WO2004053178A1 - Composite metal product and method for the manufacturing of such a product - Google Patents
Composite metal product and method for the manufacturing of such a product Download PDFInfo
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- WO2004053178A1 WO2004053178A1 PCT/SE2003/001908 SE0301908W WO2004053178A1 WO 2004053178 A1 WO2004053178 A1 WO 2004053178A1 SE 0301908 W SE0301908 W SE 0301908W WO 2004053178 A1 WO2004053178 A1 WO 2004053178A1
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Classifications
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- 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
- C22C29/04—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 carbonitrides
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- 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
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- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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- 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
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- 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
- B22F2998/10—Processes characterised by the sequence of their steps
Definitions
- the present invention concerns a composite metal product suitable to be used as a material for shearing, cutting, punching and moulding tools as well as for wearing parts and construction elements, when high demands are raised on hardness and wear resistance in combination with an adequate strength.
- the invention also relates to a method for the manufacturing of such product.
- cemented carbide materials means materials having an extremely high content of carbides which are sintered together in a binder metal, which normally consists of a cobalt base alloy. Many attempts have been made during the last fifty years to bridge this gap through the development of steel alloys having a high content of titanium carbides. An early suggested material belonging to this caterogy is known under the trade name “Ferro- TiC”, which however achieved only limited practical use. Another material having the trade name “Coronite”, which is disclosed in the US Patent No 4,145,213, is no longer on the market place, as far as is known to the applicant.
- the material according to said US Patent No 4,145,213 contains a very high content of titanium carbide in a matrix consisting of hardenable steel.
- the titanium carbides in turn contain a larger amount of nitrogen than carbon.
- the material may be produced through liquid phase sintering of a cold pressed powder body, or through liquid phase sintering of a powder body under pressure - so called pressure sintering -, through isostatic hot pressurising, or through forging of a powder body with or without the presence of liquid phase.
- This objective can be achieved through the invention by means of a composite metal product which contains 30-90 vol-% of a hard phase in the form of particles of substantially M(C,N)-carbonitride or M(C,N,O)-carbonitrideoxide 5 commonly referred to as hard phase of MX-type, where M to at least 50 atomic-% consists of titanium and
- N the atomic-% ratio between C and N shall satisfy the condition 0.1 ⁇ ⁇
- N 0.7 preferably satisfy the condition 0.2 ⁇ ⁇ 0.6, suitably satisfy the condition
- 30 atomic-%, in said hard phase of MX-type may consist of one or more of the metals which belong to the group consisting of N, ⁇ b, Ta, Hf, and Zr.
- M might consist of at least 5 and max. 30 atomic-% N and/or of at least 5 and max. 30 atomic-% ⁇ b, however, totally max. 40 atomic-%, preferably max. 30 atomic-%.
- Ta, Zr and/or Hf shall be included, the total amount of those metals should not amount to more than 3 atomic-% of the total metal content of the hard phase of MX-type.
- the metal M in said hard phase of MX-type consists of titanium to at least 70 atomic-%, preferably at least 80 atomic-%, and most conveniently to at least 90 atomic-%.
- the total content of hard phase of MX-type amounts, according to an aspect of the invention, to 30-70 vol-%, preferably to 40-60 vol-%, of the metal product.
- the said matrix consists of a hardenable steel, as has been mentioned above.
- the steel may also contain secondarily precipitated carbides, e.g. vanadium carbides, i.e. MC-carbides, which have a size too small to be observed in an optical microscope.
- the steel may contain primary carbides which are typical for high speed steels, e.g. M 6 C-carbides.
- said matrix including secondarily precipitated MC-carbides, which may exist in the matrix, and any hard phase of other type than MX-type, which may exist in the matrix may have the following chemical composition in weight-%:
- the invention also aims at providing a method for manufacturing, with good reproducibility, a composite metal product which contains 30-90 vol-% of a hard phase having the form of particles, which consist mainly of M(C,N)-carbonitride or M(C,N,O)-carbonitrideoxide, commonly referred to as hard phase of MX-type, which particles are substantially homogenously distributed in a matrix of hardenable steel.
