JP2014525386A - 湿潤環境において安定な超耐熱材料及びその製造方法 - Google Patents
湿潤環境において安定な超耐熱材料及びその製造方法 Download PDFInfo
- Publication number
- JP2014525386A JP2014525386A JP2014527718A JP2014527718A JP2014525386A JP 2014525386 A JP2014525386 A JP 2014525386A JP 2014527718 A JP2014527718 A JP 2014527718A JP 2014527718 A JP2014527718 A JP 2014527718A JP 2014525386 A JP2014525386 A JP 2014525386A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- hafnium
- tantalum
- substrate
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003779 heat-resistant material Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 23
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 22
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- LRTTZMZPZHBOPO-UHFFFAOYSA-N [B].[B].[Hf] Chemical compound [B].[B].[Hf] LRTTZMZPZHBOPO-UHFFFAOYSA-N 0.000 claims abstract description 8
- XTDAIYZKROTZLD-UHFFFAOYSA-N boranylidynetantalum Chemical compound [Ta]#B XTDAIYZKROTZLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 84
- 239000010410 layer Substances 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 35
- 239000002131 composite material Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 21
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 20
- 239000011253 protective coating Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 229910026551 ZrC Inorganic materials 0.000 claims description 13
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 239000011153 ceramic matrix composite Substances 0.000 claims description 9
- 239000011241 protective layer Substances 0.000 claims description 9
- 239000011819 refractory material Substances 0.000 claims description 6
- 229910010293 ceramic material Inorganic materials 0.000 claims description 5
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 40
- 229910052710 silicon Inorganic materials 0.000 description 40
- 239000010703 silicon Substances 0.000 description 40
- 230000003647 oxidation Effects 0.000 description 20
- 238000007254 oxidation reaction Methods 0.000 description 20
- 238000005245 sintering Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 230000002787 reinforcement Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 150000003482 tantalum compounds Chemical class 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910001362 Ta alloys Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 150000002363 hafnium compounds Chemical class 0.000 description 2
- QKQUUVZIDLJZIJ-UHFFFAOYSA-N hafnium tantalum Chemical compound [Hf].[Ta] QKQUUVZIDLJZIJ-UHFFFAOYSA-N 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000002490 spark plasma sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229910016006 MoSi Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- MELCCCHYSRGEEL-UHFFFAOYSA-N hafnium diboride Chemical compound [Hf]1B=B1 MELCCCHYSRGEEL-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- RCKBMGHMPOIFND-UHFFFAOYSA-N sulfanylidene(sulfanylidenegallanylsulfanyl)gallane Chemical compound S=[Ga]S[Ga]=S RCKBMGHMPOIFND-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
