WO2012132489A1 - Matériau à base de molybdène - Google Patents

Matériau à base de molybdène Download PDF

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Publication number
WO2012132489A1
WO2012132489A1 PCT/JP2012/050325 JP2012050325W WO2012132489A1 WO 2012132489 A1 WO2012132489 A1 WO 2012132489A1 JP 2012050325 W JP2012050325 W JP 2012050325W WO 2012132489 A1 WO2012132489 A1 WO 2012132489A1
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Prior art keywords
molybdenum
plate
crystal
molybdenum material
plate material
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PCT/JP2012/050325
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English (en)
Japanese (ja)
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角倉　孝典
瀧田　朋広
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株式会社アライドマテリアル
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Priority to EP12765740.1A priority Critical patent/EP2690185A4/fr
Priority to US14/007,129 priority patent/US20140014235A1/en
Priority to KR1020137028078A priority patent/KR101587837B1/ko
Priority to CN201280014329.2A priority patent/CN103459631B/zh
Publication of WO2012132489A1 publication Critical patent/WO2012132489A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
    • B22F2003/175—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging by hot forging, below sintering temperature
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
    • B22F2003/185—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers by hot rolling, below sintering temperature
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2200/00—Crystalline structure

Definitions

  • the present invention relates to a molybdenum material.
  • Molybdenum material may be used for parts that require heat resistance at high temperatures, such as high-temperature structural materials and component materials.
  • a pure molybdenum material in which a specific element is not intentionally added to the material it recrystallizes when used at about 1000 ° C. or more, and changes to an equiaxed grain structure. When the equiaxed grain structure is generated, the grain boundary slip is likely to occur, so that the creep resistance is deteriorated, and as a result, it is easily deformed.
  • Non-Patent Document 1 a method for increasing the primary recrystallization temperature by using a TZM alloy (a molybdenum alloy containing titanium, zirconium, and carbon) as described in Non-Patent Document 1 is known.
  • a TZM alloy a molybdenum alloy containing titanium, zirconium, and carbon
  • Non-Patent Document 1 a method for increasing the primary recrystallization temperature by using a TZM alloy (a molybdenum alloy containing titanium, zirconium, and carbon) as described in Non-Patent Document 1 is known.
  • the TZM alloy has a recrystallization temperature of about 1400 ° C, which is higher than that of a pure molybdenum material, it forms an equiaxed grain structure after recrystallization. It was easy.
  • Non-Patent Document 2 As a method of making a material excellent in creep resistance even after recrystallization, as described in Non-Patent Document 2, a combination of Al, Si, and K, or as described in Non-Patent Document 3 is used. , A method of forming a laminated structure of long crystal grains in which the structure after recrystallization is elongated in the processing direction by subjecting a molybdenum sintered body to which a rare earth oxide such as La 2 O 3 is added to plastic processing at a high processing rate Is known (Non-Patent Documents 2 and 3).
  • additives for improving properties and structure control cause cracking during plastic processing such as forging and rolling into molybdenum materials, and affect the yield of non-defective products, as well as bending properties due to structure anisotropy, etc.
  • the size of the molybdenum material must be limited.
  • the fired product in contact with the molybdenum material may react with the additive in the molybdenum material, There was a possibility that the type of the fired product was limited.
  • the primary recrystallized crystal grains of about several tens of ⁇ m gradually grow to several tens of ⁇ m to several hundreds of ⁇ m as heat energy is supplied. For example, when a certain temperature is reached or at a certain temperature, When heated for a long time, it grows rapidly and becomes crystal grains of mm units or more. This rapid grain growth phenomenon is called secondary recrystallization.
  • Patent Document 1 a molybdenum plate material having a purity of 99.9% or more that is substantially free of additives is subjected to crystal grain control treatment in a hydrogen stream at 2250 ° C. for 0.5 to 5 hours, and a diameter of 15 to 150 mm. It is possible to obtain a plate material having excellent creep resistance at 1800 ° C. by forming a large disk-shaped crystal grain (Patent Document 1).
  • Patent Document 1 Since the technique described in Patent Document 1 does not use an additive, the above-described cracking at the time of plastic working, the problem of non-defective yield reduction, the problem of reaction with the object to be fired, and the plastic working at a high working rate are also necessary. Therefore, it can be said that it is a good technique with no structural anisotropy or characteristic anisotropy.
  • the molybdenum plate material described in Patent Document 1 has a heat treatment temperature required to cause secondary recrystallization of 2250 ° C., which is very high when considered from the primary recrystallization start temperature of 1000 ° C. From the viewpoint of cost, it is desirable to further reduce the heat treatment temperature necessary for causing secondary recrystallization.