- a powder mixture which contains powder of titanium carbide, titanium nitride, and/or titanium carbonitride in such an amount that its content of titanium atoms correspond to at least 50 % of the metal atoms in said hard phase of MX-type in the final metal product, and at least the main part of other constituents of the final metal product, is milled together, that a body is formed of the milled mixture, and that said body is liquid phase sintered at a temperature between 1350 and 1600 °C and subsequently cooled, causing the liquid phase to solidify, said hard phase particles of MX-type obtaining their final composition and size during said liquid phase sintering and subsequent solidification.
- at least 90 % of the number of particles which can be observed in a viewed section of the material by means an optical microscope, have a size smaller than 1 ⁇ m.
- the contents of carbon and nitrogen are controlled during the integrated process, which comprises selection and milling of powder, milling the powder mixture, forming press bodies of the milled powder, and liquid phase sintering, such that the amounts of carbon and nitrogen in atomic-% in said
- N hard phase in the finished product will satisfy that value of the ratio which has been mentioned in the foregoing.
- the milling of the powder mixture is performed with a power supply of at least 10 MJ (megajouleVkg powder, preferably at least 20 MJ/kg powder.
- a power supply of 25 MJ/kg powder has turned out to be suitable.
- the power supply therefore, according to an aspect of the invention, should be limited to max. 50 MJ/kg powder, suitably be limited to max. 40 MJ/kg powder, in order not to make the manufacturing unnecessarily expensive.
- hard phase particles of MX-type will be evenly distributed in the said matrix.
- Evenly distributed means that not more than 0.5 % of a section of the product should consist of regions having a length of at least 8 ⁇ m in the direction of the longest extension of the region, a width crosswise said direction of the longest extension, in any section of the region, of not more than 8 ⁇ m, and an area of at least 50 ⁇ m 2 , which regions are void of hard phase particles of MX-type, and that not more than 10 %, and preferably not more than 5 % of the section of the product, consists of regions having a length of at least 6 d in the direction of the longest extension of the region, a width crosswise said direction of the longest extension, in any section of the region, of at least 6 d, and an area of at least 9 ⁇ d 2 where d is the mean value of the size of the hard phase particles of MX-type in the longest extension of the particles in the observed section, which
- the powder of titanium carbide, titaniumnitride and/ titaniumcarbonitride, which is employed in the powder mixture, may be oxidised.
- Performed experiments thus have shown that a highly oxidised powder may be used, and that there is no need to reduce such oxidised powder before use, which is a significant advantage from a cost point of view. Nor need any measures be made to prevent further oxygen take up during the continued process, which includes milling, forming press bodies and sintering.
- the content of oxygen in this hard phase is 0.01-4 atomic-% of the total content of C+N+O in the hard phase.
- Fig.1 - Fig.5 show microstructures of samples made of a powder mixture containing
- Fig.6 - Fig.10 show the microstructures of a composite product, having a chemical composition according to the invention, after sintering at varying temperatures between 1350 and 1540 °C
- Fig.l 1 shows the microstructure of a material having the same chemical composition, manufactured through hot isostatic pressing (HIP-ing)
- Fig.12 shows the microstructure of a steel with an addition of NbC according to an aspect of the invention.
- the hard phase powder consisted of vanadium carbide (NC), niobium carbide ( ⁇ bC), hafnium carbide (HfC), hafnium- titanium carbide ((Hf,Ti)C), titanium nitride (Ti ⁇ ), and titanium carbide (TiC). More specifically, there was used as hard phase commercially available powders of said hard phases with a powder grain size in the order of 1 ⁇ m. These powders contained several thousands ppm oxygen. In other words, they were highly oxidised.
- the order of the oxygen content could be estimated to about 4000 ppm (0.4 %) but could be even higher and amount to the order of 1 weight-%.
- the base metal powder consisted of a commercially available high speed steel obtained from the applicant's own production. This high speed steel is known by its trade name ASP 2030 ® , which has the chemical composition in weight-%: 1.28 C, 0.5 Si, 0.3 Mn, 4.2 Cr, 5.0 Mo, 3.1 N, 6.4 W, 8.5 Co, balance Fe and unavoidable impurities.
- This powder consisted of a gas atomised powder, which was sieved to a maximal grain size of 125 ⁇ m.
- the different powder mixtures were milled in a so called attritor mill, which is a type of ball mill having milling balls made of a ball bearing steel.
- attritor mill which is a type of ball mill having milling balls made of a ball bearing steel.
