case based on the total weight of the composition.

Further, the composition contains 3 to 50 wt .-% of the base binder alloy, preferably 4 to 40 wt .-%, in particular 4 to 30 wt .-% of the base binder alloy, each based 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. Preferably, the sintering is in the presence of liquid phase. Particularly preferably, the base binder alloy is completely or partially present in liquid form during the sintering process.

Depending on the composition, 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 at a base binder alloy content of 20% by weight, the sintering temperature could be reduced to as low as 1250 ° C, with 5% by weight base binder alloy, temperatures in excess of 1400 ° C are 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.

1. a) Bereitstellen einer Dispersion, umfassend eine Zusammensetzung, enthaltend Härteträger und Basisbindelegierung, wie zuvor definiert, in einem Lösungsmittel,
2. b) Vermahlen der Dispersion,
3. c) Herstellen eines Pulvers durch Trocknen der Dispersion,
4. d) Herstellung von Presskörpern durch Verpressen des Pulvers, oder durch Extrusion des Pulvers unter Zuhilfenahme von Plastifizierungsmitteln, und
5. e) Sintern des Presskörpers beziehungsweise des Extrudates.

In a preferred embodiment, the method according to the invention comprises the following steps:

1. a) providing a dispersion comprising a composition comprising a hardness carrier and a base binder alloy, as defined above, in a solvent,
2. b) milling the dispersion,
3. c) preparing a powder by drying the dispersion,
4. d) production of compacts by compression of the powder, or by extrusion of the powder with the aid of plasticizers, and
5. e) sintering of the compact or of the extrudate.

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. Especially preferred are alcohols, in particular aliphatic alcohols, for example ethanol, and water or mixtures thereof, such as mixtures of water and organic Solvents, especially water and alcohols. Also preferred are 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. Particularly preferably, the milling of the dispersion is carried out in a ball mill or an attritor, 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.

In a preferred embodiment, 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. Here it has proved to be advantageous to use as the solvent low-boiling solvent which can be easily distilled off under reduced pressure.

In a further preferred embodiment, 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.

Subsequently, in step e), the compact or the extrudate is sintered. In a preferred embodiment, the sintering is carried out in the presence of a protective gas atmosphere or under reduced pressure.

In another preferred embodiment, the sintered composites are further densified at elevated pressure in a separate or integrated post-densification step.

In a further preferred embodiment, 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.

A further subject of the present invention is a sintered composite material with the features of claim 10, in particular 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. In addition to this base are in the 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 present in the sintered = hard metal binder alloy thus forms only during sintering from the base alloy and the balance settings with the other components that are still contained in the carbide out. 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.

Further, 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 both in the FeNi base alloy as well as in other base alloys, and their contents are adjusted during sintering and cooling due to their temperature-dependent solubility in addition to the carbon content according to the principle of solubility 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.

In a preferred embodiment, 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. For example, W, Cr and Mo increase the hot hardness due to their solubilities on the order of not more than 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 (hard metals) 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.

The 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 most preferably be elongated (for example, ground out of a sintered round rod), but more preferably also plate-shaped for turning or milling of materials such as metals, bricks and composites. In all cases, the cemented carbide tools may preferably have one or more coatings from the classes of nitrides, borides, oxides or superhard layers (e.g., 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. It may also be in a preferred manner but also carbide parts further and arbitrary geometry and application, such as forging tools, forming tools, countersinks, components, knives, peeling plates, rollers, stamping tools, pentagonal drill bits for soldering, mining chisel, milling tools for milling processing of concrete and asphalt , Mechanical seals and any other geometry and application.

For some applications, the carbide may also have the surface resulting from sintering, and optionally subsequently coated or uncoated used.

Another object of the present invention is the use of the sintered composite material according to the invention for tools or components. In particular, the sintered composite materials according to the invention can be used for forming or comminution tools. In a particularly preferred embodiment, 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.