- C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
- C04B35/58078—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5062—Borides, Nitrides or Silicides
- C04B41/507—Borides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3804—Borides
- C04B2235/3813—Refractory metal borides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3839—Refractory metal carbides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6565—Cooling rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
- C04B2235/9684—Oxidation resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Products (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Composite Materials (AREA)
Abstract
【選択図】なし
Description
C/C材料に対して熱膨張係数が大きすぎるため、超耐熱性層でのクラックの出現及びC/C材料と前記層との界面に沿った密着性の喪失につながり、このようにして生成したクラックはひいては酸素及び水(いずれかの使用環境に存在する場合)を拡散するための経路となり、それによって、C/C基材が酸化されるに至り、その機械的物性が弱くなったり、失われることにさえなること;及び
2300℃よりも高い温度における低い耐酸化性。
前記組成物を成形して、当該組成物を高密度化する工程、
を備えることを特徴とする。
炭素相及び炭化ケイ素相を有するマトリックスによって高密度化された炭素繊維強化材でできた材料に相当するC−C/SiC;
炭化ケイ素のマトリックスによって高密度化された炭素繊維強化材でできた材料に相当するC−SiC;及び
炭化ケイ素のマトリックスによって高密度化された炭化ケイ素繊維強化材でできた材料に相当するSiC/SiC。
炭素及び窒素。
50容量%のHfB2、25容量%のHfC、及び25容量%のTaB2を含む本発明の材料;
ZrB2−ZiC(20容量%)をベースとする組成物よりも優れた耐腐食性の、参考のZrB2−SiC−Y2O3組成物を含む超耐熱材料;及び
熱構造C/SiC複合材料、
の間で、SiCのアクティブ酸化温度(約2000℃)で腐食試験中に測定された収縮速度を示す。
20 保護層
20a 上部
20b 下層
30 基材
31 SiC層
32 ZrC層
40 保護層
Claims (13)
- 酸化媒体中での高温に耐える耐熱材料であって、前記材料が少なくともホウ化ハフニウム及びホウ化タンタルを含み、前記材料においてハフニウム及びタンタルが化合物の形態でのみ存在することを特徴とする耐熱材料。
- 前記材料がホウ素を含み、タンタルに対するハフニウムの原子比率が、厳密に1を超え10未満(1<nHf/nTa<10)であり、タンタルに対するホウ素の原子比率は、5.4以上である(nB/nTa≧5.4)ことを特徴とする請求項1に記載の材料。
- 50容量%のHfB2、25容量%のHfC及び25容量%のTaB2を含むことを特徴とする請求項1又は2に記載の材料。
- 請求項1〜3のいずれか1項に記載の耐熱材料で構成されることを特徴とする酸化媒体中での高温に耐える耐熱性部品。
- 特定の材料でできている基材を備える部品であって、前記部品は酸化媒体中での高温における保護を提供するための保護コーティングを備え、前記保護コーティングが請求項1〜4のいずれか1項に記載の耐熱材料によって構成されることを特徴とする部品。
- 前記基材が炭化ケイ素をベースとするモノリシックセラミック材料又は炭素をベースとするモノリシック材料、又は炭化ケイ素を含むセラミックマトリックス複合材料でできていることを特徴とする請求項5に記載の部品。
- 前記基材がC/C複合材料でできていることを特徴とする請求項5に記載の部品。
- さらに、該部品の前記基材のC/C複合材料の近くに位置する炭化ケイ素の層及び前記炭化ケイ素層と前記保護コーティングとの間に配置された炭化ジルコニウム又は炭化ハフニウムの層を備えることを特徴とする請求項7に記載の部品。
- 酸化媒体中での高温に耐える耐熱材料から部品を製造する方法であって、前記方法は、少なくともホウ化ハフニウム及びホウ化タンタルを含む組成物を製造する工程、
前記組成物においてハフニウム及びタンタルは化合物の形態でのみ存在する; 及び
前記組成物を成形して、当該組成物を高密度化する工程、
を備えることを特徴とする。 - 特定の材料でできている基材を備える部品上に、酸化媒体中での高温に耐える保護層を製造する方法であって、前記方法は、
少なくともホウ化ハフニウム及びホウ化タンタルを含む組成物を部品上に塗布する工程、前記組成物においてハフニウム及びタンタルが化合物の形態でのみ存在する;及び
前記組成物を高密度化する工程、
を備える。 - 前記基材が、炭化ケイ素をベースとするモノリシックセラミック材料、又は炭素をベースとするモノリシック材料、又は炭化ケイ素を含むセラミックマトリックス複合材料でできていることを特徴とする請求項10に記載の方法。
- 前記基材が、C/C複合材料でできていることを特徴とする請求項10に記載の方法。
- さらに、前記部品の前記基材のC/C複合材料の近くに位置する炭化ケイ素の層を形成し、前記炭化ケイ素の層と前記保護層との間に配置された炭化ジルコニウム又は炭化ハフニウムの層を形成する工程を備えること特徴とする請求項12に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1157670 | 2011-08-31 | ||
FR1157670A FR2979341B1 (fr) | 2011-08-31 | 2011-08-31 | Materiau ultra-refractaire stable en environnement humide et son procede de fabrication |
