Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
• • 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
  • C22C29/08—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 based on tungsten carbide
• • 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
• • 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
  • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
  • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
• • 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
  • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

• the present invention provides sintered cemented carbide bodies having increased resistance to plastic deformation comprising tungsten carbide (WC), a binder metal phase and one or more solid solution phases comprising at least one of the carbides, nitrides and carbonitrides of at least one of the elements of groups IVb, Vb and VIb of the Periodic Table of Elements.
• the present invention also provides a method for producing these sintered cemented carbide bodies.
• These sintered cemented carbide bodies are useful in the manufacture of cutting tools, and especially indexable cutting inserts for the machining of steel and other metals or metal alloys.
• Sintered cemented carbide bodies and powder metallurgical methods for the manufacture thereof are known, for example, from U.S. Patent Re. 34,180 to Nemeth et al.. While cobalt has originally been used as a binder metal for the main constituent, tungsten carbide, a cobalt-nickel-iron alloy as taught by U.S Patent No. 6,024,776 turned out to be especially useful as a binder phase for tungsten carbide and other carbides, nitrides and carbonitrides of at least one of the elements titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, respectively.
• JP-A2-2002-356734 published on December 13, 2002, discloses a sintered cemented carbide body comprising WC, a binder phase consisting of at least one metal of the iron group, and one or more solid solution phases, wherein one of said solid solution phases comprises Zr and Nb while all solid solution phases other than the first one comprise at least one of the elements Ti, V, Cr, Mo, Ta and W, but must not comprise Zr and Nb.
• the best cutting results are achieved at a tantalum content of less than 1% by weight of the total composition, calculated as TaC.
• the present invention aims at achieving new sintered cemented carbide bodies having increased resistance to plastic deformation at increased temperatures and, as a result thereof, having increased wear resistance. Besides, the present invention aims at providing a powder metallurgical method of producing said sintered cemented carbide bodies. More specifically, it is an object of the present invention to provide a sintered cemented carbide body having at least two co-existing solid solution phases containing zirconium and niobium or one single homogenous solid solution phase containing zirconium and niobium.
• Another object of the present invention consists in providing a method of producing said sintered cemented carbide body comprising the step of providing a powder mixture which upon sintering provides at least two co-existing solid solution phases or one single homogenous solid solution phase containing, in each case, zirconium and niobium, and providing improved sintering activity and wettability with hard constituents of elements of groups IVb, Vb, and VIb of the periodic table of elements.
• the invention is a sintered cemented carbide body that has increased resistance to plastic deformation.
• the sintered cemented carbide body includes tungsten carbide, and a binder phase that includes at least one metal of the iron group or an alloy thereof, and one or more solid solution phases wherein each one of the solid solution phases comprises at least one of the carbides and carbonitrides of a combination of zirconium, niobium, and tungsten.
• the invention is a method of producing a sintered cemented carbide body comprising the steps of: providing a powder mixture comprising tungsten carbide, a binder metal powder comprising at least one metal of the iron group or an alloy thereof, and at least one of the carbides and carbonitrides of both zirconium and niobium; forming a green compact of said powder mixture; and vacuum sintering or sinter-HIP said green compact at a temperature of from 1400 to 1560 °C, wherein a powdered solid solution of the carbides or carbonitrides of zirconium and niobium is used to form said powder mixture.
• the invention is a cutting tool that comprises a body that includes a rake face and a flank face wherein the rake face and the flank face intersect to form a cutting edge at the intersection thereof.
• the body comprises tungsten carbide, a binder phase comprising at least one metal of the iron group or an alloy thereof, and one or more solid solution phases each one of which comprising at least one of the carbides and carbonitrides of a combination of zirconium, niobium, and tungsten.
• the invention is a sintered cemented carbide body that has increased resistance to plastic deformation.