• α) 66 bis 93 Gew.-% Nickel,
• β) 7 bis 34 Gew.-% Eisen und
• γ) 0 bis 9 Gew.-% Kobalt,

wobei die Basisbindelegierung ein Gewichtsverhältnis von Eisen : Nickel von 1 : 2 bis 1 : 13 aufweist, zur Herstellung eines Verbundwerkstoffs oder eines Werkzeugs.Another object of the present invention is the use of a base alloy comprising

• α) from 66 to 93% by weight of nickel,
• β) 7 to 34 wt .-% iron and
• γ) 0 to 9% by weight of cobalt,

wherein the base binder alloy has a weight ratio of iron: nickel of from 1: 2 to 1: 13 for producing a composite or a tool.

The invention is further illustrated by the following examples, but without being limited thereto.

Examples Example 1 (comparative example, not according to the invention)

460 g of tungsten carbide with a grain size of 0.6 μm in accordance with ASTM B330 (= type WC DS60, manufacturer: HC Starck GmbH, Goslar, Germany =) were mixed with 40 g of a customary cobalt powder (type "efp", manufacturer: Umicore, Belgium). mixed in a ball mill with 0.57 liters of 94% ethanol for 14 h at 63 rpm. In this case, 5 kg of hard metal balls were used. Two batches with different carbon contents ("high carbon" or "low carbon") were produced so that different carbon contents and thus different magnetic saturations of the hard metals or the cobalt-based binder alloys contained therein result after sintering.

From the resulting suspension, 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. Thus, the binder metal alloy in the base is cobalt, with proportions of tungsten and possibly carbon. Table 1 carbon "low carbon" "high carbon Hardness (HV 30) (kg / mm ² ) 1626 1597 Magnetic saturation (G · cm ³ / g) 123 132 Porosity (ISO 4505) <A02B00C00 <A02 <B02C00 Rupture toughness (MPa · m ^1/2 ) 9.3 9.5 Density (g / cm ³ ) 14.78 14,74

In both cases the room temperature hardness was measured in a hardness testing apparatus as Vickers hardness HV30 according to ISO 3878 as well as the hot hardness at selected temperatures up to 800 ° C. under protective gas ( FIG. 1 ). For this purpose, both hard metal approaches 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 , in the 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, up.

$$\mathrm{R}=\mathrm{Risswiderstand}=\mathrm{30}/\mathrm{Summe\; der\; L}\ddot{\mathrm{a}}\mathrm{nge\; der\; Risse}\left(\mathrm{in\; \mu m}\right)\times \mathrm{1000}$$

$$\mathrm{HV}\mathrm{30}=\mathrm{Vickersh}\ddot{\mathrm{a}}\mathrm{rte\; bei}\mathrm{30}\mathrm{kg\; Belastung}\left(\mathrm{kg}/{\mathrm{mm}}^{\mathrm{2}}\right)$$

The fracture toughness K ₁ C was determined according to the formula of Shetty: $${\mathrm{K}}_{\mathrm{1}}\mathrm{C}=\mathrm{0}.\mathrm{0028}\times \mathrm{9}.\mathrm{81}\times {\left(\mathrm{HV}\mathrm{30}/\mathrm{R}\right)}^{\mathrm{1}/\mathrm{2}}\left(\mathrm{in\; MPa}{\mathrm{m}}^{\mathrm{1}/\mathrm{2}}\right)$$

$$\mathrm{R}=\mathrm{crack\; resistance}=\mathrm{30}/\mathrm{Sum\; of\; the\; L}\ddot{\mathrm{a}}\mathrm{the\; cracks}\left(\mathrm{in\; \mu m}\right)\times \mathrm{1000}$$

$$\mathrm{HV}\mathrm{30}=\mathrm{Vickersh}\ddot{\mathrm{a}}\mathrm{at}\mathrm{30}\mathrm{kg\; load}\left(\mathrm{kg}/{\mathrm{<figure-callout\; id="2"\; label="mm"\; filenames="imgf0002.png"\; state="\{\{state\}\}">mm</figure-callout>}}^{\mathrm{2}}\right)$$