- the energy is supplied to the milling balls through the rotation of the mill housing
- the energy is supplied to the balls by means of a rotating propeller. This affords a very high velocity to the milling bodies and hence a capacity to transfer more energy to the product which is being milled. Therefore, in an attritor mill, the supply of energy/time is about fifteen times larger than in a more conventional ball mill. This is important, because it promotes the homogenisation of the material that is being milled.
- the particles that are being milled are crushed, deformed and repeatedly put together again. Due to the deformation, which is an important part of this treatment, a great amount of dislocation energy is supplied to the product that is milled, leading to a changed, higher state of energy of the milled material.
- the energy which was supplied to the milled powder in this mode amounted to about 25 MJ (Megajoule)/kg powder. No milling liquid was used during the milling. The milling was performed at atmospheric pressure. Pick up of oxygen through oxidation could take place during the handling of the powder.
- the green bodies were consolidated through liquid phase sintering in a vacuum furnace, heated by graphite electric heaters.
- the sintering temperatures were varied from 1300 to 1540 °C with a holding time of 30 min. at the sintering temperature.
- the samples Prior to mechanical tests, the samples were hardened from 1180 °C, followed by tempering at 560 °C, 3xlh.
- the powder mixtures were milled for ten hours in an attritor mill with an energy supply of about 25 MJ/kg powder, were pressed to green bodies, and were sintered in the mode described above.
- the microstructure of samples sintered at 1300, 1350 and 1400 °C were studied.
- samples of the same powder mixtures which had been consolidated through hot isostatic pressing (HIP-ing) were studied.
- HIP-ing hot isostatic pressing
- Powder mixtures with compositions according to Table III were prepared. Also these powders had the same physical character as in the series of experiments I and II. Table 3 Ingredients (gram) of the powder mixtures
- the ingredients of the powder mixtures were selected such that only the contents of carbon and nitrogen were varied, while the other elements existed in essentially equal amounts in the mixtures.
- the chemical composition of the powder mixtures contained in weight-%: 0.39 Si, 0.18 Mn, 2.66 Cr, 3.34 Mo, 4.18 W, 2.05 V, 5.60 Co and 25.3 Ti.
- the oxygen content amounted to about 0.27 weight-%.
- Balance was iron, carbon, nitrogen and unavoidable impurities.
- the contents of carbon and nitrogen in the powder mixtures are given in Table 5.
- the powder mixtures were milled in an attritor mill in the mode which has been described in the foregoing, e.g. for a period time of 10 hours, with an energy supply of 25 MJ/kg powder.
- Green bodies were made of the milled powder, and the green bodies were consolidated through HIP-ing and through liquid phase sintering, respectively.
- the liquid phase sintering was carried out at varying temperatures between 1300 and 1540 °C during a holding time of 30 minutes at the sintering temperature.
- Fig.l - Fig.5 shows the microstructures of samples of the alloys 69, 70, 71, 72 and 73 after liquid phase sintering at 1480 °C. It is evident that the alloys 70 and 71 had a comparatively homogeneous microstructure and fine hard phase particles with sizes well below 1 ⁇ m. Alloy 69 had a comparatively more coarse hard phase structure. Alloy 72 had an inferior homogeneity and a higher porosity, while alloy 73 had the poorest homogeneity and highest porosity.
- the differences can be attributed to any of the following factors: the chemical composition of the powder mixtures, chemical reactions between existing elements during the liquid phase sintering, and take up or loss of light elements during milling and sintering.
- carbon may have been taken up from heat elements of graphite at the sintering operation.
- oxygen can be taken up from the environment as well as nitrogen during the milling process.
- various elements are dissolved in the liquid phase to be incorporated in the MX-phase, so that M will consist not entirely of titanium but to some degree also of vanadium and other metals from the base alloy ASP 2030 ® .
- a minor fraction of titanium is also likely to be dissolved in the melt, despite that the solubility of titanium is low.
- reaction kinetics is comparatively low, at least for some of the alloys, which is favourable, because it makes it possible to perform the liquid phase sintering at a high temperature for a long period of time, without causing the carbides to grow to any unacceptable degree.
- Carbon can be assumed to promote the wetting between the hard phase and the liquid phase, but also a certain amount of nitrogen appears to be necessary in the hard phase, on one hand for stabilising the hard phase and, on the other hand also to allow a take up of oxygen, which will replace some carbon and/or nitrogen in the crystal lattice of the hard phase.