  • the present invention has been made in view of the above-mentioned problems, and its purpose is to cause secondary recrystallization at a lower temperature than before, and the structure after secondary recrystallization is a huge structure with few grain boundaries. It is an object to provide an industrially superior molybdenum material that is made of crystal grains and can be made to have excellent creep resistance.
  • the present inventor paid attention to the relationship between the strength of each crystal diffraction surface by X-ray diffraction and the secondary recrystallization behavior of molybdenum material, and as a result of intensive studies, it was found that in the thickness direction of the molybdenum material. On the other hand, it was found that there is a significant relationship between the peak intensity of a specific crystal diffraction plane in a certain region and the secondary recrystallization temperature.
  • the crystal diffraction planes (110) and ( 220) a molybdenum material characterized in that it has at least part of a region where each peak intensity of 220) is less than the peak intensity of (211).
  • the second aspect of the present invention is obtained by heat-treating the molybdenum material according to the first aspect at a temperature of 1700 ° C. or higher, and the average grain size of the crystal grain of the cross section of the plate material is 15 mm or more. It is the molybdenum material characterized by this.
  • a third aspect of the present invention is a structural member for a heating furnace characterized by having the molybdenum material described in the first or second aspect.
  • a fourth aspect of the present invention is a baking sheet characterized by having the molybdenum material described in the first or second aspect.
  • the present invention it is possible to cause secondary recrystallization at a lower temperature than before, and the structure after secondary recrystallization is composed of huge crystal grains with few grain boundaries so as to have excellent creep resistance. It is possible to provide an industrially superior molybdenum material that can be used.
  • FIG. 1 It is a schematic diagram which shows the structure
  • the molybdenum material according to the present invention controls the peak intensity of a specific crystal diffraction surface in a certain region with respect to the thickness direction.
  • the plate material will be described in detail as an example.
  • composition About the composition of the molybdenum board
  • the present invention when considering the contamination to the material that comes into contact when the plate material of the present invention is used at a high temperature, for example, a fired product heat-treated on the molybdenum plate material of the present invention, it is composed of 99.9% by mass or more of molybdenum.
  • the present invention is not limited to this.
  • a material containing molybdenum as a main component 98% by mass or more
  • a plate material containing 0.1 to 2.0% by mass of lanthanum oxide (La 2 O 3 ) in molybdenum Even a plate material containing 0.3 to 1.0% by mass of titanium, 0.01 to 0.10% by mass of zirconium, and 0.01 to 0.1% by mass of carbon in the same manner is lower than before. Effects such as causing secondary recrystallization at temperature can be obtained. That is, the same effect can be obtained even if the molybdenum plate material forms an alloy with the additive.
  • the molybdenum plate material of the present invention is obtained by pressure-molding / sintering molybdenum powder and subjecting it to plastic working such as rolling or forging.
  • plastic working such as rolling or forging.
  • the molybdenum powder used for obtaining the molybdenum plate material of the present invention preferably has a purity of 99.9% by mass or more.
  • the powder characteristics such as the particle size and bulk density of the raw material powder, and the method and conditions of the pressing step and the sintering step for obtaining a sintered body
  • the relative density which is a density at which plastic working is possible, is 90%. What is necessary is just to obtain the above sintered body.
  • the relative density of the sintered body is less than 90% because cracks and the like are generated due to voids in the sintered body when the plate material is plastically processed.
  • molybdenum powder having a particle size of 1.0 to 10 ⁇ m measured by Fsss method (Fischer method, Ficsher Sub-Sieve Sizer) is used. What is necessary is just to form a molded object by press-molding using an isotropic pressure press (CIP) etc.
  • CIP isotropic pressure press
  • the above-described molded body may be sintered by performing heat treatment at 1700 to 2000 ° C. in a non-oxidizing atmosphere such as hydrogen, argon, or vacuum.
  • the additive when there is an additive in addition to the main component molybdenum, the additive is uniformly dispersed in the sintered body, and the purity of the additive is set so that the yield does not deteriorate in plastic processing after sintering. What is necessary is just to set powder characteristics, such as a particle size, suitably.
  • the product of the present invention has a rolling rate per rolling of less than 20% (not including 0), so that at least one of the opposing upper and lower surfaces of the plate material is directed from the arbitrary surface toward the plate thickness direction.
  • the reason why the processing rate per rolling pass is less than 20% is that the strength of the specific crystal diffraction surface according to the present invention can be reliably controlled. If the rolling processing rate is 20% or more, crystal diffraction is achieved. This is because it is difficult to control the strength of the surface and the yield of non-defective products is lowered due to rolling cracks.
  • the lower limit of the rolling rate per pass is preferably 5% or more, more preferably 15% or more. This is because if it is less than 5%, the number of rolling passes increases and the production cost increases.
  • the thickness of the sintered body for obtaining the molybdenum plate material of the present invention there is no particular limitation on the thickness of the sintered body for obtaining the molybdenum plate material of the present invention. Therefore, for example, the thickness of the sintered body for obtaining a plate material having a thickness of 20 mm may be 50 mm or 150 mm.
  • the X-ray diffraction peak intensity of the present invention is difficult to obtain. More preferably, it is 85% or more.
  • FIG. 4A shows a schematic diagram of the crystal structure of the obtained molybdenum plate material.
  • a fibrous structure is obtained by rolling.
  • FIG. 1 shows a schematic diagram of a plate material.
  • the ND surface of the plate material is a surface to be rolled, that is, a surface in contact with the rolling roll, and corresponds to the upper and lower surfaces of the plate material defined in the present embodiment.
  • the crystal diffraction planes (110) and (220) each have at least a portion where a region where the peak intensity is less than the peak intensity of (211) exists.
  • an important plate material part that has a significant influence on secondary recrystallization that is, a region for controlling the X-ray diffraction intensity of the molybdenum plate material is at least on the upper and lower surfaces facing each other as shown in FIG. A region corresponding to one-fifth of the plate thickness from an arbitrary surface toward the plate thickness direction on one surface.
  • the “region corresponding to one-fifth of the plate thickness” corresponds to one-fifth from the substantial surface of the plate material after removing oxides inevitably generated on the surface of the plastic working material. It refers to a range of ⁇ 50 ⁇ m in depth.
  • Oxide removal is performed after the rolling process is completed, and the surface oxide layer formed during the processing is heated and reduced in a hydrogen atmosphere, or chemically treated with a mixture of aqua regia, hydrofluoric acid and nitric acid, or the like. It means removing by chemical treatment, mechanical removal by cutting or polishing, or a combination thereof.
  • the intensity of the crystal diffractive surface is controlled to at least one of the upper and lower surfaces opposite to each other, that is, the ND surface in FIG. 1, if either of the upper and lower surfaces is controlled by heat treatment at 1700 ° C. or higher.
  • the whole plate material causes secondary recrystallization, and the average particle size of crystal grains on the cross section of the plate, that is, in the TD plane and the RD plane in FIG. 1, is 15 mm or more.
  • the distance from the plate surface was limited because it was found that the X-ray diffraction intensity in the region corresponding to 1/5 of the plate thickness from the plate surface had a significant effect on the secondary recrystallization temperature. is there.
  • the recrystallization phenomenon of crystal grains is caused by rolling into the crystal grains of molybdenum plate material.
  • Secondary recrystallization is a phenomenon in which the primary recrystallized grains become enormous and coalesced.
  • the factor that greatly affects the secondary recrystallization phenomenon is the molybdenum material before the primary recrystallization. This state, that is, the site serving as the nucleus of recrystallization, is considered to exist in a region where the peak intensity of the crystal diffraction surface satisfies the above conditions.
  • only one of the ND planes in FIG. 1 may exhibit the X-ray diffraction intensity of the present invention.
  • This is a plastic processing condition, for example, in the case of rolling a plate of molybdenum during plate processing. This is due to conditions such as inversion of the upper and lower surfaces.
  • both surfaces of the ND surface are likely to exhibit the X-ray diffraction intensity of the present invention.
  • the X-ray diffraction intensity of the region corresponding to 1/5 over the entire surface of the plate material does not necessarily satisfy the above requirement, and if there is a portion satisfying the above requirement on at least a part of the plate surface, Secondary recrystallization can occur as a base point.
  • the primary recrystallization temperature is generally about 1000 ° C. to 1100 ° C., although there are some differences depending on the processing conditions, and the plate material of the present invention is also about 1000 ° C. to 1100 ° C. like the conventional material.
  • the atmosphere for causing primary recrystallization is not particularly limited as long as it is a non-oxidizing atmosphere.
  • a non-oxidizing atmosphere For example, hydrogen, argon, a vacuum atmosphere, etc. are mentioned, The atmosphere which consists of these may be sufficient.