Example 2 (according to the invention)

Example 1 was repeated except that the two batches consisted of 461.5 g tungsten carbide of 0.6 μm grain size and the binder metal base of 38.5 g of an alloy powder containing 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. Thus, 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 results after sintering at 1420 ° C for 60 min and metallographic examination are shown in the following Table 2: Table 2 carbon "low carbon" "high carbon" Hardness (HV30) 1574 1591 Magnetic saturation (G · cm ³ / g) 51 66.8 Porosity (ISO 4505) <A02B00C00 <A02B00C00 Rupture toughness (MPa · m ^1/2 ) 10.2 11 Density (g / cm ³ ) 14.83 14.81

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. However, 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 ). For this purpose, new sintered bodies were made from the existing hard metal approaches. In this case, 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. Thus, 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 conducive to 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.

It is also apparent that, advantageously, in the case of this binder-base alloy, the properties K ₁ C and hot hardness depend only slightly on the carbon content of the cemented carbide.

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 3 (= Comparative Example, not according to the invention =)

Analogous to Example 2 different approaches (from a toilet (0.6 micron particle size and 7.5% of a FeCoNi alloy powder AMPERSINT ^® MAP A6050, manufacturers were: HC Starck GmbH, Germany, composition: 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.

The inferiority of the FeCoNi base alloy in the hot hardness was in WO 2010/046224 (Example 1 and FIG. 1 ) already published.

In summary, hard metals with a FeCoNi 40/20 / 40A base binding in terms of K ₁ C and hot hardness are inferior to those which are bound with cobalt as a base for the binder alloy.

Example 4 (= Comparative Example, not according to the invention =)

Analogously to Example 1 Hard metals were 7.4 wt .-% of a FeNi 50/50 alloy powder (AMPERSINT MAP ^® A5000, manufacturer HC Starck GmbH, Germany) as a base binder alloy. The volume fraction of the base binder alloy corresponds to that of Example 1. The hard metals obtained, which were free of eta phases or carbon precipitates, had HV30 values between 1619 and 1636. 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.

Thus, 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 ). For example, 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.

Example 5 (partially according to the invention, there marked with * =)

Hard metals with different Fe / Ni ratios between 35/65 and 0/100 were prepared analogously to Example 1. In all cases, the volume fraction of the binder-base alloy was that of Example 1. The variation of the Fe: Ni ratio in the binder-base alloy was adjusted by using FeNi 50/50 as in Example 4 (= Fe _: _ Ni ratio 1 _: _ 1) and a 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 additional variation of the carbon content in the Approaches ensured that all cemented carbides were free of carbon deposits and eta phases after sintering. All hard metals were sintered together at 1420 ° C for 60 minutes.

The following Table 3 summarizes the results thus obtained: Table 3 Fe / Ni ratio HV30 K1C density Magnetic saturation (kg / mm ² ) (MPa m ^1/2 ) (g / cm ³ ) (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

Figures 2 and 3 illustrate the results of Example 4 and Examples 1 and 4 in comparison.

It becomes clear that the hardness decreases only very slightly with increasing nickel contents, while the K ₁ C rises slightly and reaches the values of the comparison hard metals from Example 1 at about 65% Ni. This also applies to the K ₁ C, whose values tend to larger relative errors at values above 10. The K ₁ C values were calculated according to the formula of Shetty from the crack lengths. Since very short crack lengths lead to large relative errors when reading the crack length under the microscope, but on the other hand short crack lengths result in high K ₁ C values, the relative error of the K ₁ C increases steadily with the measured value itself can recognize well.

Surprisingly, 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 hard metals from 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), including the K ₁ falls C on, the hardness falls off sharply and sharply.