PCT/FR2012/051851 WO2013030484A1 (fr) | 2011-08-31 | 2012-08-06 | Materiau ultra-refractaire stable en environnement humide et son procede de fabrication |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2014525386A true JP2014525386A (ja) | 2014-09-29 |
JP6002769B2 JP6002769B2 (ja) | 2016-10-05 |
Family
ID=46829801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2014527718A Active JP6002769B2 (ja) | 2011-08-31 | 2012-08-06 | 湿潤環境において安定な超耐熱材料及びその製造方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US9340460B2 (ja) |
EP (1) | EP2751049B1 (ja) |
JP (1) | JP6002769B2 (ja) |
KR (1) | KR101942604B1 (ja) |
CN (1) | CN103764594B (ja) |
BR (1) | BR112014003863A2 (ja) |
FR (1) | FR2979341B1 (ja) |
WO (1) | WO2013030484A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016014142A (ja) * | 2011-08-19 | 2016-01-28 | ワッカー ケミー アクチエンゲゼルシャフトWacker Chemie AG | オルガニルオキシシラン末端ポリマーに基づく架橋性材料 |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10954167B1 (en) * | 2010-10-08 | 2021-03-23 | Advanced Ceramic Fibers, Llc | Methods for producing metal carbide materials |
CN104529456B (zh) * | 2014-12-03 | 2017-03-22 | 武汉理工大学 | 一种B4C‑HfB2高温共晶自生复合陶瓷的制备方法 |
CN106699233B (zh) * | 2016-11-23 | 2020-08-25 | 中南大学 | 含化学气相共沉积硼化锆/铪-硼化钽的复合涂层及其制备方法 |
IT201800010441A1 (it) * | 2018-11-20 | 2020-05-20 | Consiglio Nazionale Ricerche | Procedimento per ottenere ceramici ultra-refrattari compositi rinforzati con fibre |
CN113045339B (zh) * | 2020-10-30 | 2022-07-26 | 南京航空航天大学 | C-C复合材料表面抗氧化ZrB2-SiC-Y2O3-SiC涂层及其制备方法 |
US12071383B2 (en) | 2021-04-21 | 2024-08-27 | Honeywell International Inc. | Contact joule heating for sintering high temperature coatings |
US11866377B2 (en) | 2021-04-21 | 2024-01-09 | Honeywell International Inc. | High temperature interfaces for ceramic composites |
CN113248261B (zh) * | 2021-06-16 | 2022-05-10 | 北京理工大学 | 一种二硅化钼包覆硼化钽-碳化铪球形粉体及其制备方法 |
FI4129958T3 (fi) * | 2021-08-03 | 2024-03-26 | Fraunhofer Ges Forschung | Menetelmä pinnoitettujen substraattien valmistamiseksi sekä pinnoitettu substraatti ja sen käyttö |
CN113956050A (zh) * | 2021-10-11 | 2022-01-21 | 南京航空航天大学 | C-C复合材料表面耐烧蚀ZrB2-SiC-La2O3-SiC涂层及其制备方法 |
CN115636674A (zh) * | 2022-10-27 | 2023-01-24 | 广东工业大学 | 一种高硬度和高韧性的氮化硅轴承球及其制备方法和应用 |
CN116082053B (zh) * | 2023-02-24 | 2024-05-03 | 中南大学 | 一种陶瓷改性碳/碳复合材料的快速制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5579852A (en) * | 1978-12-07 | 1980-06-16 | Agency Of Ind Science & Technol | High strength, high density hard material |
JPS55128560A (en) * | 1979-03-27 | 1980-10-04 | Agency Of Ind Science & Technol | Boride based ultrahard heat resistant material |
JPS59232970A (ja) * | 1983-05-13 | 1984-12-27 | 三菱マテリアル株式会社 | 耐摩耗性のすぐれたサイアロン基セラミツクス |
JPH08510983A (ja) * | 1992-12-18 | 1996-11-19 | アエロスパシアル・ソシエテ・ナシオナル・アンデユストリエル | 炭素をベースとする材料の酸化防止保護 |
JPH11314985A (ja) * | 1998-04-30 | 1999-11-16 | Kawasaki Heavy Ind Ltd | 耐熱・耐酸化性炭素繊維強化炭素材料 |
