EP2690185A1 - Matériau à base de molybdène - Google Patents

Matériau à base de molybdène Download PDF

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Publication number
EP2690185A1
EP2690185A1 EP12765740.1A EP12765740A EP2690185A1 EP 2690185 A1 EP2690185 A1 EP 2690185A1 EP 12765740 A EP12765740 A EP 12765740A EP 2690185 A1 EP2690185 A1 EP 2690185A1
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EP
European Patent Office
Prior art keywords
molybdenum
plate member
molybdenum material
diffraction
region
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Ceased
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EP12765740.1A
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German (de)
English (en)
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EP2690185A4 (fr
Inventor
Takanori KADOKURA
Tomohiro Takida
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ALMT Corp
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ALMT Corp
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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

  • This invention relates to a molybdenum material.
  • Non-Patent Document 1 a method for raising the primary recrystallization temperature by the use of a TZM alloy (molybdenum alloy containing titanium, zirconium, and carbon) (Non-Patent Document 1).
  • the recrystallization temperature of the TZM alloy is about 1400°C and thus is higher than that of the pure molybdenum material
  • the TZM alloy forms an equiaxed grain structure after recrystallization and thus is easily deformed like the pure molybdenum material at the recrystallization temperature or higher.
  • Non-Patent Document 2 As the method for achieving a material which is excellent in creep resistance even after recrystallization, there is known a combination of Al, Si, and K as described in Non-Patent Document 2 or, as described in Non-Patent Document 3, a method of applying high-rate plastic working to a molybdenum sintered body added with a rare earth oxide such as La 2 O 3 so that the structure after recrystallization becomes a laminated structure of elongated coarse grains which are elongated in a working direction (Non-Patent Documents 2 and 3).
  • the additive and the structure control for the property improvement may cause the occurrence of cracks in the plastic working, such as forging or rolling, of the molybdenum material to adversely affect the product yield and may further cause anisotropy in bending properties or the like due to structural anisotropy, and therefore, the size of the molybdenum material should be limited.
  • the molybdenum material is used in contact with a firing workpiece or the like made of other elements, the firing workpiece or the like in contact with the molybdenum material and the additive in the molybdenum material may react with each other and therefore there is a possibility that the kind of firing workpiece may be limited.
  • Non-Patent Document 4 a phenomenon that a fibrous structure formed by plastic working such as rolling is newly changed into a crystal grain of about 20 to 30 ⁇ m by a heat treatment at 1000°C to 1100°C using as a nucleus a strain generated by the plastic working is called primary recrystallization or simply recrystallization while a phenomenon that a material comprising primary recrystallized grains is heat-treated at a higher temperature so that the adjacent primary recrystallized grains repeat combination and growth to be changed into a giant crystal grain is called secondary recrystallization (Non-Patent Document 4).
  • primary recrystallized grains of about several ten ⁇ m are gradually enlarged to several ten ⁇ m to several hundred ⁇ m while being supplied with thermal energy and, when, for example, they reach a certain temperature or they are heated at a certain temperature for a long time, they rapidly grow into a crystal grain on the order of mm or more. This rapid grain enlargement phenomenon is called secondary recrystallization.
  • Patent Document 1 a molybdenum plate member with a purity of 99.9% or more containing substantially no additives is subjected to a grain control treatment for 0.5 to 5 hours in a hydrogen flow at 2250°C, thereby forming giant disk-shaped crystal grains each having a diameter of 15 to 150mm, so that the plate member can be excellent in creep resistance at 1800°C (Patent Document 1).
  • Patent Document 1 uses no additives and thus is free of the problem of the occurrence of cracks in the plastic working to cause the reduction in product yield and the problem of the reaction with the firing workpiece and, further, the technique does not require the high-rate plastic working and thus is free of the structural anisotropy and the anisotropy in properties. Therefore, this technique can be said to be an excellent technique.
