WO2005106055A1 - High melting point metal based alloy material exhibiting high strength and high recrystallization temperature and method for production thereof - Google Patents
High melting point metal based alloy material exhibiting high strength and high recrystallization temperature and method for production thereof Download PDFInfo
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- WO2005106055A1 WO2005106055A1 PCT/JP2005/008069 JP2005008069W WO2005106055A1 WO 2005106055 A1 WO2005106055 A1 WO 2005106055A1 JP 2005008069 W JP2005008069 W JP 2005008069W WO 2005106055 A1 WO2005106055 A1 WO 2005106055A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/34—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in more than one step
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1078—Alloys containing non-metals by internal oxidation of material in solid state
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0005—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C37/00—Cast-iron alloys
- C22C37/04—Cast-iron alloys containing spheroidal graphite
-
- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Definitions
- the present invention relates to a high-temperature heat-resistant material, in particular, a high-strength oxide-dispersion-strengthened high-melting-point metal having a high melting point and one of Mo, W, and Cr as a mother phase.
- the present invention relates to a system alloy material and a method for producing the same.
- TZM alloy maximum operating temperature 1400 ° C of Plansee (PLANSEE AG.)
- Ti, Zr, and C are added to Mo
- the alloy is difficult to cure.
- Mo alloys which are typical examples of refractory metal-based alloy materials, exhibit low temperature embrittlement as a result of recrystallization once heated to a temperature higher than the recrystallization temperature (1000-1300 ° C).
- a major problem is that the strength at high temperatures decreases.
- the present inventors have proposed a multi-stage internal process in which a Mo—Ti alloy is first subjected to nitriding at a temperature lower than the recrystallization upper limit temperature, and then the temperature is increased stepwise to perform a nitriding treatment to generate TiN particles. Nitriding method was developed (Patent Document 1).
- the recrystallization temperature of the Mo alloy material obtained by this method reaches 1600 ° C due to the pinning effect of the precipitated TiN particles (Patent Document 1).
- the present inventors performed a multi-stage internal nitriding treatment on a metal alloy containing Mo as a matrix and at least one of Ti, Zr, Hf, V, Nb and Ta as a solid solution.
- a method for performing external nitridation treatment (Patent Document 2).
- a high corrosion resistance, high strength, high toughness Mo alloy material was obtained.
- the present inventors reported a study on a carbonization treatment method in which a small amount of carbon was deposited and then carbon was diffused at the grain boundary by vacuum heating as a method of strengthening the crystal grain boundaries of the Mo-based material. (Non-Patent Document 1).
- Non-Patent Document 2 reported a study on a method of controlling the material structure and toughening the carbonized TZM alloy using a diluted CO gas.
- the present inventors have reported a study on the material structure when a recrystallized Mo—Ti alloy is heat-treated with C 2 gas (Non-Patent Document 3).
- Patent Document 1 JP 2001-073060 A
- Patent Document 2 JP 2003-293116 A
- Non-Patent Document 1 Hoshika Tetsushi et al. "Powder and Powder Metallurgy” 49 (2002) 32-36
- Non-Patent Document 2 Naoki Nomura et al. “Summary of the Lectures of the Powder and Powder Metallurgy Association 2002 Fall Meeting”
- Non-Patent Document 3 Naoki Nomura et al. "Summary of the Lectures of the Powder and Powder Metallurgy Association 2003 Autumn Meeting"
- the inventors of the present invention have been conducting research on structure control and toughening of a Mo-based material by nitriding or carbonizing for many years, but the temperature is gradually increased from the nitriding below the upper limit of recrystallization temperature.
- the multi-stage internal nitriding alloy material which is raised and nitrided, is further carbonized to be stable without recrystallization for a long time even when used in a high temperature and high vacuum of at least 1600 ° C.
- the company succeeded in developing a refractory metal-based alloy material that has superior strength at room temperature and high temperature (for example, 1500 ° C) compared to commercially available Mo alloys.