JP2002201033A (ja) * | 2000-12-28 | 2002-07-16 | Canon Inc | 光学素子成形用型 |
US7854912B1 (en) * | 2007-03-23 | 2010-12-21 | The United States Of America As Represented By The Secretary Of The Navy | High strength Zr (Hf or Ti)-Ta-B ceramics |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1384883A (en) * | 1972-01-11 | 1975-02-26 | Inst Metallurg Im Aa Baikova A | Method for applying nonmetallic coatings |
JPS5837274B2 (ja) * | 1980-08-26 | 1983-08-15 | 工業技術院長 | 高強度複合焼結材料 |
JPS63282166A (ja) * | 1987-05-11 | 1988-11-18 | Agency Of Ind Science & Technol | 高密度金属ホウ化物基セラミックス焼結体 |
US5036028A (en) * | 1988-05-03 | 1991-07-30 | Agency Of Industrial Science And Technology | High density metal boride-based ceramic sintered body |
JP3700010B2 (ja) * | 1994-11-24 | 2005-09-28 | 中部電力株式会社 | プラズマアーク電極材料 |
US7722421B2 (en) * | 2006-03-31 | 2010-05-25 | General Electric Company | High temperature ceramic composite for selective emission |
DE102006035792A1 (de) * | 2006-07-28 | 2008-01-31 | Patent-Treuhand-Gesellschaft für elektrische Glühlampen mbH | Glühlampe mit einem carbidhaltigen Leuchtkörper |
FR2925044B1 (fr) | 2007-12-13 | 2010-03-12 | Snecma Propulsion Solide | Procede de realisation d'une couche de carbure refractaire sur une piece en materiau composite c/c. |
CN101306959B (zh) * | 2008-07-07 | 2011-05-18 | 中国人民解放军国防科学技术大学 | 耐超高温陶瓷涂层的制备方法 |
US8673794B1 (en) * | 2009-08-28 | 2014-03-18 | Lockheed Martin Corporation | Multiphase eutectic ceramics |
US8865301B2 (en) * | 2012-01-26 | 2014-10-21 | The United States Of America, As Represented By The Secretary Of The Navy | Refractory metal boride ceramics and methods of making thereof |
-
2011
- 2011-08-31 FR FR1157670A patent/FR2979341B1/fr active Active
-
2012
- 2012-08-06 WO PCT/FR2012/051851 patent/WO2013030484A1/fr active Application Filing
- 2012-08-06 US US14/241,948 patent/US9340460B2/en not_active Expired - Fee Related
- 2012-08-06 KR KR1020147004983A patent/KR101942604B1/ko active IP Right Grant
- 2012-08-06 JP JP2014527718A patent/JP6002769B2/ja active Active
- 2012-08-06 CN CN201280041723.5A patent/CN103764594B/zh active Active
- 2012-08-06 BR BR112014003863-5A patent/BR112014003863A2/pt not_active Application Discontinuation
- 2012-08-06 EP EP12756767.5A patent/EP2751049B1/fr active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5579852A (en) * | 1978-12-07 | 1980-06-16 | Agency Of Ind Science & Technol | High strength, high density hard material |
JPS55128560A (en) * | 1979-03-27 | 1980-10-04 | Agency Of Ind Science & Technol | Boride based ultrahard heat resistant material |
JPS59232970A (ja) * | 1983-05-13 | 1984-12-27 | 三菱マテリアル株式会社 | 耐摩耗性のすぐれたサイアロン基セラミツクス |
JPH08510983A (ja) * | 1992-12-18 | 1996-11-19 | アエロスパシアル・ソシエテ・ナシオナル・アンデユストリエル | 炭素をベースとする材料の酸化防止保護 |
JPH11314985A (ja) * | 1998-04-30 | 1999-11-16 | Kawasaki Heavy Ind Ltd | 耐熱・耐酸化性炭素繊維強化炭素材料 |