- M 6 C- carbides enter the liquid phase during the sintering operation and that they may form a network around the M(C,N,O)-particles during the solidification, an effect which can be minimised, e.g. through selection of a suitable base alloy having a lower content of W and Mo.
- the hard phase particles In order to investigate the significance of the chemical composition of, in the first place, the hard phase particles, the chemical composition of the hard phase, and also the chemical composition of the matrix alloy, has been studied by means of various techniques. EDS-analysis (Energy Dispersive Spectroscopy) and Thermo-Calc calculation were employed. The Thermo-Calc calculated compositions of the hard phase and the matrix at the hardening temperature 1180 °C, of some selected alloys which had been sintered at 1480 °C, are given in Tables 6 and 7. The oxygen content has not been considered at the Thermo-Calc calculations. It is considered to be negligible in the matrix but may amount to about 4 atomic-% of the total content of C+N+O in the hard phase.
- Fig. 1 shows that alloy 69, through sintering at 1480 °C, obtained a very good homogeneity, containing hard phase particles with a mean size of about 0.8 ⁇ m, and that just very few particles had a size exceeding 1 ⁇ m.
- the homogeneity is more and more impaired and the hard phase particles are smaller and smaller, the higher the nitrogen fraction of the hard phase is, which is illustrated by Figs. 4-5.
- samples of alloy 71 were examined after liquid phase sintering at temperatures varying between 1350 and 1540 °C.
- Figs. 6-11 The microstructure after sintering at 1480 °C has been shown in Fig. 3.
- Fig. 6 shows that the microstructure after sintering at 1350 °C was almost as inhomogenous as after HIP-ing, Fig. 11, but that the microstructure achieved a good homogeneity with very evenly distributed hard phase particles, with particle sizes well below 1 ⁇ m, through sintering at a temperature exceeding 1480 °C, as is shown in Figs. 9 and 10.
- Table 6 and Table 8 The latter table shows that also an increased sintering temperature efficiently improves the homogeneity of the microstructure, if the value of the ratio
- C + N regions in terms of percent of a studied area of a section of the material, which maj or regions are void of any visible particles of said MX-phase and have a length of at least 6 d in the direction of the longest extension of the regions, a width, in any section of the region, of at least 6 d in a direction crosswise said longest extension, and an area of at least 9 ⁇ d 2 , where d is the mean value of the sizes of hard phase particles of MC-type in the longest extension of the particles in the viewed area of the section.
- the samples which were produced in the series of experiments IN were also subjected to mechanical tests. After hardening through dissolution treatment at 1180 °C, cooling to room temperature, and tempering three times at 560 °C, each time for 1 hour, the hardness at Nicker hardness tests amounted to between about 1080 and 1180 HN30, when the samples had a nominal composition. Take up of carbon and nitrogen increased the hardness up to between 1250 and 1300 HN30 for some alloys.
- the powder mixtures contained the base metal alloy ASP 2030 and a variant thereof, respectively, and carbon in the form of graphite powder.
- the variant had a lower content of Mo and W than ASP 2030 ® , and is referred to as ASP 20XX in the following.
- the powder mixture of alloy 110 also contained a minor amount of vanadium carbide, NC.
- the powders had the same physical character as the powders in the foregoing series of experiments.
- the ingredients are given in Table 9. Table 9 Ingredients (gram) of the powder mixtures
- the powder mixtures were milled in the same mode as in the series of experiments IV.
- Green bodies were prepared of the milled powders, and the green bodies were liquid phase sintered at temperatures varying between 1400 and 1540 °C during a holding time of 30 minutes at the sintering temperature.
- alloy 110 Besides Ti(C,N) and a matrix, alloy 110 also contained M 6 C- carbides, in which M substantially consisted of molybdenum and tungsten, and MC- carbides, which substantially consisted of vanadium carbides. In spite of the presence of vanadium carbides, the V-content of the hard phase was about 50 % less than what could be expected in view of the total composition of the alloy.
- the contents of niobium and vanadium in the hard phase of alloy 110 amounted to about 4 atomic-% and about 5 atomic-%, respectively, of the total content of M in the hard phase.
- alloy 160 the content of niobium in the hard phase amounted to about 15 atomic-% of the content of metal M.