- the present invention provides (l) one of Mo, W, and Cr as a parent phase and at least one of Ti, Zr, Hf, V, Nb, and Ta as a solid solution metal.
- a force-purifying material obtained by carbonizing a processing material containing solid solution metal nitride particles dispersed and precipitated in a matrix by a multi-stage nitriding treatment of an alloy processing material using a carbon source in which oxygen coexists.
- a high-strength, high-recrystallization temperature, high-melting point metal-based alloy material containing carbon segregated at the grain boundary by the carbonization treatment and oxide particles converted from the nitride particles. is there.
- the present invention also provides (2) the high strength and high recrystallization temperature of (1), wherein the surface of the alloy material has a processed structure and the inside is a recrystallized structure. Melting point metal-based alloy material.
- the present invention also provides: (3) the above (1) or (2), wherein Mo is used as a mother phase, Ti is used as a solid solution metal, and the recrystallization temperature is 1600 ° C or higher.
- Refractory metal alloy material is used.
- the present invention provides (4) one of Mo, W, and Cr as a mother phase, and at least one of Ti, Zr, Hf, V, Nb, and Ta as a solid solution metal.
- a carbon source containing oxygen coexisting in the alloy material was used.
- the present invention also provides: (5) performing the first-stage nitriding treatment at a temperature not higher than the recrystallization upper limit temperature of the alloy processing material and at a temperature not lower than the recrystallization lower limit temperature-(minus) 200 ° C; Then, the nitride particles of the solid solution metal are dispersed and formed, and then the second stage nitriding treatment is performed at a temperature equal to or higher than the recrystallization lower limit temperature of the alloy material obtained by the first stage nitriding treatment.
- the present invention also provides (6) the high melting point of (4) or (5), wherein the carbonization treatment is performed using an inert gas containing from 0 :! to 5% by volume of CO. Manufacturing method of metal alloy material
- the present inventor has proposed that a high melting point metal working material in which nitride particles are dispersed and contained in a matrix phase is carbonized using a carbon source in which oxygen coexists, thereby obtaining a grain boundary due to carbon grain boundary segregation. It was found that not only the strengthening phenomenon occurs but also that the diffusion of oxygen converts the nitride particles into oxide particles, causing a dispersion precipitation phenomenon (internal oxidation) of the solid solution metal oxide particles.
- the material becomes brittle. Formation of MoC film by coexistence of oxygen (Carbonization of Mo itself)
- the oxide particles thus generated have a pinning effect of inhibiting the movement of crystal grain boundaries similarly to nitride particles, but are thermodynamically more stable than nitride particles.
- Oxide particles dispersed and precipitated in high-melting-point metal do not decompose for a long time even at high temperature and high vacuum, and remain stable.
- the recrystallization brittleness seen in the case of nitride particles is improved, and the recrystallization temperature is improved. As it increases, it increases resistance to high-temperature deformation.
- the alloy material obtained by the multi-stage nitriding treatment and the carbonization treatment has a structure in which a rolled structure is maintained at least on the surface, and oxide particles of a solid solution metal are dispersed and precipitated from the surface to the inner layer. It is.
- the strength increases due to carbon grain boundary segregation, and the recrystallization temperature increases due to precipitation hardening of the oxide particles.
- Mo-Ti alloys exhibit strength characteristics that are 2-3 times higher than conventional commercial Mo alloys over a wide range from room temperature to 1600 ° C, and the high temperature of 1700 ° C at which multi-stage internal nitride recrystallizes. ⁇ Has excellent heat resistance without recrystallization even under high vacuum.
- the present invention provides a refractory metal-based heat-resistant alloy material which is stable under high temperature and high vacuum for a long period of time and exhibits excellent heat resistance without recrystallization.
- the rolled structure maintained on the surface of the alloy material has the effect of inhibiting the propagation of cracks, so that it has excellent impact resistance.
- the production method of the present invention is a method in which an alloy material is processed into an arbitrary shape, then calo-heat treated using a nitriding atmosphere, and then heat-treated using a carbon source in which oxygen coexists. Products can be easily handled.
- Ti, Zr, Hf, V, Nb, and Ta are suitable as the solid solution metal. Since all of these metals form more stable nitrides than Group 6A elements such as Mo and W, they are necessary for controlling the structure by the first-stage multi-stage internal nitridation. In addition, since all of these oxides are more stable than their nitrides, a conversion reaction from nitride particles to oxide particles occurs by C ⁇ gas heat treatment after multi-stage nitriding. The content is about 0 :! to 5. Owt%, more preferably about 0.3 to 2.0%. If it is less than 0. lwt%, the amount of precipitated particles is too small to prevent recrystallization. 5. When Owt% is exceeded, nitriding-C ⁇ gas heat The material after the treatment becomes brittle and is difficult to use in practice.
- the multi-stage internal nitride material is obtained by disposing a metal element dissolved in a metal alloy material containing one of Mo, W, and Cr as a mother phase in a nitriding atmosphere. Alloy fine particles formed by dispersing and containing fine nitrides formed in the matrix in the matrix, and at least the surface side of the processed material has nitride precipitate particles while maintaining a processed structure such as rolling. Have a grain-grown structure.
- the alloy processing material is subjected to a first-stage nitriding treatment at a temperature not higher than the recrystallization upper limit temperature of the alloy and not lower than the recrystallization lower limit temperature (minus) 200 ° C or more.
- the nitride particles of the molten metal element are dispersed and formed, and then the second-stage nitriding treatment is performed at a temperature equal to or higher than the lower limit of recrystallization of the alloy processing material obtained in the first-stage nitriding treatment.
- This is a method in which nitride particles dispersed and formed by the treatment are grown and stabilized.
- the recrystallization temperature of the alloy processing material mainly depends on the manufacturing conditions of the alloy material such as the degree of work and has a certain range between the upper limit value and the lower limit value of the recrystallization. 950 ⁇ : 1020 ° C for Ti alloy processed materials. The temperature at which recrystallization occurs decreases as the degree of processing increases.
- the reason why the first-stage nitriding treatment is performed at the recrystallization upper limit temperature or lower is that if the nitriding treatment is performed at a higher temperature, the material is recrystallized and becomes brittle. The reason for this is that at a lower temperature, the diffusion rate of nitrogen is too slow, and it is difficult to perform internal nitriding to a depth sufficient for practical use.
- the number of stages of the multi-stage nitriding treatment is at least two. However, as the nitriding treatment of the third and subsequent stages, the recrystallization temperature of the alloy processing material obtained by the preceding nitriding treatment is not lower than the lower limit temperature. A method of heating at a temperature to further grow and stabilize the nitride particles dispersedly formed by the preceding nitriding treatment can also be carried out.
- the distribution density of the precipitated TiN particles in the obtained internal nitride layer increases from the surface toward the inside (the surface portion is large and the inside is small) ) Occurs.
- recrystallization of the internal nitride layer obtained in the first-stage nitridation in a nitrogen atmosphere The temperature is highest near the surface (eg, 1400 ° C (maximum recrystallization temperature)) and lowest at the tip of the internal nitride layer (eg, 950 ° C (minimum recrystallization temperature)).
- the thickness of the inner nitrided layer obtained by the first-stage nitridation defines the theoretical maximum thickness that can leave the working structure such as rolling finally as it is.
- the second-stage nitriding is performed just above the recrystallization minimum temperature to increase the precipitation density of the TiN particles near the tip of the inner nitride layer obtained by the first-stage nitriding, and to increase the It is necessary to increase the size.
- the recrystallization minimum temperature after the second-stage nitriding increases.
- the work structure such as rolling can be left thickest, but the number of nitriding steps increases. , The time is too long. The same is true for the third and subsequent stages of nitriding.