JP2002201033A (ja) * | 2000-12-28 | 2002-07-16 | Canon Inc | 光学素子成形用型 |
US7854912B1 (en) * | 2007-03-23 | 2010-12-21 | The United States Of America As Represented By The Secretary Of The Navy | High strength Zr (Hf or Ti)-Ta-B ceramics |
Non-Patent Citations (1)
Title |
---|
JPN5014010190; SCITI DILETTA: SCRIPTA MATERIALIA V63 N6, 20100901, P601-604, ELSEVIER * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016014142A (ja) * | 2011-08-19 | 2016-01-28 | ワッカー ケミー アクチエンゲゼルシャフトWacker Chemie AG | オルガニルオキシシラン末端ポリマーに基づく架橋性材料 |
Also Published As
Publication number | Publication date |
---|---|
BR112014003863A2 (pt) | 2018-08-14 |
EP2751049A1 (fr) | 2014-07-09 |
FR2979341A1 (fr) | 2013-03-01 |
FR2979341B1 (fr) | 2020-01-31 |
KR101942604B1 (ko) | 2019-01-25 |
EP2751049B1 (fr) | 2020-04-29 |
US20150175487A1 (en) | 2015-06-25 |
KR20140089335A (ko) | 2014-07-14 |
US9340460B2 (en) | 2016-05-17 |
WO2013030484A1 (fr) | 2013-03-07 |
CN103764594B (zh) | 2015-12-23 |
CN103764594A (zh) | 2014-04-30 |
JP6002769B2 (ja) | 2016-10-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6002769B2 (ja) | 湿潤環境において安定な超耐熱材料及びその製造方法 | |
Tang et al. | Design, preparation and properties of carbon fiber reinforced ultra-high temperature ceramic composites for aerospace applications: a review | |
JP6717589B2 (ja) | シリコン含有基材のための結合層 | |
JP5953947B2 (ja) | 耐環境被覆されたセラミックス基複合材料部品及びその製造方法 | |
US9938198B2 (en) | Method for integral joining infiltrated ceramic matrix composites | |
EP2931679B1 (en) | Composite components with coated fiber reinforcements | |
JP2015508382A (ja) | セラミックマトリックス複合材を製造する方法およびそれによって形成されたセラミックマトリックス複合材 | |
JP5969998B2 (ja) | 酸化環境において2000℃を超える高温で部品を使用する方法 | |
WO2018212139A1 (ja) | 炭化ケイ素セラミックス | |
EP2210868B1 (en) | Composite material | |
CN104529498A (zh) | 放电等离子烧结一步制备多层环境障碍涂层的方法 | |
CN110963799B (zh) | 一种液相硅辅助成形热防护类Z-pins硅化物陶瓷棒结构的制备方法 | |
Zamharir et al. | Challenges toward applying UHTC-based composite coating on graphite substrate by spark plasma sintering | |
US20160160374A1 (en) | Methods of forming an article using electrophoretic deposition, and related article | |
CN109437974B (zh) | 一种具有Mo-Si-B-O高温抗氧化涂层的C/SiC复合材料及其制备方法 | |
Zamharir et al. | Synthesis and Sintering | |
Kravetskii et al. | Increase in the refractoriness of carbon composite materials with use of heat-resistant ceramic coatings | |
JPH11268978A (ja) | 炭素繊維強化炭素複合材料及びその製造方法 | |
CN118284588A (zh) | 在由具有陶瓷基体的复合材料制成的部件上沉积环境屏障的方法 | |
JPH09268063A (ja) | セラミックス基繊維複合材料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150406 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160310 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160510 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160713 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160816 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160905 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6002769 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |