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 PDF

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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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temperature
stage
alloy
alloy material
recrystallization
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PCT/JP2005/008069
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French (fr)
Japanese (ja)
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Masahiro Nagae
Tetsuo Yoshio
Jun Takada
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Japan Science And Technology Agency
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Priority to EP05737380A priority Critical patent/EP1752551A4/en
Priority to US11/579,143 priority patent/US20080017278A1/en
Publication of WO2005106055A1 publication Critical patent/WO2005106055A1/en

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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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Abstract

A high melting point metal based alloy material exhibiting high strength and a high recrystallization temperature, characterized in that it is a worked material which is produced by a method comprising providing an alloy worked material having one metal of Mo, W and Cr as a base phase and at least one of Ti,Zr, Hf, V, Nb and Ta as a metal forming a solid solution with the base phase, subjecting the alloy worked material to a multi-step nitriding treatment, to thereby form a worked material containing particles of a nitride of the above metal forming a solid solution with the base phase, being precipitated and dispersed in the base phase, and then subjecting the above worked material containing particles of a nitride to a carbonizing treatment by the use of a carbon source co-existing with oxygen, and in that it contains the carbon segregated at a grain boundary due to the carbonizing treatment and oxide particles converted from the above nitride particles.

Description

明 細 書  Specification
高強度'高再結晶温度の高融点金属系合金材料とその製造方法 技術分野  High-strength 'high-melting-point refractory metal-based alloy materials and their manufacturing methods
[0001] 本発明は、高温耐熱材料、特に、高融点金属である Mo， W， Crの 1種を母相とす る酸化物粒子分散強化型の高強度'高再結晶温度の高融点金属系合金材料とその 製造方法に関する。  [0001] 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.
[0002] 現在、高融点金属系耐熱合金として、 Moに Ti, Zr,及び Cを添加したプランゼー 社 (PLANSEE AG. )の TZM合金 (最高使用温度 1400°C)がほぼ独占的に使用 されているが、該合金は難カ卩ェ性である。  [0002] Currently, as a refractory metal-based heat-resistant alloy, TZM alloy (maximum operating temperature 1400 ° C) of Plansee (PLANSEE AG.), In which Ti, Zr, and C are added to Mo, is almost exclusively used. However, the alloy is difficult to cure.
[0003] 高融点金属系合金材料の代表例である Mo合金は、一旦、その再結晶温度 (1000 〜1300°C)以上に加熱されると、再結晶が起こる結果、低温脆性を示すことや、高温 での強度が低下することが大きな問題点である。この問題を解決すベぐ本発明者ら は、 Mo— Ti合金をまず再結晶上限温度以下で窒化処理し、次に段階的に温度を 上げて窒化処理を行って TiN粒子を生成させる多段内部窒化法を開発した (特許文 献 1)。この方法により得られる Mo合金材料は析出した TiN粒子のピン止め効果によ つて再結晶温度が 1600°Cに達する（特許文献 1)。  [0003] 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. In order to solve this problem, 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).
[0004] さらに、本発明者らは、 Moを母相とし、 Ti, Zr, Hf， V, Nb， Taの少なくとも 1種を 固溶した合金力卩ェ材に多段内部窒化処理を行い、次レ、で外部窒化処理を行う方法 を開発した（特許文献 2)。この方法によって、高耐食性、高強度、高靭性の Mo合金 加工材が得られた。さらに、本発明者らは、 Mo系材料の結晶粒界を強化する方法と して、微量の炭素を蒸着した後、真空加熱により炭素を粒界拡散させる炭化処理方 法についての研究を報告した（非特許文献 1)。また、本発明者らは、希薄 COガスを 用いた TZM合金の炭化処理による材料組織の制御と強靭化方法についての研究 を報告した (非特許文献 2)。また、本発明者らは、再結晶化した Mo— Ti系合金を C 〇ガス熱処理した場合の材料組織にっレ、ての研究を報告した（非特許文献 3)。  [0004] Furthermore, 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. We have developed a method for performing external nitridation treatment (Patent Document 2). By this method, a high corrosion resistance, high strength, high toughness Mo alloy material was obtained. Furthermore, 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). In addition, the present inventors reported a study on a method of controlling the material structure and toughening the carbonized TZM alloy using a diluted CO gas (Non-Patent Document 2). In addition, 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).
[0005] 特許文献 1 :特開 2001— 073060号公報  Patent Document 1: JP 2001-073060 A
特許文献 2 :特開 2003— 293116号公報  Patent Document 2: JP 2003-293116 A
非特許文献 1：星加哲志他「粉体および粉末冶金」 49(2002)32-36 非特許文献 2：野村直紀他「粉体粉末冶金協会平成 14年秋季大会講演概要集」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”
(2002) 201 (2002) 201
非特許文献 3：野村直紀他「粉体粉末冶金協会平成 15年秋季大会講演概要集」 Non-Patent Document 3: Naoki Nomura et al. "Summary of the Lectures of the Powder and Powder Metallurgy Association 2003 Autumn Meeting"
(2003) 31 (2003) 31
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 本発明者らが開発した上記の多段内部窒化法により、 Mo— Ti系合金で再結晶温 度が 1600°Cに達するものが得られる力 TiN粒子の高温 ·高真空中での安定性が 不十分なため、合金表面からの TiN粒子の分解 ·脱窒素反応が徐々に進行する結 果、長期間の使用では再結晶が起こり脆ィ匕するという問題点が残った。 [0006] By the above-described multi-stage internal nitriding method developed by the present inventors, a force capable of obtaining a Mo-Ti based alloy having a recrystallization temperature reaching 1600 ° C. Stability of TiN particles at high temperature and high vacuum. Due to the insufficient properties, the decomposition and denitrification of the TiN particles from the alloy surface gradually proceeded, and as a result, there was a problem that long-term use resulted in recrystallization and brittleness.
課題を解決するための手段  Means for solving the problem
[0007] 本発明者らは、長年、 Mo系材料の窒化処理や炭化処理による組織制御と強靭化 についての研究を行ってきたが、再結晶上限温度以下の窒化処理から段階的に温 度を上げて窒化処理する多段内部窒化処理した合金材料をさらに炭化処理すること によって、少なくとも 1600°Cの高温 ·高真空中で使用しても、長期間に亘り再結晶化 することなく安定であって、市販の Mo合金に比べて室温及び高温 (例えば、 1500°C) での強度がともに優れる高融点金属系合金材料の開発に成功した。  [0007] 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.
[0008] すなわち、本発明は、（l) Mo, W, Crのうちの 1種を母相とし、 Ti, Zr, Hf， V, Nb ， Taのうちの少なくとも 1種を固溶金属とする合金加工材の多段窒化処理によって母 相中に分散析出した固溶金属の窒化物粒子を含む加工材を、さらに酸素が共存す る炭素源を用いて炭化処理した力卩ェ材であって、該炭化処理によって粒界偏析して レ、る炭素と、該窒化物粒子から変換された酸化物粒子とを含有すること特徴とする高 強度 ·高再結晶温度の高融点金属系合金材料、である。  [0008] That is, 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.
[0009] また、本発明は、 （2)合金材料の表面部は加工組織が維持され、内部は再結晶組 織であること特徴とする上記（1)の高強度'高再結晶温度の高融点金属系合金材料 、である。  [0009] 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.
[0010] また、本発明は、 （3) Moを母相とし、 Tiを固溶金属とし、再結晶温度が 1600°C以 上であることを特徴とする上記（1)又は（2)の高融点金属系合金材料、である。 [0011] さらに、本発明は、（4) Mo， W， Crのうちの 1種を母相とし、 Ti, Zr， Hf, V, Nb, T aのうちの少なくとも 1種を固溶金属とする合金加工材を窒化雰囲気中において多段 内部窒化処理することによって固溶金属の窒化物粒子を母相中に分散含有させた 後、該合金力卩ェ材に酸素が共存する炭素源を用いた炭化処理を行うことを特徴とす る上記（1)又は（2)の高融点金属系合金材料の製造方法、である。 [0010] 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. [0011] Further, 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. After the multi-step internal nitriding treatment of the alloy material to be processed in a nitriding atmosphere to disperse and contain the solid solution metal nitride particles in the matrix, a carbon source containing oxygen coexisting in the alloy material was used. The method for producing a refractory metal-based alloy material according to the above (1) or (2), wherein carbonization is performed.
[0012] また、本発明は、 （5)第 1段窒化処理を、該合金加工材の再結晶上限温度以下で 、かつ再結晶下限温度—（マイナス） 200°C以上の温度で行レ、、固溶金属の窒化物 粒子を分散形成させ、次いで、第 2段窒化処理を、第 1段窒化処理で得られた該合 金加工材の再結晶下限温度以上の温度で行い、第 1段窒化処理により分散形成さ れた窒化物粒子を粒成長させ安定化させることを特徴とする上記 (4)の高融点金属 系合金材料の製造方法、である。  [0012] 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. (4) The method for producing a refractory metal alloy material according to the above (4), wherein the nitride particles dispersedly formed by the nitriding treatment are grown and stabilized.
[0013] また、本発明は、 （6) COを 0.：!〜 5容積％含有する不活性ガスを用いて炭化処理 を行うことを特徴とする上記 (4)又は（5)の高融点金属系合金材料の製造方法、であ る  [0013] 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
[0014] 本発明者は、母相中に窒化物粒子を分散含有させた高融点金属加工材を酸素が 共存する炭素源を用いて炭化処理を行うことによって、炭素の粒界偏析による粒界 強化現象が起こることのみならず、酸素の拡散によって窒化物粒子が酸化物粒子に 変換されて固溶金属の酸化物粒子の分散析出現象 (内部酸化)が起こることを見出し た。  [0014] 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.
[0015] 酸素が共存する炭素源を用いて炭化処理を行うことによって酸化物粒子が形成さ れる理由は、明確ではないが、加熱処理温度が低い場合は、加工材の表面に非常 に薄い Mo C皮膜が生成し、加工材内部への酸素の拡散が阻害される結果、 Mo C  [0015] The reason why oxide particles are formed by carbonization using a carbon source in which oxygen coexists is not clear, but when the heat treatment temperature is low, very thin Mo As a result of the formation of a C film and the inhibition of diffusion of oxygen into the workpiece, Mo C
2 2 皮膜と加工材との界面からの炭素のみの拡散が可能になり内部炭化が起こるが、高 温で加熱処理を行った場合には、加工材の表面に Mo C皮膜が生成しにくいので酸  22 2 Only carbon can be diffused from the interface between the film and the processed material, causing internal carbonization.However, when heat treatment is performed at a high temperature, a MoC film is not easily formed on the surface of the processed material. Acid
2  2
素の拡散が起こるからと考えられる。例えば、 CHガスを 2容積 %含んだアルゴンガス  It is considered that elementary diffusion occurs. For example, argon gas containing 2% by volume of CH gas
4  Four
で同様な熱処理を行うと、熱処理温度に関係なく非常に厚い MoC皮膜が生成し、  When a similar heat treatment is performed, a very thick MoC film is generated regardless of the heat treatment temperature,
2  2
材料は脆くなる。酸素が共存することによって MoC皮膜の生成 (Moそのものの炭化  The material becomes brittle. Formation of MoC film by coexistence of oxygen (Carbonization of Mo itself)
2  2
反応)が抑制されるので炭素の粒界拡散と酸素の粒内拡散が同時に起こると考えら れる。 Reaction) is suppressed, so it is thought that carbon grain boundary diffusion and oxygen intragranular diffusion occur simultaneously. It is.
[0016] このようにして生成した酸化物粒子は、窒化物粒子と同様に結晶粒界の移動を阻 止するピン止め効果を有するが、窒化物粒子に比べて熱力学的に安定であるため、 高融点金属中に分散析出した酸化物粒子は高温 ·高真空中でも長期間分解せず安 定に存在し、窒化物粒子の場合に見られる再結晶脆ィヒは改善され、再結晶温度も高 まるので、高温変形に対する抵抗力を高める。  [0016] 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.
[0017] 多段窒化処理及び炭化処理により得られる該合金材料は、少なくとも表面には加 ェ圧延組織が維持され、かつ、表面から内層にかけて固溶金属の酸化物粒子が分 散析出している構造である。このように、炭素の粒界偏析により強度が増大するととも に、酸化物粒子の析出硬化により、再結晶温度が向上する。例えば、 Mo— Ti合金 では室温から 1600°Cまでの広い範囲で従来の巿販 Mo合金よりも 2〜3倍の強度特 性を示し、多段内部窒化材が再結晶化する 1700°Cの高温 ·高真空下においても全 く再結晶化しなレ、優れた耐熱性を有する。  [0017] 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. As described above, the strength increases due to carbon grain boundary segregation, and the recrystallization temperature increases due to precipitation hardening of the oxide particles. For example, 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.
発明の効果  The invention's effect
[0018] 本発明は、高温 ·高真空下で長期間に亘り安定で再結晶化しない優れた耐熱性を 示す高融点金属系耐熱合金材料を提供する。合金材料の表面部に維持された圧延 組織がクラックの伝播を阻害する効果を有することにより耐衝撃性にも優れる。さらに 、本発明の製造法は、合金材料を任意形状へ加工した後に窒化雰囲気を用いてカロ 熱処理し、次いで酸素が共存する炭素源を用いて加熱処理する手法であり、予め加 ェした複雑形状製品にも容易に対応できる。  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. Further, 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.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0019] 本発明の高融点金属系合金材料において、固溶金属としては、 Ti, Zr, Hf, V, N b, Taが適する。これらの金属はいずれも Mo, Wなどの 6A族元素よりも安定な窒化 物を形成するため、第一段目の多段内部窒化による組織制御に必要である。また、 これらの酸化物はいずれもそれらの窒化物より安定であるため、多段窒化処理後の C〇ガス熱処理によって窒化物粒子→酸化物粒子への変換反応が起こる。含有量と しては約 0.：!〜 5. Owt%、より好ましくは約 0. 3〜2. 0¾«である。 0. lwt%未満では 析出粒子が少なすぎて再結晶を抑制できなレ、。 5. Owt%を超えると窒化- C〇ガス熱 処理後の材料が脆くなり、実用上使用困難である。 [0019] In the refractory metal alloy material of the present invention, 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〇 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〇 gas heat The material after the treatment becomes brittle and is difficult to use in practice.
[0020] これらの固溶金属を含有する高融点金属系合金材料は所望の形状に加工された 後、多段内部窒化処理する。この多段内部窒化材及びその製造方法自体は、上記 の特許文献 1 (特開 2001-073060号公報）に示されるように公知の手段である。  [0020] These refractory metal-based alloy materials containing a solid solution metal are processed into a desired shape and then subjected to a multi-stage internal nitriding treatment. The multi-stage internal nitride material and the manufacturing method itself are known means as shown in Patent Document 1 (Japanese Patent Application Laid-Open No. 2001-073060).
[0021] すなわち、多段内部窒化材は、 Mo, W, Crのうちの 1種を母相とする合金力卩ェ材 中に固溶された金属元素を窒化雰囲気中におレ、て内部窒化することによって形成さ れた微細窒化物を母相中に分散含有する該合金力卩ェ材であって、加工材の少なくと も表面側は圧延などの加工組織を維持したまま窒化物析出粒子が粒成長した組織 を有している。  [0021] That is, 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.
[0022] また、その製造方法は、該合金加工材を第 1段窒化処理を、該合金の再結晶上限 温度以下で、かつ再結晶下限温度 （マイナス） 200°C以上の温度で行い、固溶金 属元素の窒化物粒子を分散形成させ、次いで、第 2段窒化処理を、第 1段窒化処理 で得られた該合金加工材の再結晶下限温度以上の温度で行い、第 1段窒化処理に より分散形成された窒化物粒子を粒成長させ安定化させる方法である。  [0022] Further, in the production method, 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.
[0023] 合金加工材の再結晶温度は主に加工度などの合金素材の作製条件に依存し、再結 晶上限値と下限値の一定の幅を有し、例えば、 Mo- 1. Owt%Ti合金加工材では 9 50〜： 1020°C位である。再結晶を起こす温度は加工度が大きいほど低くなる。  [0023] 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.
[0024] 第 1段窒化処理を再結晶上限温度以下とするのは、それより高温で窒化処理する と材料が再結晶化して脆くなるからであり、再結晶下限温度マイナス 200°C以上の温 度とするのは、これよりもさらに低い温度では窒素の拡散速度が遅すぎて、実用上十 分な深さまで内部窒化するのが困難なためである。  [0024] 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.
[0025] 多段窒化処理の段階数は少なくとも 2段階であればょレ、が、第 3段階以降の窒化処 理として、前段の窒化処理で得られた該合金加工材の再結晶下限温度以上の温度 で加熱して、前段の窒化処理によって分散形成された窒化物粒子を更に粒成長させ 安定化させる方法も実施できる。  [0025] 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.
[0026] 例えば、第 1段窒化を 900°Cで行うと、得られた内部窒化層内では表面から内部へ 向けて析出 TiN粒子の分布密度に勾配 (表面部は数が多ぐ内部では少ない)が発 生する。その結果、第 1段窒化で得られた内部窒化層の窒素雰囲気中での再結晶 温度は、表面付近が最も高く (例えば、 1400°C (再結晶上限温度))、内部窒化層先端 が最も低く (例えば、 950°C (再結晶下限温度))なる。 [0026] For example, when the first-stage nitriding is performed at 900 ° C, 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. As a result, 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)).
[0027] 第 1段窒化で得られた内部窒化層の厚さが圧延などの加工組織を最終的にそのま ま残すことが出来る理論上の最大厚さを規定するが、圧延などの加工組織を最大限 に残すためには、第 2段階の窒化を再結晶下限温度の直上として第 1段窒化で得ら れた内部窒化層先端付近の TiN粒子の析出密度を上げて、なおかつ TiN粒子のサ ィズを大きくする必要がある。これによつて、第 2段窒化後の再結晶下限温度 (内部窒 化層先端付近の再結晶温度)が上昇する。もちろん、第 1段窒化温度より高ぐ再結 晶下限温度未満の温度で第 2段窒化を行えば、圧延などの加工組織を最も厚く残す ことが可能であるが、窒化の工程数が多くなり、時間も長くなりすぎる。第 3段以降の 窒化処理を行う場合にも全く同様なことが言える。  [0027] 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. In order to maintain the maximum possible precipitation, 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. As a result, the recrystallization minimum temperature after the second-stage nitriding (the recrystallization temperature near the tip of the inner nitrided layer) increases. Of course, if the second-stage nitriding is performed at a temperature higher than the first-stage nitriding temperature and lower than the lower limit of recrystallization, 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.
[0028] 窒化物粒子の形態は、窒化処理温度に依存するが、例えば、 900°C→1200°C→ 1600°Cの 3段階の窒化処理では、第 1段窒化後の粒子は直径約 1〜2應の円盤状 粒子で、試料内部に向力うにつれて析出量は減少する。最表面付近では殆ど全て の合金元素が窒化物として析出している。第 2段窒化後には十数應程度に粒成長し 、圧延などの加工組織内の析出 TiN粒子の分布密度勾配は緩やかになる。第 3段窒 化後には TiN粒子は長さ 50〜 150應程度の棒状粒子へと成長し、材料表面部に残 つている圧延などの加工組織内ではほぼ全ての Tiが窒化物として存在している。  [0028] 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. After the third-stage nitridation, 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.
[0029] このように、多段内部窒化によって再結晶温度を上昇させた高融点金属系合金材 料に対して、酸素が共存する炭素源を用いて炭化処理を行う。この炭化処理の結果 、材料表面部は圧延組織が維持され、内部は再結晶組織である特徴的な二層構造 となる。この炭化処理により母相の微細組織には全く影響を及ぼすことなぐ多段内 部窒化によって析出した窒化物粒子のみを酸化物粒子へと変換することが可能であ る。  [0029] As described above, 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. As a result of this carbonization treatment, a rolled structure is maintained on the surface of the material, and the inside has a characteristic two-layer structure having a recrystallized structure. By this carbonization treatment, it is possible to convert only nitride particles precipitated by multi-stage internal nitridation into oxide particles without affecting the microstructure of the parent phase at all.
[0030] 粒界偏析する炭素の量は約 30〜150ppm(wt%)程度である。これより少ないと粒界 強化の効果が期待できない。多段窒化で残存した圧延などの加工組織内の窒化物 は全て酸化物粒子へと変化する。このとき、サイズと形態が変化する。例えば、長さ 5 0〜： 150nmの棒状 TiN粒子 (アスペクト比： 4〜7)が長さ 30〜60nm (アスペクト比： 2〜 3)の酸化物粒子へと変化する。そして、サイズが小さくなつた分、粒子の数は多くなる [0030] 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. For example, 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
[0031] 酸素が共存する炭素源としては、例えば、希薄 C〇ガスを用いることができる。この 希薄 C〇ガスは、 COを 0. 1〜5容積％含有する不活性ガスとすることが好ましい。 C 〇濃度が 5容積％より高濃度になると高融点金属の炭化が顕著に起きるので望ましく なレ、。希薄 C〇ガスはカーボンポテンシャルの制御が容易であり、炭素濃度を調整す ることによって合金材料表面に硬くて脆い炭化物層の生成を抑制できる。 [0031] As a carbon source in which oxygen coexists, for example, a diluted C 用 い る gas can be used. It is preferable that the diluted C gas be an inert gas containing 0.1 to 5% by volume of CO. If the C〇 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〇 gas, and by adjusting the carbon concentration, the formation of a hard and brittle carbide layer on the alloy material surface can be suppressed.
[0032] 希薄 COガスに限らず、高融点金属系合金材料の周囲に固体炭素、炭化水素など の炭素源をおいて酸素を共存させる方法でも炭化処理は可能である。例えば、加工 材を炭素源と直接接触させずに、炭素粉末を加工材の近傍に置いた状態で、ロータ リーポンプなどによる真空引きを行いながら熱処理を行うと希薄 COガスを用いた場 合と同様な反応が起こる。あまり真空度が良くない条件では、雰囲気中の微量酸素 が炭素と反応する結果、 COガスが生成し、これが反応に関与することになる。炭素 粉末とアルミナ粉末との混合粉末中に加工材を坦め込んで低真空状態で反応させ ても同様な反応が起こる。しかしながら、固体炭素源を用いた場合は、加熱温度が低 い場合に、加工材料の表面に硬くて脆い高融点金属の炭化物層が生成しやすいの で、希薄 COガスを用いる炭化処理法がより好ましレ、。  [0032] 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. For example, if 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. Under conditions where 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. However, when 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.
実施例 1  Example 1
[0033] 試験片として、 Mo_ l . Owt%Ti合金圧延材（厚さ l.Omm X幅 2.5mm X長さ 25mm) を 2個用いた。この合金圧延材の再結晶下限温度は 900°C、上限温度は 1020°Cで あった。これに、第 1段階を 900°Cで 64時間、第 2段階を 1200°Cで 25時間、第 3段 階を 1500°Cで 25時間の多段内部窒化処理を行った。再結晶下限温度と上限温度 は、それぞれ、第 1段階処理後 950°Cと 1400°C、第 2段階処理後 1250°Cと 1600°C 、第 3段階処理後 1600°Cと 1800°C (窒素雰囲気中で)であった。窒化処理は、 latm の Nガス気流中で行った。 2個の試験片のうち一つをそのまま比較例とした。もう一 [0033] Two Mo_l.Owt% Ti alloy rolled materials (thickness l.Omm x width 2.5mm x length 25mm) were used as test pieces. The minimum recrystallization temperature of this rolled alloy was 900 ° C and the maximum temperature was 1020 ° C. This was followed by a multi-stage internal nitriding treatment of the first stage at 900 ° C for 64 hours, the second stage at 1200 ° C for 25 hours, and the third stage at 1500 ° C for 25 hours. 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
2 2
つの試験片を 1500°Cで 16時間、希薄 COガス雰囲気を用いて炭化処理を行った。 COガスの濃度は、 Ar/C〇 = 49/1 (CO濃度 2容積％)とした。  The two specimens were carbonized at 1500 ° C for 16 hours in a dilute CO gas atmosphere. The concentration of CO gas was set to Ar / C〇 = 49/1 (CO concentration 2% by volume).
[0034] 図 1に、処理後の試験片の光学顕微鏡組織を示す。多段窒化材、多段窒化 +炭 化処理材とも表面に圧延組織が維持されていることが分かる。図 2に、処理後の試験 片の TEM組織を示す。多段窒化材の棒状の TiN粒子が多段窒化 +炭化処理材で は楕円形の Ti酸化物に変わっているのが分かる。図 3に、同じく三点曲げ試験の結 果を示す。 C〇ガスによる処理後も機械的特性は変化していないことがわかる。 DBT T (延性一脆性遷移温度)も変わらなレ、。 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〇 gas. DBT T (ductile-brittle transition temperature) also changes.
[0035] 図 4に、試験片の再結晶温度を調べるために、第 1段階を 1600°C、 1時間と、第 2 段階を 1700°C、 1時間の条件で真空処理した後の光学顕微鏡組織を示す。比較例 の多段窒化材では、圧延組織直下が白く見え、再結晶を起こしているのに対して、実 施例の多段窒化 +炭化処理材では 1700°Cの加熱でも再結晶を起こしていないこと が分かる。図 5に、処理前の試験片、多段窒化材、多段窒化 +炭化処理材の 1500 °Cでの高温 3点曲げ試験結果を示す。多段窒化材及び多段窒化 +炭化処理材は 処理なしの試験片と比べて強度が大きく向上していることが分かる。 [0035] 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. In the multi-stage nitrided material of the comparative example, 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.
産業上の利用可能性  Industrial applicability
[0036] 本発明の高融点金属系合金材料は、現在の TZM合金を凌ぐ耐熱性を有し、超高 温環境に対応した耐熱構造材料等に使用される。具体的には、例えば、超高温部材 用ボルト及びナット、超高温炉用ヒーター、フィラメント、反射板、半導体部品の焼成 用ボートやヒートシンク、熱間加工用金型及びダイス、航空宇宙用ガス噴射ノズル、 溶融金属の急冷凝固金型及び射出成型金型などが挙げられる。 [0036] 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. Specifically, for example, bolts and nuts for ultra-high temperature members, heaters for ultra-high temperature furnaces, filaments, reflectors, boats and heat sinks for firing semiconductor components, molds and dies for hot working, gas injection nozzles for aerospace And a rapidly solidified mold of molten metal and an injection mold.
図面の簡単な説明  Brief Description of Drawings
[0037] [図 1]実施例 1における処理後の試験片の光学顕微鏡組織を示す図面代用写真で ある。  FIG. 1 is a drawing substitute photograph showing an optical microscope structure of a test piece after treatment in Example 1.
[図 2]実施例 1における処理後の試験片の TEM組織を示す図面代用写真である。  FIG. 2 is a drawing-substituting photograph showing a TEM structure of a test piece after treatment in Example 1.
[図 3]実施例 1における処理後の試験片の三点曲げ試験の結果を示すグラフである。  FIG. 3 is a graph showing the results of a three-point bending test of a test piece after the treatment in Example 1.
[図 4]実施例 1における処理後の試験片を高温加熱した後の光学顕微鏡組織を示す 図面代用写真である。  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.
[図 5]処理前の試験片、多段窒化材、多段窒化 +炭化処理材の 1500°Cでの高温 3 点曲げ試験結果を示すグラフである。  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.

Claims

請求の範囲 The scope of the claims
[1] Mo, W, Crのうちの 1種を母相とし、 Ti, Zr, Hf, V, Nb, Taのうちの少なくとも 1種 を固溶金属とする合金力卩ェ材の多段窒化処理によって母相中に分散析出した固溶 金属の窒化物粒子を含む加工材を、さらに酸素が共存する炭素源を用いて炭化処 理した加工材であって、該炭化処理によって粒界偏析している炭素と、該窒化物粒 子から変換された酸化物粒子とを含有すること特徴とする高強度'高再結晶温度の 高融点金属系合金材料。  [1] Multi-stage nitriding of alloy alloys using one of Mo, W, and Cr as a matrix and at least one of Ti, Zr, Hf, V, Nb, and Ta as a solid solution metal This is a processed material containing solid solution metal nitride particles dispersed and precipitated in the parent phase by a carbon source using a carbon source in which oxygen coexists. A high melting point metal alloy material having a high strength and a high recrystallization temperature, characterized by containing carbon and oxide particles converted from the nitride particles.
[2] 合金材料の表面部は加工組織が維持され、内部は再結晶組織であること特徴とす る請求の範囲第 1項記載の高強度'高再結晶温度の高融点金属系合金材料。  [2] The high-strength, high-melting-point refractory metal alloy material according to claim 1, wherein the surface of the alloy material has a processed structure and the inside has a recrystallized structure.
[3] Moを母相とし、 Tiを固溶金属とし、再結晶温度が 1600°C以上であることを特徴と する請求の範囲第 1項記載の高融点金属系合金材料。  3. The refractory metal alloy material according to claim 1, wherein Mo is used as a mother phase, Ti is used as a solid solution metal, and the recrystallization temperature is 1600 ° C. or more.
[4] Mo, W， Crのうちの 1種を母相とし、 Ti， Zr, Hf, V, Nb, Taのうちの少なくとも 1種 を固溶金属とする合金力卩ェ材を窒化雰囲気中において多段内部窒化処理すること によって固溶金属の窒化物粒子を母相中に分散含有させた後、該合金加工材に酸 素が共存する炭素源を用いた炭化処理を行うことを特徴とする請求の範囲第 1項記 載の高融点金属系合金材料の製造方法。  [4] An alloy alloy containing 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 in a nitriding atmosphere After the nitride particles of the solid-solution metal are dispersed and contained in the matrix by multi-stage internal nitriding treatment, the carbonization treatment is performed by using a carbon source in which oxygen is present in the alloy processing material. A method for producing a refractory metal-based alloy material according to claim 1.
[5] 第 1段窒化処理を、該合金加工材の再結晶上限温度以下で、かつ再結晶下限温 度—（マイナス） 200°C以上の温度で行レ、、固溶金属の窒化物粒子を分散形成させ 、次いで、第 2段窒化処理を、第 1段窒化処理で得られた該合金力卩ェ材の再結晶下 限温度以上の温度で行い、第 1段窒化処理により分散形成された窒化物粒子を粒 成長させ安定化させることを特徴とする請求の範囲第 4項記載の高融点金属系合金 材料の製造方法。  [5] The first-stage nitriding treatment is performed at a temperature not higher than the upper limit of recrystallization of the alloy processing material and at a temperature lower than the lower limit of recrystallization— (minus) 200 ° C, and the solid solution metal nitride particles are formed. Then, a second-stage nitriding treatment is performed at a temperature equal to or higher than the lower limit temperature of the recrystallization of the alloy material obtained in the first-stage nitriding treatment, and the second-stage nitriding treatment is dispersed and formed by the first-stage nitriding treatment. 5. The method for producing a refractory metal-based alloy material according to claim 4, wherein the nitrided particles are grown and stabilized.
[6] COを 0.：!〜 5容積％含有する不活性ガスを用いて炭化処理を行うことを特徴とす る請求の範囲第 4項記載の高融点金属系合金材料の製造方法。  [6] The method for producing a refractory metal-based alloy material according to claim 4, wherein carbonization is performed using an inert gas containing from 0 to! 5% by volume of CO.
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