  • the average grain size of the crystal grains in the cross section of the plate is desirably 15 mm or more. This is because the crystal grain size is necessary for obtaining good creep resistance. Further, in Patent Document 1, the maximum crystal grain size is set to 150 mm because of the economic burden of processing temperature and processing time. However, if the product of the present invention is used, the crystal grains become relatively large at a low temperature and in a short time. Depending on the conditions, a single crystal can be used.
  • the crystal grain size after secondary recrystallization can be increased according to the size of the plate, so that the maximum crystal
  • the particle size is not limited.
  • the average crystal grain size refers to three arbitrary lines parallel to the upper and lower surfaces of the plate material, and the crystal grain size is calculated for each line as shown in FIG. It is an average value in the case of.
  • the molybdenum material of the present invention is basically not limited in size.
  • the dimensions of the molybdenum material are determined by a heating furnace, which is a manufacturing facility, and a plastic processing apparatus such as rolling, forging, and wire drawing.
  • a heating furnace which is a manufacturing facility
  • a plastic processing apparatus such as rolling, forging, and wire drawing.
  • the molybdenum material of the present invention which is a large plate having a length of 1500 mm, a width of 1000 mm, and a thickness of 20 mm, could be obtained.
  • Example 1 and Comparative Example 1 Molybdenum plates were produced under various processing conditions, and the relationship between the peak strength in the thickness direction and the secondary recrystallization temperature, the creep resistance after secondary recrystallization, and the like were evaluated. The specific procedure is as follows.
  • Example 1 of the present invention a sintered body having a thickness of 20 mm was rolled up to a plate thickness of 1.0 to 3.0 mm, and a sintered body having a thickness of 150 mm was rolled on a plate material having a thickness of 10 or 20 mm. Made.
  • Example 1 the oxide on the surface was reduced in an atmosphere of hydrogen at 800 ° C. and then removed with aqua regia, and then washed with pure water to obtain a sample of Example 1.
  • the strength ratio of (211) is higher than that of (110) and (220) near the center in the thickness direction, and the strength of (110) and (220) is 0. It turns out that it is a near value. In the region of 300 ⁇ m from the surface corresponding to 1/5 of the plate thickness, the strengths of (110) and (220) are less than the strength of (211). In the other samples of Example 1, the distribution of each crystal plane had the same tendency. The crystal structure was in a state represented by the schematic diagram of FIG. 4A.
  • composition of the obtained sample was measured. Specifically, the metal component was measured using a plasma emission analyzer ICPS-8100 manufactured by Shimadzu Corporation. O and C were measured as gas impurities, O was measured with TC-600 manufactured by LECO, and C was measured with WC-230 manufactured by LECO.
  • the composition of the sample was composed of 98.0% by mass or more of molybdenum and other inevitable impurities.
  • inevitable impurities include metal impurities such as Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Si, Sn, Ti, Zr, and Zn, and gas impurities such as O and C.
  • the purity excluding was defined as molybdenum purity.
  • Example 1 ⁇ Preparation of Sample of Comparative Example 1 and X-Ray Diffraction>
  • two sintered bodies having a width of 300 mm, a length of 400 mm, and a thickness of 20 mm and 150 mm were obtained.
  • rolling of 2 to 3 passes was performed.
  • Reheating at 1200 ° C. was repeated to finally obtain molybdenum plate materials having plate thicknesses of 1.0, 1.5, 2.0, 3.0, 10, and 20 mm.
  • the rolling rate per pass was set to 20 to 23%.
  • Example 1 As in Example 1, a sintered body with a thickness of 20 mm was rolled to a plate thickness of 1.0 to 3.0 mm, and a sintered body with a thickness of 150 mm was used for a plate material with a thickness of 10 or 20 mm.
  • the sample of Comparative Example 1 was obtained by rolling.
  • the change in the X-ray peak intensity in the plate thickness direction was measured in the same manner as in Example 1 using a sample having a plate thickness of 1.5 mm in Comparative Example 1, and the results shown in Table 2 and FIG. 6 were obtained.
  • the peak intensities of the crystal diffraction planes (110) and (220) in the region of 1/5 from the plate surface to the plate thickness direction are (211) or more. It was a board material.
  • Example 1 ⁇ Secondary recrystallization temperature measurement>
  • each sample obtained in Example 1 and Comparative Example 1 was heat-treated in a hydrogen stream from 1600 to 2200 ° C. for 1 hour to a maximum of 10 hours, and the TD surface of the plate material after the heat treatment (see FIG. 1)
  • the average crystal grain size was calculated by the above-mentioned line segmentation method, and the secondary recrystallization temperature was evaluated.
  • Example 1 The samples obtained in Example 1 and Comparative Example 1 were subjected to primary recrystallization at 1000 ° C. to 1100 ° C., specifically until reaching the above temperatures.
  • the average crystal grain was measured by observing the structure on the TD plane of FIG. 1 and calculating the crystal grain diameter.
  • the test piece was cut so that the length of each plate was 30 mm, adjusted so that the crystal grain size could be observed by polishing and etching, and the crystal grain size was calculated by the line segment method. More specifically, as shown in FIG. 3, with respect to one test piece, three arbitrary lines parallel to the upper and lower surfaces of the plate material are drawn, the crystal grain size is calculated with each line, and the average value is calculated as the average value.
  • the average crystal grain size of the sample was used.
  • the crystal grain size after the secondary recrystallization is 1 mm or more, and it may be difficult to specify the crystal grain size because it takes the form of structure as shown in the schematic diagram of FIG. 4C. Therefore, all crystal grain sizes of 15 mm or more are described as “15 mm or more”. The results are shown in FIG.
  • the sample of Example 1 has a crystal grain size of 15 mm or more when heated at 1700 ° C. or higher and at least 10 hours in all regions of the TD surface, whereas the sample of Comparative Example 1 has 2000 It was only in the case of a plate thickness of 1.0 mm that it became enlarging to 15 mm or more by heat treatment at 0 ° C., and other samples of Comparative Example 1 could not obtain crystal grains of 15 mm or more unless heated at 2200 ° C. . At 1600 ° C., the average crystal grain size was 100 ⁇ m or less in both Example 1 and Comparative Example 1, and secondary recrystallization did not occur. In addition, there was no remarkable difference in arbitrary three which measured the average crystal grain size. The crystal structure in which secondary recrystallization occurred was similar to that shown as a schematic diagram in FIG.
  • test piece of Example 1 was heated in a hydrogen stream at 1800 ° C. for 5 hours, subjected to secondary recrystallization, and processed to have a size of 20 mm wide ⁇ 150 mm long.
  • the plate thickness was 1.0, 1.5, 2.0, 3.0, 10, 20 mm.
  • the test piece of Comparative Example 1 was similarly heat-treated and processed into a predetermined size. Each sample of Comparative Example 1 was not secondary recrystallized.
  • the test piece 1 was set on the tungsten jigs 2 and 2 '.
  • the distance between the jigs 2 and 2 ' was 100 mm, and a load 3 was applied to the center of the test piece on the jigs 2 and 2'.
  • the load during the test was 125 g at a plate thickness of 1 mm, 280 g at a plate thickness of 1.5 mm, 500 g at a plate thickness of 2 mm, and 1.1 kg at a plate thickness of 3 mm.
  • the safety was set to 12.5 kg in consideration of test safety.
  • the specimen was heated at 1800 ° C. for up to 100 hours in a hydrogen stream, and the amount of deformation of the sample was measured.
  • the amount of deformation was expressed as a difference in the position of the upper surface of the test piece 1 before the test and the test piece 1 'after the test, and was measured using a micro gauge.
  • the test was interrupted at that time with respect to the one deformed by 20 mm, and the test was not performed under a longer heating time condition.
  • Comparative Example 2 Of the plate material of Example 1, a plate having a thickness of 1.5 mm was removed by polishing the area from the both surfaces to a depth of 1/5 + 50 ⁇ m, and placed in a hydrogen stream at 1600-2200 ° C. for 1 hour up to a maximum of 10 hours. Then, the microstructure of the TD surface (see FIG. 1) of the heat-treated sample was observed, the average crystal grain size was calculated by the above-mentioned line segmentation method, and the secondary recrystallization temperature was evaluated.
  • the plate material did not cause enlarging of crystal grains due to secondary recrystallization unless it was heat-treated up to 2200 ° C.
  • Example 1 had nuclei that originated from secondary recrystallization at lower temperatures than in the past in the region of 1/5 depth from both surfaces.
  • the molybdenum plate material is manufactured by rolling.
  • the peak control of the X-ray diffraction surface described in the embodiment and the examples is possible even for a molybdenum plate material by other forging processes. If it is, secondary recrystallization can be performed in the same manner.
  • the shape of molybdenum is a plate shape.
  • the recrystallization phenomenon is basically the same, so the X-rays described above are used.
  • the peak of the diffraction surface is controlled, it is considered that secondary recrystallization can be performed at a low temperature. In this case, it is only necessary that the peak intensity of the X-ray diffraction plane in the region corresponding to the depth of one fifth of the diameter of the wire rod from the surface of the wire rod toward the central axis satisfies the above-described conditions.
  • the present invention relates to high-temperature structural materials and component materials, in particular, parts that support the wall surface and other components constituting the high-temperature furnace, more specifically, a base plate, a heater, a reflector such as a reflector, and a bolt. It is used as a base plate for firing and used in the production of sintered bodies such as ceramics, MIM (metal injection molding) products and rare earth magnets.
  • a base plate for firing and used in the production of sintered bodies such as ceramics, MIM (metal injection molding) products and rare earth magnets.
  • the present invention relates to a member for a single crystal growth furnace, specifically, for example, a member constituting a furnace for a single crystal growth furnace when secondary alumina is melted to produce a sapphire single crystal or after secondary recrystallization. Therefore, it can be used as a member used for pulling sapphire single crystals.

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  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Metal Rolling (AREA)

Abstract

La présente invention aborde le problème consistant à se procurer un matériau à base de molybdène, avantageux du point de vue industriel, qui est apte à une recristallisation secondaire à une température inférieure à celle d'un matériau à base de molybdène classique et qui peut être converti par la recristallisation secondaire en un matériau qui présente une structure comprenant de très gros grains ayant des joints de grains réduits et présente ainsi une excellente résistance au fluage. Lorsqu'il est analysé par une mesure de diffraction des rayons X, ce molybdène présente, dans la totalité ou une partie de la région correspondant à la profondeur selon l'épaisseur de la feuille d'un cinquième de l'épaisseur totale à partir de la surface, des zones qui contiennent chacune un domaine tel que les intensités de pic des plans de diffraction (110) et (220) sont chacune inférieures à l'intensité de pic du plan de diffraction (211).
PCT/JP2012/050325 2011-03-25 2012-01-11 Matériau à base de molybdène WO2012132489A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP12765740.1A EP2690185A4 (fr) 2011-03-25 2012-01-11 Matériau à base de molybdène
US14/007,129 US20140014235A1 (en) 2011-03-25 2012-01-11 Molybdenum material
KR1020137028078A KR101587837B1 (ko) 2011-03-25 2012-01-11 몰리브덴재
CN201280014329.2A CN103459631B (zh) 2011-03-25 2012-01-11 钼材料

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JP2011-068071 2011-03-25
JP2011068071A JP5160660B2 (ja) 2011-03-25 2011-03-25 モリブデン材

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US (1) US20140014235A1 (fr)
EP (1) EP2690185A4 (fr)
JP (1) JP5160660B2 (fr)
KR (1) KR101587837B1 (fr)
CN (1) CN103459631B (fr)
WO (1) WO2012132489A1 (fr)

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AT14576U1 (de) * 2014-08-20 2016-01-15 Plansee Se Metallisierung für ein Dünnschichtbauelement, Verfahren zu deren Herstellung und Sputtering Target
US20180244535A1 (en) 2017-02-24 2018-08-30 BWXT Isotope Technology Group, Inc. Titanium-molybdate and method for making the same
CN108145157B (zh) * 2017-12-25 2020-03-27 安泰天龙钨钼科技有限公司 一种高性能钼铼合金棒材的制备方法
CN114669620A (zh) * 2022-03-08 2022-06-28 成都联虹钼业有限公司 一种精密陶瓷烧结用承烧钼板及其制备工艺

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JP5160660B2 (ja) 2013-03-13
KR20140002010A (ko) 2014-01-07
EP2690185A1 (fr) 2014-01-29
CN103459631B (zh) 2016-06-08
CN103459631A (zh) 2013-12-18
JP2012201930A (ja) 2012-10-22
KR101587837B1 (ko) 2016-01-22
EP2690185A4 (fr) 2014-12-24
US20140014235A1 (en) 2014-01-16

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