Claims (15)

1. Process for producing a composite material, which comprises providing a composition containing

   a) from 50 to 97% by weight of at least one hardness carrier comprising at least 50% by weight of tungsten carbide, based on the total weight of the hardness carrier,

   b) from 50 to 3% by weight of a base binder alloy comprising

   α) from 66 to 93% by weight of nickel,

   β) from 34 to 7% by weight of iron and

   γ) from 0 to 9% by weight of cobalt,

   where the base binder alloy has a weight ratio of iron:nickel of from 1:2 to 1:13 and the proportions by weight α, β and γ of the base binder alloy add up to 100% by weight, and

   c) up to 30% by weight of one or more of the elements selected from the group consisting of W, Mo, Cr, V, Ta, Nb, Ti, Zr, Hf, Re, Ru, Al, Mn, B, N and C, where the total weight of base binder alloy, hardness carrier and optionally present additives adds up to 100% by weight, and sintering said composition.
2. Process according to Claim 1, characterized in that the base binder alloy has a weight ratio of iron:nickel from 1:2.5 to 1:12, preferably from 1:3 to 1:10 and in particular from 1:3 to 1:9, especially preferably from 1:4 to 1:8, for example from 1:4 to 1:7.
3. Process according to Claim 1 or 2, characterized in that the base binder alloy comprises from 66 to 90% by weight, preferably from 70 to 90% by weight, of nickel.
4. Process according to at least one of Claims 1 to 3, characterized in that the base binder alloy contains less than 8% by weight of cobalt, preferably less than 5% by weight of cobalt.
5. Process according to at least one of Claims 1 to 4, characterized in that the base binder alloy contains less than 0.1% by weight of molybdenum, preferably less than 0.08% by weight, in particular less than 0.02% by weight, of molybdenum.
6. Process according to at least one of Claims 1 to 5, characterized in that the hardness carrier is selected from the group consisting of carbides, nitrides, borides and carbonitrides.
7. Process according to at least one of Claims 1 to 6, characterized in that the hardness carrier comprises one or more elements of transition groups 4A, 5A and 6A of the Periodic Table.
8. Process according to any of the preceding claims, characterized in that the base binder alloy is present as alloy powder.
9. Process according to at least one of the preceding claims, which comprises the steps:

   a) provision of a dispersion comprising a composition containing hardness carrier (s) and base binder alloy powder in a solvent,

   b) milling of the dispersion,

   c) production of a powder by drying of the dispersion,

   d) production of compacts by pressing the powder or by extrusion of the powder with the aid of plasticizing agents and

   e) sintering of the compact or of the extruder.
10. Sintered composite material containing at least one hardness carrier and a binder alloy,
    the hardness carrier comprising at least 50% by weight of tungsten carbide, based on the total weight of the hardness carrier, the binder alloy consisting of the elements Fe and Ni and optionally Co and up to 30% by weight of one or more of the elements selected from the group consisting of W, Mo, Cr, V, Ta, Nb, Ti, Zr, Hf, Re, Ru, Al, Mn, B, N and C,
    where the binder is obtainable from a base binder alloy comprising from 66 to 93% by weight of nickel, from 7 to 34% by weight of iron and from 0 to 9% by weight of cobalt and has a weight ratio of iron:nickel of from 1:2 to 1:13.
11. Sintered composite material according to Claim 10, characterized in that the base binder alloy contains less than 0.5% by weight of cobalt.
12. Sintered composite material according to Claim 10 or 11, characterized in that the base binder alloy has a weight ratio of iron:nickel from 1:2.5 to 1:12, preferably from 1:3 to 1:10 and in particular from 1:3 to 1:9, especially preferably from 1:4 to 1:8, for example from 1:4 to 1:7.
13. Use of the sintered composite material according to any of Claims 10 to 12 for tools or parts.
14. Use according to Claim 13, characterized in that the tools are forming or comminution tools.
15. Use according to Claim 13 or 14, characterized in that the tool is a tool for the cutting machining of metallic tools or for the forming of metal workpieces at high temperatures, for example a tool for forging, wire drawing or rolling.

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