- the morphology of the nitride particles depends on the nitriding temperature. For example, in three stages of nitriding at 900 ° C ⁇ 1200 ° C ⁇ 1600 ° C, the particles after the first stage nitriding have a diameter of about 1 2 ⁇ 2 disk-shaped particles, the amount of precipitation decreases as the force moves toward the inside of the sample. Near the outermost surface, almost all alloying elements are precipitated as nitrides. After the second-stage nitriding, the grains grow to about a dozen or so, and the distribution density gradient of precipitated TiN particles in the working structure such as rolling becomes gentle.
- the TiN particles grow into rod-like particles with a length of about 50 to 150 mm, and almost all of the Ti exists as nitrides in the processing structure such as rolling remaining on the surface of the material. I have.
- the refractory metal-based alloy material whose recrystallization temperature has been raised by multi-stage internal nitridation is carbonized using a carbon source in which oxygen coexists.
- a rolled structure is maintained on the surface of the material, and the inside has a characteristic two-layer structure having a recrystallized structure.
- the amount of carbon segregated at the grain boundary is about 30 to 150 ppm (wt%). If less than this, the effect of strengthening the grain boundaries cannot be expected.
- All the nitrides in the work structure such as the rolling that remained in the multi-stage nitridation change to oxide particles. At this time, the size and form change.
- a rod-shaped TiN particle (aspect ratio: 4 to 7) with a length of 50 to 150 nm has a length of 30 to 60 nm (aspect ratio: 2 to 7). It changes to oxide particles of 3). And as the size decreases, the number of particles increases
- a diluted C ⁇ ⁇ ⁇ gas can be used as a carbon source in which oxygen coexists. It is preferable that the diluted C gas be an inert gas containing 0.1 to 5% by volume of CO. If the C ⁇ concentration is higher than 5% by volume, carbonization of the refractory metal occurs significantly, which is desirable. It is easy to control the carbon potential of dilute C ⁇ gas, and by adjusting the carbon concentration, the formation of a hard and brittle carbide layer on the alloy material surface can be suppressed.
- the carbonization treatment is not limited to lean CO gas, but may be performed by a method in which oxygen is coexisted with a carbon source such as solid carbon and hydrocarbon around the high melting point metal alloy material.
- a carbon source such as solid carbon and hydrocarbon around the high melting point metal alloy material.
- the heat treatment is performed while the processing material is not in direct contact with the carbon source and the carbon powder is placed in the vicinity of the processing material while performing vacuum evacuation using a rotary pump or the like, the same as when using a dilute CO gas Reaction occurs.
- the degree of vacuum is not very good, trace amounts of oxygen in the atmosphere react with carbon, resulting in the generation of CO gas, which is involved in the reaction.
- a similar reaction occurs even when a processing material is carried in a mixed powder of carbon powder and alumina powder and reacted under low vacuum.
- a solid carbon source is used, a hard and brittle refractory metal carbide layer is likely to be formed on the surface of the processed material when the heating temperature is low. I like it
- the recrystallization lower limit temperature and upper limit temperature are 950 ° C and 1400 ° C after the first stage treatment, 1250 ° C and 1600 ° C after the second stage treatment, and 1600 ° C and 1800 ° C after the third stage treatment, respectively. Under a nitrogen atmosphere). The nitriding treatment was performed in a latm N gas stream. One of the two test pieces was used as a comparative example as it was. Another
- the two specimens were carbonized at 1500 ° C for 16 hours in a dilute CO gas atmosphere.
- FIG. 1 shows an optical microscope structure of the test piece after the treatment.
- Multi-stage nitriding material, multi-stage nitriding + charcoal It can be seen that the rolled structure is maintained on the surface of each of the chemically treated materials.
- Fig. 2 shows the TEM structure of the treated test piece. It can be seen that the rod-shaped TiN particles of the multi-stage nitriding material have been changed to elliptical Ti oxides in the multi-stage nitriding and carbonizing material.