- the chemical contents of C and N in the hard phases amounted to about 4.6 weight-% C and 3.6 weight-% nitrogen in alloy 110, and to about 5.1 weight-% C and
- a tool member was manufactured of alloy no 110 in the form of a cutter bit, intended to be used as an insert in a single tooth cutter. Prior to assembling, the insert was hardened from 1100 °C, followed by tempering at 560 °C/3xlh. The cutting capacity of the insert was compared with that of an equal insert, made of the highly qualified, powder metallurgy manufactured high speed steel ASP 2030 ® . A relative productivity in terms of cutting capacity was achieved by means of the insert made of the alloy according to the invention, which was about two times larger (80-100 % larger) than that of the known high speed steel. In this connection, it should also be mentioned that the material of the invention was manufactured at an experimental scale, i.e.
- the tool member - the insert - on the other hand was made of a sintered carbide material, one should also have reason to count on an additional increase of the cutting capacity, which confirms that the composite metal product of the invention may fill the gap between high speed steels and sintered carbide materials.
- Alloy no 160 was studied with reference to the microstructure after a heat treatment, which comprised hardening from 1150 °C, but which in other respects was performed in the same way as for alloy no 110 according to the above; see Fig. 12, which shows a homogenous microstructure of essentially evenly distributed, rounded carbides in the hardened and tempered matrix.
- the toughness was not quantified in terms of absolute magnitudes at toughness measurements. In comparison with samples which had been manufactured through HIP- ing, however, no systematic difference could be notified between HIP-ed samples and samples which had been subjected to liquid phase sintering according to the invention.
- This steel alloy provides, in the finished product, a matrix which can be hardened to a hardness > 500 HV30.
- the chemical composition of that high speed steel is the most suitable one, in order, in combination with the other constituents of the powder mixture, to provide a matrix having an optimal chemical composition.
- ASP 2030 ® has a comparatively high content of metals, which may form M 6 C-carbides. It is true that carbides of that type can be dissolved during the liquid phase sintering according to the invention, but it is also true that they can be re-established in the matrix and/or on the M(C,N)- and/or on the M(C,N,O)- phase particles, which may be disadvantageous.
- a high speed steel having a lower content of W and Mo may be more suitable, as has been demonstrated in the foregoing with reference to the use of the alloy ASP 20XX in the series of experiments V.
- other steel alloys are conceivable, high speed steels as well as other hardenable steels, e.g. cold work steels.
- a base alloy there should preferably be used a steel alloy, which in combination with other constituents provides a matrix in the finished material, which matrix can be hardened to a hardness ⁇ 500 HV30 after tempering.
- the content of hard phase in the powder mixture can be varied.
- titanium carbide-, titanium nitride-, and/or titanium carbonitride powders one may thus, at least for certain applications, consider moderate additions of other carbides or nitrides of MX-type, such as VC, NbC, TaC, ZrC, HfC, and/or (HfTi)C and corresponding nitrides, however not more than 30 mol-% of the total content of the achieved hard phase of MX- type in the finished product.
- MX-type such as VC, NbC, TaC, ZrC, HfC, and/or (HfTi)C and corresponding nitrides
- stimulating the generation of mixed carbonitrides may be that the formation of a dense material is accelerated even when sintering at a relatively low temperature, which could justify the addition of a certain amount of VC and/or NbC in the powder mixture or a higher content of vanadium and/or niobium in the base metal alloy.
- niobium carbide in the powder mixture also might stimulate the milling.
- mixed carbonitrides will be harder than pure titanium carbonitrides or pure titanium carbonitrideoxides, which could increase the hardness of the manufactured metal product.
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP03812741A EP1570096A1 (en) | 2002-12-12 | 2003-12-09 | Composite metal product and method for the manufacturing of such a product |
US10/532,603 US20060048603A1 (en) | 2002-12-12 | 2003-12-09 | Composite metal product and method for the manufacturing of such a product |
AU2003302772A AU2003302772A1 (en) | 2002-12-12 | 2003-12-09 | Composite metal product and method for the manufacturing of such a product |
JP2004558962A JP2006509908A (en) | 2002-12-12 | 2003-12-09 | Composite metal products and methods of manufacturing such products |
Applications Claiming Priority (2)
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SE0203668A SE524583C2 (en) | 2002-12-12 | 2002-12-12 | Composite metal product and process for making such |
SE0203668-9 | 2002-12-12 |
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WO2004053178A1 true WO2004053178A1 (en) | 2004-06-24 |
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PCT/SE2003/001908 WO2004053178A1 (en) | 2002-12-12 | 2003-12-09 | Composite metal product and method for the manufacturing of such a product |
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US (1) | US20060048603A1 (en) |
EP (1) | EP1570096A1 (en) |
JP (1) | JP2006509908A (en) |
AU (1) | AU2003302772A1 (en) |
SE (1) | SE524583C2 (en) |
WO (1) | WO2004053178A1 (en) |
Cited By (2)
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JP2007516752A (en) * | 2003-12-31 | 2007-06-28 | クロス,ヘニング | Intervertebral disc implant |
US9850558B2 (en) | 2013-06-10 | 2017-12-26 | Sumitomo Electric Industries, Ltd. | Cermet, method for producing cermet, and cutting tool |
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AT507215B1 (en) * | 2009-01-14 | 2010-03-15 | Boehler Edelstahl Gmbh & Co Kg | WEAR-RESISTANT MATERIAL |
EP2369031B1 (en) * | 2010-03-18 | 2016-05-04 | Oerlikon Trading AG, Trübbach | Coating on a nial2o4 basis in spinel structure |
US10047014B2 (en) * | 2014-10-13 | 2018-08-14 | Zhiguo XING | Plasma-sprayed tin coating having excellent hardness and toughness, the preparation method therefor, and a mold coated with said tin coating |
CN105296802B (en) * | 2015-11-03 | 2017-03-22 | 华南理工大学 | High-tenacity dual-scale structural titanium alloy and preparation method and application thereof |
CN105420612B (en) * | 2015-12-14 | 2017-10-20 | 布库 | A kind of knotter jaw alloy material and preparation method thereof |
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JPS59133352A (en) * | 1983-01-14 | 1984-07-31 | Fuji Die Kk | Hot rolling roll made of extremely high alloy steel |
JPH07173568A (en) * | 1990-12-26 | 1995-07-11 | Hitachi Tool Eng Ltd | Super hard alloy |
US6124040A (en) * | 1993-11-30 | 2000-09-26 | Widia Gmbh | Composite and process for the production thereof |
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2002
- 2002-12-12 SE SE0203668A patent/SE524583C2/en not_active IP Right Cessation
-
2003
- 2003-12-09 WO PCT/SE2003/001908 patent/WO2004053178A1/en active Application Filing
- 2003-12-09 US US10/532,603 patent/US20060048603A1/en not_active Abandoned
- 2003-12-09 JP JP2004558962A patent/JP2006509908A/en not_active Withdrawn
- 2003-12-09 AU AU2003302772A patent/AU2003302772A1/en not_active Abandoned
- 2003-12-09 EP EP03812741A patent/EP1570096A1/en not_active Withdrawn
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US4145213A (en) * | 1975-05-16 | 1979-03-20 | Sandvik Aktiebolg | Wear resistant alloy |
JPS59133352A (en) * | 1983-01-14 | 1984-07-31 | Fuji Die Kk | Hot rolling roll made of extremely high alloy steel |
JPH07173568A (en) * | 1990-12-26 | 1995-07-11 | Hitachi Tool Eng Ltd | Super hard alloy |
US6124040A (en) * | 1993-11-30 | 2000-09-26 | Widia Gmbh | Composite and process for the production thereof |
Non-Patent Citations (2)
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DATABASE WPI Week 198436, Derwent World Patents Index; Class M21, AN 1984-223142, XP002990418 * |
DATABASE WPI Week 199536, Derwent World Patents Index; Class L02, AN 1995-273162, XP002990419 * |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2007516752A (en) * | 2003-12-31 | 2007-06-28 | クロス,ヘニング | Intervertebral disc implant |
US9850558B2 (en) | 2013-06-10 | 2017-12-26 | Sumitomo Electric Industries, Ltd. | Cermet, method for producing cermet, and cutting tool |
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EP1570096A1 (en) | 2005-09-07 |
SE524583C2 (en) | 2004-08-31 |
SE0203668L (en) | 2004-06-13 |
AU2003302772A1 (en) | 2004-06-30 |
SE0203668D0 (en) | 2002-12-12 |
US20060048603A1 (en) | 2006-03-09 |
JP2006509908A (en) | 2006-03-23 |
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