  • the heat treatment temperature required for causing the secondary recrystallization of the molybdenum plate member is 2250°C which is quite high in consideration of the primary recrystallization start temperature being 1000°C. Therefore, in terms of the productivity and the energy cost, it is desirable to lower the heat treatment temperature required for causing the secondary recrystallization.
  • This invention has been made in view of the above-mentioned problem and it is an object of this invention to provide an industrially advantageous molybdenum material which is capable of causing secondary recrystallization to occur at a temperature lower than conventional and which, after the secondary recrystallization, can have a structure that comprises giant crystal grains with less grain boundaries and thus is excellent in creep resistance.
  • the present inventors have paid attention to the relationship between the intensities of crystal diffraction planes by X-ray diffraction of a molybdenum material and the secondary recrystallization behavior of the molybdenum material and, as a result of intensive studies, have found that there is a significant relationship between the peak intensities of specific crystal diffraction planes in a certain region in a thickness direction of the molybdenum material and the secondary recrystallization temperature of the molybdenum material.
  • the present inventors have found that enlargement of crystal grains due to secondary recrystallization can be achieved at a temperature lower than that of the prior art by controlling those peak intensities, and have completed this invention.
  • a molybdenum material characterized by having, in at least a part thereof, a portion having a region where peak intensities of (110) and (220) diffraction planes are each less than a peak intensity of a (211) diffraction plane, as measured by X-ray diffraction, in a region at a depth of one-fifth of an entire thickness in a thickness direction from a surface.
  • a molybdenum material characterized by being obtained by heat-treating the molybdenum material according to the first aspect at 1700°C or more, wherein the average grain size of crystal grains in a cross-section of the plate member by a linear analysis method is 15mm or more.
  • a heating furnace structural member characterized by comprising the molybdenum material according to the first or second aspect.
  • a firing floor plate characterized by comprising the molybdenum material according to the first or second aspect.
  • an industrially advantageous molybdenum material which is capable of causing secondary recrystallization to occur at a temperature lower than conventional and which, after the secondary recrystallization, can have a structure that comprises giant crystal grains with less grain boundaries and thus is excellent in creep resistance.
  • a molybdenum material according to this invention is such that the peak intensities of specific diffraction planes in a certain region in a thickness direction are controlled.
  • the conditions of the molybdenum material of this invention will be described in detail by using a plate member as an example.
  • composition of a molybdenum plate member of this invention is sufficient if it is mainly composed of molybdenum.
  • the plate member of this invention preferably contains 99.9mass% or more molybdenum, but not limited thereto.
  • molybdenum is a main component (98mass% or more)
  • a material in which molybdenum is a main component 98mass% or more
  • a plate member containing molybdenum and 0.1 to 2.0mass% lanthanum oxide (La 2 O 3 ) or a plate member containing molybdenum, 0.3 to 1.0mass% titanium, 0.01 to 0.10mass% zirconium, and 0.01 to 0.1mass% carbon it is also possible to obtain an effect such that secondary recrystallization occurs at a temperature lower than conventional. That is, even if a molybdenum plate member with an additive is in the form of an alloy, the same effect is obtained.
  • the molybdenum plate member of this invention is obtained by pressing a molybdenum powder and sintering and then applying thereto plastic working such as rolling or forging.
  • plastic working such as rolling or forging.
  • a method for obtaining the molybdenum plate member by rolling will be described.
  • the manufacturing method is not limited thereto.
  • the molybdenum powder for use in obtaining the molybdenum plate member of this invention preferably has a purity of 99.9mass% or more.
  • the powder properties such as the particle size and bulk density of the material powder and the methods and conditions of a pressing process and a sintering process for obtaining a sintered body are satisfactory if it is possible to obtain a sintered body having a relative density of 90% or more which is a density large enough for plastic working.
  • the relative density of the sintered body is less than 90%, this causes the occurrence of cracks or the like due to voids in the sintered body when plastic working is applied to the sintered body to form a plate member, which is thus not preferable.
  • a pressed body may be formed by the molybdenum powder with use of a known single-shaft press machine, a known cold isostatic press machine (CIP), or the like.
  • a pressed body sintering method the above-mentioned pressed body may be sintered by a heat treatment at 1700 to 2000°C in a non-oxidizing atmosphere such as hydrogen, argon, or vacuum.
  • the powder properties such as the purity and particle size of the additive may be properly set so that the additive is uniformly dispersed in the sintered body and that the yield is not degraded in plastic working after the sintering.
  • a product of this invention is such that, by setting the rolling rate per rolling pass to less than 20% (not including 0), the peak intensities of the (110) and (220) diffraction planes can each be controlled to less than the peak intensity of the (211) diffraction plane, as measured by X-ray diffraction, in a region at a depth of one-fifth of the plate thickness in a plate thickness direction from an arbitrary portion of at least one of upper and lower surfaces, facing each other, of a plate member.
  • the reason for setting the rolling rate to less than 20% per rolling pass is that this condition can surely control the intensities of the specific diffraction planes according to this invention, while if the rolling rate is set to 20% or more, it is difficult to control the intensities of the crystal diffraction planes and further the product yield is reduced due to rolling cracks or the like.
  • the lower limit of the rolling rate per pass is preferably 5% or more and more preferably 15% or more. This is because if it is less than 5%, the number of rolling passes increases to raise the manufacturing cost.
  • the thickness of the sintered body for obtaining the molybdenum plate member of this invention may be 50mm or 150mm.
  • the unit is %) is at least 50% or more, it is difficult to obtain the X-ray diffraction peak intensities of this invention. More preferably, it is 85% or more.
  • Fig. 4A shows an exemplary diagram of the structure of an obtained molybdenum plate member, wherein a fibrous structure is exhibited due to the rolling.
  • Fig. 1 shows a schematic diagram of the plate member.
  • ND plane of the plate member are surfaces to be rolled, i.e. surfaces to be brought into contact with rolling rolls, and correspond to upper and lower surfaces of the plate member as defined in this embodiment.
  • the molybdenum plate member of this invention has, in at least a part thereof, a portion having a region where the peak intensities of the (110) and (220) diffraction planes are each less than the peak intensity of the (211) diffraction plane, as measured by X-ray diffraction, in a region at a depth of one-fifth of the plate thickness in a plate thickness direction from at least one of upper and lower surfaces, facing each other, of the plate member.
  • an important portion, which significantly affects secondary recrystallization, of the plate member in this invention, i.e. a region in which the X-ray diffraction intensities of the molybdenum plate member are controlled, is, as shown in Fig. 2 , set to a region at one-fifth of the plate thickness in a plate thickness direction from an arbitrary portion of at least one of upper and lower surfaces, facing each other, of the plate member.
  • a region at one-fifth of the plate thickness represents a range of ⁇ 50 ⁇ m of a depth corresponding to one-fifth from a substantial surface of the plate member, wherein the substantial surface is a surface after removing an oxide which is inevitably produced at a surface of a plastically worked material.
  • the oxide removal is carried out after the rolling and removes an oxide layer of the surface produced during the rolling by a heat-reduction treatment in a hydrogen atmosphere, a chemical treatment using aqua regia, a mixture of hydrofluoric acid and nitric acid, or the like, mechanical removal by cutting, grinding, or the like, or a combination thereof.
  • the factor that largely affects the secondary recrystallization phenomenon is considered to be a state of the molybdenum plate member before the primary recrystallization such that portions to be nuclei for the recrystallization are present in the region where the peak intensities of the crystal diffraction planes satisfy the above-mentioned conditions.
  • the X-ray diffraction intensities in the region at one-fifth of the plate thickness do not necessarily satisfy the above-mentioned conditions over the entire surface of the plate member. If a portion satisfying the above-mentioned conditions is present in at least a part of the surface of the plate member, secondary recrystallization occurs starting from that portion.
  • the primary recrystallization temperature is generally about 1000°C to 1100°C although there is some difference depending on the processing conditions. Also in the case of the plate member of this invention, it is about 1000°C to 1100°C as the conventional one.
  • Fig. 4B shows an exemplary diagram of a primary recrystallized structure.
  • An atmosphere for causing primary recrystallization is not particularly limited as long as it is a non-oxidizing atmosphere.
  • a hydrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or the like can be given and it may alternatively be an atmosphere in a combination thereof.
  • the average size of crystal grains in a plate cross-section is preferably 15mm or more. This is because it is the grain size necessary for obtaining excellent creep resistance.
  • the maximum grain size is set to 150mm in terms of economic load for the treatment temperature and time.
  • grains can be enlarged at a relatively low temperature in a relatively short time and, depending on the conditions, can be formed into a single crystal. Even if the size of the plate member increases, if a heating furnace having a size capable of heat-treating it is prepared, the grain size after secondary recrystallization can be increased according to the size of the plate member and therefore the maximum crystal grain size is not limited.
  • the average grain size referred to herein represents a value obtained by drawing three arbitrary lines parallel to plate member upper and lower surfaces of a single test piece as shown in Fig. 3 , calculating grain sizes along the respective lines, and averaging them.
  • a molybdenum material of this invention there is basically no limitation to the size of a molybdenum material of this invention.
  • the size of the molybdenum material is determined by manufacturing facilities such as a heating furnace and a plastic working machine such as a rolling, forging, or wire drawing machine. In an experiment by the present inventors, it was possible to obtain a molybdenum material of this invention in the form of a large-size plate member with a length of 1500mm, a width of 1000mm, and a thickness of 20mm as one example.
  • Molybdenum plate members were prepared under various processing conditions and the relationship between the peak intensities in a plate thickness direction and the secondary recrystallization temperature, the creep resistance after secondary recrystallization, and so on were evaluated. Specific sequences were as follows.
  • a molybdenum powder having a purity of 99.9mass% and a particle size of 4 ⁇ m as measured by the Fsss method was used as a starting material.
  • the molybdenum powder was filled into rubber molds, pressed at a pressure of 2 ton/cm 2 by CIP (Cold Isostatic Pressing), and sintered in a hydrogen atmosphere at 1800°C for 10 hours, thereby obtaining two sintered bodies having a width of 300mm, a length of 400mm, and thicknesses of 20mm and 150mm.
  • the relative densities of the obtained sintered bodies were respectively 94.2% and 94.4%.
  • Example 1 of this invention the plate members having the plate thicknesses of 1.0 to 3.0mm were prepared by rolling the sintered body having the thickness of 20mm while the plate members having the plate thicknesses of 10 and 20mm were prepared by rolling the sintered body having the thickness of 150mm.
  • Example 1 a surface oxide was removed by aqua regia after a reducing treatment in a hydrogen atmosphere at 800°C and, thereafter, washing with pure water was carried out, thereby obtaining samples of Example 1.
  • X-ray diffraction apparatus manufactured by Rigaku Corporation
  • scan speed 1 deg/min
  • divergence slit 1 degree
  • scattering slit 1 degree
  • receiving slit 0.15mm
  • measurement angle 2 ⁇ 30 to 120 degrees.
  • the magnitudes of the intensities of the (110), (220), and (211) planes as the output measurement results were compared.
  • the data herein were obtained by automatically performing background processing, smoothing processing, and K ⁇ 2 removal of measured raw data using device software.
  • polishing was carried out to polish each sample to a plate thickness direction depth where X-ray diffraction was to be carried out and X-ray diffraction was carried out at that depth.
  • This operation was repeated a plurality of times until a predetermined depth was reached, thereby measuring changes in peak density in the plate thickness direction of the ND plane in X-ray diffraction.
  • Table 1 shows one example (plate member thickness 1.5mm) of changes in peak density in the plate thickness direction of the ND plane in X-ray diffraction of the obtained molybdenum plate member.
  • Fig. 5 shows a graph representing Table 1.
  • the crystal structure was in a state typified by the exemplary diagram of Fig. 4A .
  • metal components were measured using a plasma emission spectrometer ICPS-8100 manufactured by Shimadzu Corporation.
  • ICPS-8100 plasma emission spectrometer
  • gas impurities O and C were measured such that O was measured using TC-600 manufactured by LECO Corporation while C was measured using WC-230 manufactured by LECO Corporation.
  • the composition of each sample was composed of 98.0mass% or more molybdenum and the balance inevitable impurities.
  • the inevitable impurities were metal impurities of Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni, ) Pb, Si, Sn, Ti, Zr, and Zn and gas impurities of O and C.
  • the purity excluding these impurities was defined as a molybdenum purity.
  • Example 2 In the same manner as in Example 1, two sintered bodies having a width of 300mm, a length of 400mm, and thicknesses of 20mm and 150mm were obtained, then these sintered bodies were heated at 1500°C for 20 minutes, and then rolling in two to three passes and reheating at 1200°C were repeated, thereby finally obtaining molybdenum plate members having plate thicknesses of 1.0, 1.5, 2.0, 3.0, 10, and 20mm.
  • the rolling rate per pass was set to 20 to 23%.
  • the plate members having the plate thicknesses of 1.0 to 3.0mm were prepared by rolling the sintered body having the thickness of 20mm while the plate members having the plate thicknesses of 10 and 20mm were prepared by rolling the sintered body having the thickness of 150mm, thereby obtaining samples of Comparative Example 1.
  • the sample of Comparative Example 1 was the plate member in which the peak intensities of the (110) and (220) diffraction planes were respectively not less than the peak intensity of the (211) diffraction plane in a region at one-fifth in the plate thickness direction from a surface of the plate member.
  • Example 1 and Comparative Example 1 were heat-treated in a hydrogen atmosphere at 1600 to 2200°C for 1 hour to 10 hours at maximum. Then, the structure of a TD plane (see Fig. 1 ) of each plate member after the heat treatment was observed to calculate an average grain size using the above-mentioned linear analysis method, thereby evaluating the secondary recrystallization temperature.
  • Example 1 In the samples obtained in Example 1 and Comparative Example 1, primary recrystallization occurred before the above-mentioned temperature was reached, specifically, at 1000°C to 1100°C.
  • the structural observation of the TD plane in Fig. 1 was carried out to calculate the grain size.
  • Each plate member was cut into a test piece having a length of 30mm.
  • the test piece was adjusted by polishing and etching to enable observation of grain sizes and then the grain size was calculated by the linear analysis method. More specifically, three arbitrary lines parallel to plate member upper and lower surfaces of a single test piece were drawn as shown in Fig. 3 , then grain sizes were calculated along the respective lines, and the average value thereof was defined as an average grain size of the sample.
  • the grain size becomes 15mm or more by heating at 1700°C or more and for at least 10 hours in the entire region of the TD plane in each sample of Example 1, while, in Comparative Example 1, grains were enlarged to 15mm or more by a heat treatment at 2000°C only in the case of the sample having the plate thickness of 1.0mm and grains of 15mm or more were not obtained unless heating at 2200°C was carried out in the case of the other samples of Comparative Example 1.
  • the crystal grain sizes were 100 ⁇ m or less and thus secondary recrystallization did not occur in Example 1 and Comparative Example 1. There was no significant difference among the three arbitrary lines used for measuring the average grain size.
  • the structure having been subjected to the secondary recrystallization was similar to that shown in the exemplary diagram of Fig. 4C .
  • Example 1 For each sample of Example 1, the measurement of the grain size in the molybdenum plate member cross-section was carried out by observing the TD plane. However, the same structure was obtained also on an RD plane.
  • Patent Document 1 there is no description about the rolling conditions, crystal planes, or the like of the molybdenum plate member. However, on checking up with the results this time, it is considered that all the samples of Comparative Example 1 in which the grains were enlarged by heating at 2200°C regardless of the heating time are the plate members substantially corresponding to that of Patent Document 1. That is, it is seen that, in each sample of Example 1, the enlargement of grains occurred at a low temperature compared to the products similar to that of Patent Document 1.
  • Example 1 the creep resistance of the samples of Example 1 and Comparative Example 1 was evaluated based on the deformation amount in a load test at 1800°C.
  • test pieces of Example 1 were heated in a hydrogen atmosphere at 1800°C for 5 hours to cause secondary recrystallization and were processed to a size of width 20mm x length 150mm.
  • the plate thicknesses were 1.0, 1.5, 2.0, 3.0, 10, and 20mm.
  • Test pieces of Comparative Example 1 were also heat-treated and processed into the predetermined size in the same manner. Secondary recrystallization did not occur in any of the samples of Comparative Example 1.
  • a test piece 1 was set on tungsten jigs 2 and 2'.
  • the distance between the jigs 2 and 2' was set to 100mm and a load 3 was applied to a middle portion of the test piece on the jigs 2 and 2'.
  • the load was set to 125g for the thickness 1 mm, 280g for the thickness 1.5mm, 500g for the thickness 2mm, and 1.1 kg for the thickness 3mm. Taking into account the safety of the test, the load was set to 12.5kg for the thicknesses 10mm and 20mm.
  • the test piece was heated in a hydrogen atmosphere at 1800°C for 100 hours at maximum and the deformation amount of the sample was measured.
  • the deformation amount is, as shown in Fig. 8 , given by a difference between positions of upper surfaces of the test piece 1 before the test and a test piece 1' after the test and was measured using a micro-gauge. Taking into account the safety of the test, the test was stopped when the test piece was deformed by 20mm so that the test under the longer heating time conditions was not performed.
  • Fig. 9 shows measured deformation amounts.
  • stop means that the test was stopped due to the deformation amount having reached 20mm.
  • this plate member like the samples of Comparative Example 1, did not cause enlargement of grains due to secondary recrystallization unless heated to 2200°C.
  • nuclei serving to cause secondary recrystallization to occur at a temperature lower than conventional were formed in regions at a depth of one-fifth from both surfaces of the sample of Example 1.
  • the molybdenum plate member is manufactured by rolling in the above-mentioned embodiment and Example, even a molybdenum plate member by forging or the like can similarly cause secondary recrystallization as long as the peak control of X-ray diffraction planes described in the embodiment and the Example is carried out.
  • the shape of molybdenum is the plate shape.
  • a shape other than the plate shape for example, a wire or rod shape
  • the recrystallization phenomenon is basically the same, it is considered to be possible to cause secondary recrystallization to occur at a low temperature similarly as long as the peak control of X-ray diffraction planes described above is carried out.
  • This invention is applicable to high-temperature structural and component materials, in particular, a wall surface forming a high temperature furnace and other components supporting constituent materials, more specifically, materials forming a high temperature furnace body, such as a base plate, a heater, a reflector, and fasteners such as bolts, and firing floor plates for use in the manufacture of sintered products such as ceramics, MIM (metal injection molding) products , and rare earth magnets.
  • this invention is also applicable to members of a single crystal growth furnace, specifically, for example, members forming a single crystal growth furnace for manufacturing a sapphire single crystal by melting alumina and members for use in lifting a sapphire single crystal because of less deformation after secondary recrystallization.

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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Metal Rolling (AREA)
EP12765740.1A 2011-03-25 2012-01-11 Matériau à base de molybdène Ceased EP2690185A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011068071A JP5160660B2 (ja) 2011-03-25 2011-03-25 モリブデン材
PCT/JP2012/050325 WO2012132489A1 (fr) 2011-03-25 2012-01-11 Matériau à base de molybdène

Publications (2)

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EP2690185A1 true EP2690185A1 (fr) 2014-01-29
EP2690185A4 EP2690185A4 (fr) 2014-12-24

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EP12765740.1A Ceased EP2690185A4 (fr) 2011-03-25 2012-01-11 Matériau à base de molybdène

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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)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2016025968A1 (fr) * 2014-08-20 2016-02-25 Plansee Se Métallisation pour un élément à couche mince, procédé pour sa fabrication et cible de pulvérisation

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Publication number Priority date Publication date Assignee Title
US11286172B2 (en) 2017-02-24 2022-03-29 BWXT Isotope Technology Group, Inc. Metal-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
WO2024162198A1 (fr) * 2023-02-01 2024-08-08 株式会社アライドマテリアル Maille de molybdène et son procédé de cuisson

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US5102474A (en) * 1987-11-09 1992-04-07 Schwarzkopf Technologies Corporation Process for manufacturing semi-finished products from sintered refractory metal alloys
JPH05140615A (ja) * 1991-04-23 1993-06-08 Toho Kinzoku Kk 耐熱性モリブデン板
JPH06158252A (ja) * 1992-11-18 1994-06-07 Toshiba Corp 高成形性モリブデン板、その製造方法および反射板
US20100108501A1 (en) * 2007-01-12 2010-05-06 Nippon Steel Materials Co., Ltd Mo-based sputtering target plate and method for manufacturing the same

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JPS61143548A (ja) * 1984-12-14 1986-07-01 Tokyo Tungsten Co Ltd モリブデン板
US5102474A (en) * 1987-11-09 1992-04-07 Schwarzkopf Technologies Corporation Process for manufacturing semi-finished products from sintered refractory metal alloys
JPH05140615A (ja) * 1991-04-23 1993-06-08 Toho Kinzoku Kk 耐熱性モリブデン板
JPH06158252A (ja) * 1992-11-18 1994-06-07 Toshiba Corp 高成形性モリブデン板、その製造方法および反射板
US20100108501A1 (en) * 2007-01-12 2010-05-06 Nippon Steel Materials Co., Ltd Mo-based sputtering target plate and method for manufacturing the same

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FUJII T ET AL: "Secondary recrystallization kinetics in molybdenum sheet", JOURNAL OF THE LESS-COMMON METALS, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 99, no. 1, 1 May 1984 (1984-05-01), pages 77-86, XP024082005, ISSN: 0022-5088, DOI: 10.1016/0022-5088(84)90336-9 [retrieved on 1984-05-01] & YOO ET AL: "Secondary recrystallization of molybdenum sheet doped with CaO and MgO under hydrogen atmosphere", INTERNATIONAL JOURNAL OF REFRACTORY METALS AND HARD MATERIALS, ELSEVIER PUBLISHERS, BARKING, GB, vol. 13, no. 4, 1 January 1995 (1995-01-01), pages 195-203, XP022576168, ISSN: 0263-4368 *
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YOO ET AL: "Recrystallization of molybdenum wire doped with lanthanum oxide", INTERNATIONAL JOURNAL OF REFRACTORY METALS AND HARD MATERIALS, ELSEVIER PUBLISHERS, BARKING, GB, vol. 13, no. 4, 1 January 1995 (1995-01-01), pages 221-227, XP022576172, ISSN: 0263-4368 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016025968A1 (fr) * 2014-08-20 2016-02-25 Plansee Se Métallisation pour un élément à couche mince, procédé pour sa fabrication et cible de pulvérisation
US11047038B2 (en) 2014-08-20 2021-06-29 Plansee Se Metallization for a thin-film component, process for the production thereof and sputtering target

Also Published As

Publication number Publication date
CN103459631A (zh) 2013-12-18
CN103459631B (zh) 2016-06-08
KR101587837B1 (ko) 2016-01-22
KR20140002010A (ko) 2014-01-07
WO2012132489A1 (fr) 2012-10-04
EP2690185A4 (fr) 2014-12-24
JP2012201930A (ja) 2012-10-22
JP5160660B2 (ja) 2013-03-13
US20140014235A1 (en) 2014-01-16

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