- Figure 3 shows the results of the three-point bending test. It can be seen that the mechanical properties did not change even after the treatment with C ⁇ gas. DBT T (ductile-brittle transition temperature) also changes.
- FIG. 4 shows an optical microscope after vacuum processing at 1600 ° C for 1 hour in the first stage and 1700 ° C for 1 hour in the second stage in order to examine the recrystallization temperature of the test piece. Indicates the organization.
- the area immediately below the rolled structure looks white and recrystallized, whereas in the case of the multi-stage nitrided and carbonized material in the example, recrystallization did not occur even at 1700 ° C heating. I understand.
- Figure 5 shows the results of a high-temperature three-point bending test at 1500 ° C of the test specimen, the multi-stage nitrided material, and the multi-stage nitrided and carbonized material before the treatment. It can be seen that the strength of the multi-stage nitride material and the multi-stage nitridation and carbonization treatment material is greatly improved as compared with the test piece without treatment.
- the refractory metal-based alloy material of the present invention has heat resistance higher than that of the current TZM alloy, and is used as a heat-resistant structural material compatible with an ultra-high temperature environment.
- a heat-resistant structural material compatible with an ultra-high temperature environment.
- FIG. 1 is a drawing substitute photograph showing an optical microscope structure of a test piece after treatment in Example 1.
- FIG. 2 is a drawing-substituting photograph showing a TEM structure of a test piece after treatment in Example 1.
- FIG. 3 is a graph showing the results of a three-point bending test of a test piece after the treatment in Example 1.
- FIG. 4 is a photograph substituted for a drawing, showing an optical microscope structure after heating a test piece after treatment in Example 1 at a high temperature.
- FIG. 5 is a graph showing the results of a high-temperature three-point bending test at 1500 ° C. of a test piece before treatment, a multi-stage nitride material, and a multi-stage nitriding + carbonized material.
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP05737380A EP1752551A4 (en) | 2004-04-30 | 2005-04-27 | High melting point metal based alloy material exhibiting high strength and high crystallization temperature and method for production thereof |
US11/579,143 US20080017278A1 (en) | 2004-04-30 | 2005-04-27 | High Melting Point Metal Based Alloy Material Lexhibiting High Strength and High Recrystallization Temperature and Method for Production Thereof |
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JP2004-135752 | 2004-04-30 | ||
JP2004135752A JP4255877B2 (en) | 2004-04-30 | 2004-04-30 | High-strength and high recrystallization temperature refractory metal alloy material and its manufacturing method |
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WO2005106055A1 true WO2005106055A1 (en) | 2005-11-10 |
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PCT/JP2005/008069 WO2005106055A1 (en) | 2004-04-30 | 2005-04-27 | High melting point metal based alloy material exhibiting high strength and high recrystallization temperature and method for production thereof |
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US (1) | US20080017278A1 (en) |
EP (1) | EP1752551A4 (en) |
JP (1) | JP4255877B2 (en) |
KR (1) | KR100845042B1 (en) |
TW (1) | TWI262953B (en) |
WO (1) | WO2005106055A1 (en) |
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DE102009002985A1 (en) * | 2009-05-11 | 2010-11-18 | Robert Bosch Gmbh | Process for carbonitriding |
FR2997557B1 (en) | 2012-10-26 | 2016-01-01 | Commissariat Energie Atomique | NANOFIL ELECTRONIC DEVICE WITH TRANSITION METAL BUFFER LAYER, METHOD OF GROWING AT LEAST ONE NANOWIL, AND DEVICE MANUFACTURING METHOD |
FR2997420B1 (en) * | 2012-10-26 | 2017-02-24 | Commissariat Energie Atomique | PROCESS FOR GROWING AT LEAST ONE NANOFIL FROM A TWO-STEP NITRIDE TRANSITION METAL LAYER |
US10597757B2 (en) | 2014-04-23 | 2020-03-24 | Questek Innovations Llc | Ductile high-temperature molybdenum-based alloys |
US10363182B2 (en) * | 2014-07-14 | 2019-07-30 | Hill-Rom Services, Inc. | Patient control arm with phone dock and head of bed lockout |
AT16308U3 (en) * | 2018-11-19 | 2019-12-15 | Plansee Se | Additively manufactured refractory metal component, additive manufacturing process and powder |
CN110129645B (en) * | 2019-05-24 | 2021-02-19 | 安泰科技股份有限公司 | Multifunctional tungsten alloy gradient material and preparation method thereof |
Citations (4)
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JPH05263179A (en) * | 1992-03-17 | 1993-10-12 | Kubota Corp | Chromium base heat resistant sintered alloy and its manufacture |
JP2001073060A (en) * | 1999-09-06 | 2001-03-21 | Japan Science & Technology Corp | High melting point metallic alloy material having high toughness and high strength |
JP2001295023A (en) * | 2000-04-06 | 2001-10-26 | Allied Material Corp | High melting point metallic material having surface hardened layer and its producing method |
JP2003293070A (en) * | 2002-03-29 | 2003-10-15 | Japan Science & Technology Corp | Mo-ALLOY WORK MATERIAL WITH HIGH STRENGTH AND HIGH TOUGHNESS, AND ITS MANUFACTURING METHOD |
Family Cites Families (4)
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US3458366A (en) * | 1965-10-01 | 1969-07-29 | Gen Electric | Wrought chromium base alloy |
US4265662A (en) * | 1977-12-29 | 1981-05-05 | Sumitomo Electric Industries, Ltd. | Hard alloy containing molybdenum and tungsten |
US4514234A (en) * | 1983-02-10 | 1985-04-30 | Tokyo Shibaura Denki Kabushiki Kaisha | Molybdenum board and process of manufacturing the same |
JP4302930B2 (en) * | 2002-03-29 | 2009-07-29 | 国立大学法人 岡山大学 | High corrosion resistance, high strength, high toughness Nitrided Mo alloy processed material and its manufacturing method |
-
2004
- 2004-04-30 JP JP2004135752A patent/JP4255877B2/en not_active Expired - Lifetime
-
2005
- 2005-04-27 KR KR1020067022235A patent/KR100845042B1/en not_active IP Right Cessation
- 2005-04-27 US US11/579,143 patent/US20080017278A1/en not_active Abandoned
- 2005-04-27 WO PCT/JP2005/008069 patent/WO2005106055A1/en active Application Filing
- 2005-04-27 EP EP05737380A patent/EP1752551A4/en not_active Withdrawn
- 2005-04-29 TW TW094114036A patent/TWI262953B/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05263179A (en) * | 1992-03-17 | 1993-10-12 | Kubota Corp | Chromium base heat resistant sintered alloy and its manufacture |
JP2001073060A (en) * | 1999-09-06 | 2001-03-21 | Japan Science & Technology Corp | High melting point metallic alloy material having high toughness and high strength |
JP2001295023A (en) * | 2000-04-06 | 2001-10-26 | Allied Material Corp | High melting point metallic material having surface hardened layer and its producing method |
JP2003293070A (en) * | 2002-03-29 | 2003-10-15 | Japan Science & Technology Corp | Mo-ALLOY WORK MATERIAL WITH HIGH STRENGTH AND HIGH TOUGHNESS, AND ITS MANUFACTURING METHOD |
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EP1752551A1 (en) | 2007-02-14 |
US20080017278A1 (en) | 2008-01-24 |
KR20070004896A (en) | 2007-01-09 |
JP4255877B2 (en) | 2009-04-15 |
JP2005314768A (en) | 2005-11-10 |
EP1752551A4 (en) | 2010-09-15 |
TWI262953B (en) | 2006-10-01 |
KR100845042B1 (en) | 2008-07-08 |
TW200535254A (en) | 2005-11-01 |
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