• the sintered cemented carbide body includes tungsten carbide, and a binder phase that includes at least one metal of the iron group or an alloy thereof, and one or more solid solution phases wherein each one of the solid solution phases comprises at least one of the carbides and carbonitrides of a combination consisting of zirconium, niobium, and tungsten
• FIG. 1 is an isometric view of a cutting tool of the present invention wherein the cutting tool is a CNMG style of cutting tool;
• FIGS. 2A is a photomicrograph that shows the unetched microstructure of Sample (A), which is a sintered cemented carbide body, at 1, 500-fold magnification (10 micrometer scale) wherein Sample (A) was produced according to the present invention as disclosed hereinafter, and Sample (A) has a porosity of ⁇ A02 as shown in FIG. 2 A;
• FIG. 2B is a photomicrograph that shows the unetched microstructures of Sample (B), which is a sintered cemented carbide body, at 1, 500-fold magnification (10 micrometer scale) wherein Sample (B) was produced according to a conventional process as disclosed hereinafter, and Sample (B) has a residual porosity of A08 as shown in FIG. 2B;
• FIG. 3 A is a photomicrograph of a sintered bending strength test rod, in cross section, which was made according to the present invention as described hereinafter and does not show sinter distortion;
• FIG. 3B is a photomicrograph of a sintered bending strength test rod, in cross section, which was made in a conventional fashion as described hereinafter and very clearly shows a sinter distortion;
• FIG. 4 is a photomicrograph (20 micrometer scale) showing the unetched microstructure of an embodiment of the sintered cemented carbide body of the present invention wherein there is shown a binder enriched surface zone free of solid solution carbide wherein the binder enriched surface zone begins at and extends inwardly from the surface of the substrate and one single homogeneous solid solution phase (MC); and
• FIG. 5 is a photomicrograph (20 micrometer scale) showing the unetched microstructure of an other embodiment of the sintered cemented carbide body of the present invention wherein there is shown a binder enriched surface zone free of solid solution carbide wherein the binder enriched surface zone begins at and extends inwardly from the surface of the substrate and underneath the binder enriched surface zone free of solid solution phase there is shown a zone in which a single phase MCI exists (MCI is light brown), and underneath the MCI zone there is a zone that has two coexisting solid solution carbide phases wherein one solid solution phase is MC land it is light brown and the other solid solution phase is MC 2 and it is dark brown.
• MCI single phase MCI
• FIG. 1 there is shown a cutting tool, i.e., a sintered cemented carbide body, generally designated as 20.
• Cutting tool 20 has a rake face 22 and flank faces 24. There is a cutting edge 26 at the intersection of the rake face 22 and the flank faces 24.
• the cutting tool 20 further contains an aperture 28 by which the cutting tool 20 is secured to a tool holder.
• the style of cutting tool shown in FIG. 5 is a CNMG style of cutting tool.
• the illustration in FIG. 1 of a CNMG style of cutting tool should not be considered to limit the scope of the invention. It should be appreciated that the present invention is a new cemented carbide material that can be used as a cutting tool wherein the geometry of the cutting tool can be any known cutting tool geometry.
• the composition of the cutting tool i.e., a sintered cemented carbide body
• the composition contains tungsten carbide and a binder, as well as one or more solid solution phases that comprise the carbides and/or the carbonitrides of a combination of zirconium, mobium and tungsten as exemplified by the formulae (Zr,Nb,W)C and/or (Zr,Nb,W)CN.
• just one of the solid solution phases consists of a carbide or carbonitride of a combination of zirconium, niobium and tungsten.
• the solid solution phase consisting of a carbide or carbonitride of a combination of zirconium, niobium and tungsten is the sole solid solution phase of the body wherein no other element such as titanium, hafnium, vanadium, tantalum, chromium, and molybdenum is present in said solid solution phase.
• one of the solid solution phases comprises a carbide or carbonitride of a combination of zirconium, niobium and tungsten and at least one carbide, nitride or carbonitride of one or more of titanium, hafnium, vanadium, tantalum, chromium, and molybdenum wherein the solid solution phase may be either the sole solid solution phase of the body or one of two or more different solid solution phases.
• each solid solution phase comprising a carbide or carbonitride of a combination of zirconium, niobium and tungsten, and at least one carbide, nitride or carbonitride of one or more of titanium, hafnium, vanadium, tantalum, chromium and molybdenum, respectively.
• the solid solution phase comprises a carbide or carbonitride of a combination of zirconium, niobium and tungsten, and at least one carbide, nitride or carbonitride comprising one or more other metals
• said at least one other metal is one or more of titanium, tantalum and hafnium.
• the binder alloy preferably comprises cobalt, a CoNi-alloy or a CoNiFe-alloy, each of which may or may not contain additional alloying elements such as chromium and tungsten.
• the binder alloy preferably comprises between about 3 weight percent to about to 15 weight percent of the total body.
• the total contents of a carbide or carbonitride of a combination of zirconium, niobium and tungsten of the one or more solid solution phase(s) comprise between about 1 weight percent and about 15 weight percent of the total body.
• those embodiments of the present invention wherein the total content of the elements titanium, hafnium, vanadium, tantalum, chromium and molybdenum does not exceed about 8 weight percent of the total body.
• titanium comprises between about 1 weight percent and about 8 weight percent of the total body
• tantalum comprises between about 1 weight percent and about 7 weight percent of the total body
• hafnium comprises between about 1 weight percent and about 4 weight percent of the total body.
• the cemented carbide body has a mass ratio Nb/(Zr + Nb) of greater than about 0.5, and more preferably greater than or equal to about 0.6, the formation of a single homogeneous solid solution phase or the formation of two or more coexisting solid solution phases within the sintered cemented carbide body is remarkably increased.
• the sintered cemented carbide body comprises at least one of said nitrides or carbonitrides and comprises an outermost zone being free of any solid solution phase but binder enriched up to a depth of about 50 micrometers ( ⁇ m) from an uncoated surface of said body. Embodiments of this type are shown in FIGS. 4 and 5 hereof.
• binder enrichment and formation of a surface zone free of solid solution carbide is induced during sintering once at least one nitride or carbonitride is present in the starting powder mixture. Due to the formation of free nitrogen during sintering, diffusion of binder metal from the bulk towards the surface, and diffusion of solid solution phase from the surface zone towards the bulk will take place, resulting in a binder enriched surface zone being free of any solid solution phase. Due to these diffusion processes, two or more coexisting different solid solution phases showing a concentration gradient between the surface and the center of the body are formed underneath of the binder enriched zone, according to a still more preferred embodiment of the present invention.
• SSC solid solution carbide
• said one single and homogeneous solid solution phase will be located underneath of the binder enriched zone such that the single solid solution phase is homogeneous throughout said body, except in the binder enriched zone.
• one or more wear resistant layers deposited according to well-known physical vapor deposition (PVD) or chemical vapor deposition (CVD) methods are coated over a surface of the sintered cemented carbide body.
• these wear resistant coatings comprise one or more of the carbides, nitrides, carbonitrides, oxides or borides of a metal of the groups IVb, Vb and VIb of the periodic table of elements, and alumina.
• a solid solution of a carbide or carbonitride of a combination of zirconium and niobium having a mass ratio Nb/(Zr + Nb) of greater than about 0.5, and preferably greater than or equal to about 0.6 or more is used as the powdered solid solution of a carbide or carbonitride of a combination of zirconium and niobium.
• the powdered solid solution of a carbide or carbonitride of a combination of zirconium, niobium and tungsten preferably comprises between about 1 weight percent and about 15 weight percent of the total powder mixture.
• cobalt powder, powders of cobalt and nickel or powders of cobalt and nickel and iron or powders of a cobalt-nickel alloy or powders of a cobalt-nickel-iron alloy are used as the binder metal powders, within the method of the present invention.
• the binder metal powders may include additional elements, preferably one or more of chromium and tungsten.
• the binder metal powder comprises between about 3 weight percent and about 15 weight percent of the total powder mixture.
• the powder mixture additionally comprises at least one carbide, nitride or carbonitride of one or more of titanium, hafnium, vanadium, tantalum, chromium, and molybdenum.
• the powder mixture comprises at least one of the elements titanium, hafmum, vanadium, tantalum, chromium and molybdenum in an amount of between about 1 weight percent and about 8 weight percent of the total powder mixture.
• the present inventors have surprisingly found that due to the addition of zirconium and niobium in the form of a powdered solid solution of a carbide or carbonitride of a combination of zirconium and niobium to the starting powder mixture, instead of using zirconium carbide plus mobium carbide or zirconium carbonitride plus niobium carbonitride, each individually, either one single homogeneous solid solution phase comprising the carbides and/or the carbonitrides of a combination of zirconium, niobium and tungsten, or two or more coexisting solid solution phases comprising the carbides and/or the carbonitrides of a combination of zirconium, niobium and tungsten, and at least one carbide, nitride or carbonitride of one or more of titanium, hamium, vanadium, tantalum, chromium and molybdenum, depending on the compounds added to the starting powder mixture, are formed during
• Another advantage of the use of a powdered solid solution of a carbide or carbonitride of a combination of zirconium and niobium as part of the starting powder mixture according to the present invention is the fact that tantalum can be added to the composition for improving binder phase distribution and toughness in an amount of about 1 weight percent or more of the total starting powder mixture.
• each one of these figures is a photomicrograph at 1500X (each photomicrograph as a 10 micrometer scale) that shows the unetched microstructures of two samples; namely, Sample (A) and Sample (B), respectively.
• Sample (A) was produced according to the present invention using (Zr,Nb)C in the starting powder mixture and whereas Sample (B) was conventionally made by using individual carbides; namely, ZrC and NbC instead of (Zr,Nb)C in the starting powder mixture.
• FIG. 2A shows that Sample (A) has a porosity of less than A02
• FIG. 2B shows that Sample (B) has a porosity of A08.
• FIG. 2A shows that Sample (A) has a porosity of less than A02
• FIG. 2B shows that Sample (B) has a porosity of A08.
• FIG. 2A shows that Sample (A) has a porosity of less than A02
• FIG. 2B shows that Sample (B) has a porosity of
• the microstructure of Sample (A) obtained by using the (Zr,Nb)C solid solution in the starting powder is much more homogeneous in terms of porosity as compared with the microstructure (see FIG. 2B) of Sample (B), which is the conventionally prepared sintered cemented carbide body using ZrC + NbC as part of the starting powder mixture.
• FIG. 3 A and FIG. 3B are photomicrographs of sintered bending strength test rods wherein each is in cross section.
• FIG. 3B shows the microstructure of Sample (B) that is made in a conventional fashion using ZrC and NbC in the starting powder mixture wherein there is a sinter distortion that can be seen very clearly.
• FIG. 3 A shows the microstructure of Sample (A) that was made according to the present invention using a solid solution carbide of zircomum and niobium (Zr,Nb)C wherein FIG. 3 A does not show sinter distortion. This comparison shows that, with respect to sinter distortion, Sample (A) is much better with the present invention than with the conventional sample (B).
• a further advantage of using a powdered solid solution of a carbide or carbonitride of a combination of zirconium and niobium as part of the starting powder mixture consists in the lower affinity to oxygen, as compared to conventional methods of producing sintered cemented carbide bodies, whereby it is not necessary to have a reducing sintering atmosphere. Due to the avoidance of any controlling and monitoring of the reducing quality of the sintering atmosphere, sintering becomes easier and less expensive according to the present invention as compared to the prior art.
• FIG. 4 is a photomicrograph of an embodiment of the sintered cemented carbide body of the present invention wherein there is shown a binder enriched surface zone free of solid solution carbide and one single homogeneous solid solution phase (MC).
• FIG. 4 shows that the present invention allows the production of sintered cemented carbide bodies having one single homogeneous solid solution phase.
• FIG. 5 is a photomicrograph of an other embodiment of the sintered cemented carbide body of the present invention wherein there is shown a binder enriched surface zone free of solid solution carbide. Underneath the binder enriched surface zone free of solid solution phase there is shown a zone in which a solid solution phase MCI exists. MCI is light brown. Underneath the zone containing only MCI solid solution phase, there is a zone that contains two coexisting solid solution phases. One solid solution phase is MC land it is light brown. The other solid solution phase is MC 2 and it is dark brown.
• FIG. 1 is a binder enriched surface zone free of solid solution carbide.
• Powder mixtures A and B having the compositions (weight percent) given in Table 2 were prepared.
• TRS bars ISO 3327, type B
• the compacts were sinter-HIPped at temperatures between 1430 and 1520 degrees Centigrade.
• the resulting sintered cemented carbide bodies were metallurgically tested. The results of these tests are shown in FIGS. 2A and 2B and FIGS. 3A and 3B.
• Sample A shows a porosity of ⁇ A02 (see FIG. 2A)
• sample B prioror art comparative example
• shows a high residual porosity see FIG. 2B
• strong sinter distortion see FIG. 3B
• the density is reported in grams per cubic centimeter
• the magnetic saturation is reported in .1 micro testla cubic meter per kilogram
• the coercive force (He) is reported in oersteds
• the hardness is reported as a Vickers Hardness Number using a 30 kilogram load
• the porosity was ascertained per a visual inspection.
• the test methods used to determine the properties set forth in Table 3, as well as throughout the entire patent application, are described below.
• the method to determine density was according to ASTM Standard B31 l-93(2002)el entitled "Test Method for Density Determination for Powder Metallurgy (P/M) Materials Containing Less Than Two Percent Porosity.
• the method used to determine the magnetic saturation was along the lines of ASTM Standard B886-03 entitled “Standard Test Methods for Determination of MAGNETIC Saturation (Ms) of Cemented Carbides.
• the method to determine coercive force was ASTM Standard B887-03 entitled “Standard Test Method for Determination of Coercivity (Hcs) for Cemented Carbides.
• the method to determine the Vickers hardness was along the lines of ASTM Standard E92- 82(2003)el entitled “Standard Test Method for VICKERS Hardness of Metallic Materials”.
• the method used to determine the porosity was along the lines of ASTM Standard B276-91(2000) entitled “Standard Test Method for Apparent Porosity in Cemented Carbides”.
• CVD coated (same coatings as in Example 2) cutting inserts from powder mixtures C to G were subjected to a wear turning test under the following parameters:
• Test pieces were pressed and sintered with powder mixtures D, C, F and G. These test pieces were subjected to a hot hardness test (Vickers hardness) under the following conditions :
• Test temperatures room temperature RT, 400, 600, 800 and 900°C
• the Vickers hardness (hot hardness) test shows for the sintered bodies according to the present invention a clearly increased resistance against plastic deformation at higher temperatures as compared to the prior art.
• the compositions of the solid solution carbide (SSC) phase of samples C, D, E and F were analyzed by scanning electron microscopy (SEM) with the assistance of ED AX. In samples D, E and F two different SSC-phases could be identified by optical microscopy, whereas sample C showed one single
• Powder mixtures L and M were prepared according to the compositions given in Table 14 (the compositions are set forth in weight percent below: Table 14 Starting Powder Mixtures for Samples L and M Co (Zr,Nb)C TiC 1" TiN TiCN TaC NbC WC4 50/50 70/30 L 6.3 4.0 0.8 1.2 1.0 0.3 balance M 6.3 1.7 0.8 5.4* balance *as (Ta,Nb)C 70/30 fas (W,Ti)C 50/50 Cutting inserts were pressed from powder mixtures L and M in geometry CNMG120412-UN, then sintered (sinter-HIP 1505°C/85 min) and CVD coated.
• Table 14 Starting Powder Mixtures for Samples L and M Co (Zr,Nb)C TiC 1" TiN TiCN TaC NbC WC4 50/50 70/30 L 6.3 4.0 0.8 1.2 1.0 0.3 balance M 6.3 1.7 0.8 5.4* balance *as (Ta,Nb)C 70/30
• the resulting sintered bodies had the following properties as reported in Table 15. In addition to the properties reported for the above examples, Table 15 also reports the depth of the cobalt-enriched SSC-free zone in micrometers and the volume percent of cubic carbides present except for tungsten carbide. Table 15 Selected Properties of Cutting Inserts of Samples L and M
• Powder mixtures N and O were prepared having the compositions (in weight percent) given in Table 19. Table 19 Starting Powder Compositions for Samples N and O Co (Zr,Nb)C (Zr,Nb)C TiC 1" TiCN TaC NbC WC3 50/50 40/60 70/30
• step (c) vacuum sintering or sinter-HJJP said green compact at a temperature of wherein in step (a) a powdered solid solution of the carbides or carbonitrides of zirconium and niobium is used to form said powder mixture.
• the sintered cemented carbide bodies of the present invention have increased resistance to plastic deformation, resulting in improved wear resistance and extended life time of cutting tools produced from said sintered cemented carbide bodies. Besides, a considerable minimization of porosity and sinter distortion as compared to prior art sintered cemented carbide bodies, is obtained by the present invention.

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• Chemical & Material Sciences (AREA)
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