WO2022254139A1 - Procede de revetement d'une piece en alliage refractaire et piece ainsi revetue - Google Patents
Procede de revetement d'une piece en alliage refractaire et piece ainsi revetue Download PDFInfo
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- WO2022254139A1 WO2022254139A1 PCT/FR2022/051021 FR2022051021W WO2022254139A1 WO 2022254139 A1 WO2022254139 A1 WO 2022254139A1 FR 2022051021 W FR2022051021 W FR 2022051021W WO 2022254139 A1 WO2022254139 A1 WO 2022254139A1
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- WIPO (PCT)
- Prior art keywords
- layer
- ceramic
- alloy
- coating
- powder
- Prior art date
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 74
- 239000011248 coating agent Substances 0.000 title claims abstract description 65
- 229910000753 refractory alloy Inorganic materials 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 106
- 239000000919 ceramic Substances 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 78
- 239000000945 filler Substances 0.000 claims abstract description 71
- 238000011282 treatment Methods 0.000 claims abstract description 64
- 238000010438 heat treatment Methods 0.000 claims abstract description 50
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011733 molybdenum Substances 0.000 claims abstract description 29
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 229910002058 ternary alloy Inorganic materials 0.000 claims abstract description 21
- 238000009792 diffusion process Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- 229910045601 alloy Inorganic materials 0.000 claims description 38
- 239000000956 alloy Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000004132 cross linking Methods 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000197 pyrolysis Methods 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- -1 siloxanes Chemical class 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 238000002468 ceramisation Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 3
- 239000011224 oxide ceramic Substances 0.000 claims description 3
- 229920003257 polycarbosilane Polymers 0.000 claims description 3
- 229920001709 polysilazane Polymers 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011863 silicon-based powder Substances 0.000 claims description 3
- 238000004320 controlled atmosphere Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 98
- 239000000047 product Substances 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910001182 Mo alloy Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 241000894007 species Species 0.000 description 7
- 229910000601 superalloy Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910002056 binary alloy Inorganic materials 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000011253 protective coating Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005524 ceramic coating Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- 238000005495 investment casting Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229910002059 quaternary alloy Inorganic materials 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282337 Nasua nasua Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229910003575 SiAlCO Inorganic materials 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- CPTCUNLUKFTXKF-UHFFFAOYSA-N [Ti].[Zr].[Mo] Chemical compound [Ti].[Zr].[Mo] CPTCUNLUKFTXKF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000012700 ceramic precursor Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000012704 polymeric precursor Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011214 refractory ceramic Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/10—Cores; Manufacture or installation of cores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C23/00—Tools; Devices not mentioned before for moulding
- B22C23/02—Devices for coating moulds or cores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/12—Treating moulds or cores, e.g. drying, hardening
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/18—Finishing
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
Definitions
- TITLE PROCESS FOR COATING A PART IN REFRACTORY ALLOY AND PART
- the invention lies in the field of protective coatings for refractory alloy parts subjected to oxidation, for example foundry cores.
- the present invention relates more specifically to a process for coating a refractory alloy part and a refractory alloy part coated with such a protective coating.
- foundry cores are conventionally placed in foundry moulds, prior to the injection of the liquid metal, so as to produce one or more cavities or recesses in the mechanical elements which will be produced. during this manufacturing process.
- foundry cores are conventionally made of refractory ceramics.
- foundry cores made of refractory alloys as a replacement or in addition to the ceramic cores conventionally used.
- refractory alloys typically molybdenum alloys
- a protective layer to preserve their mechanical characteristics, in particular when they are subjected to very high temperatures encountered for example during manufacturing processes of blades in superalloy for turbomachinery.
- shells in refractory material are made around a wax model of the mechanical element to be produced, so as to form a mold of the model of this mechanical element.
- the wax is then evacuated in an autoclave under steam.
- the shell is heated to be consolidated, in order to make an imprint of the external shape of the mechanical element to be made.
- a core can be placed initially in the wax model and be present before the casting of the constituent material of the mechanical element to be produced, the core defining the internal shape of this mechanical element.
- Molybdenum for example, when it is uncoated, reacts with oxygen from 400° C, to form up to 650° C molybdenum dioxide (MOO2), then molybdenum trioxide beyond 650° C, molybdenum trioxide being very volatile.
- MOO2 molybdenum dioxide
- the oxidation rate of molybdenum follows a known linear increase between 400°C and 650°C, then an exponential increase beyond and up to 1700°C.
- TZM alloy a molybdenum-based alloy comprising zirconium and titanium
- TZM alloy a molybdenum-based alloy comprising zirconium and titanium
- the superalloy used for the manufacture of the mechanical element (for example a turbine engine blade) is melted and cast under vacuum in the shell. It then comes into contact with the refractory alloy which constitutes the core.
- This casting step carried out under vacuum, at a temperature above 1500°C, in particular leads to phenomena of diffusion of superalloy elements into the refractory alloy of the core.
- An inter-diffusion of the elements of the refractory alloy of the core towards the superalloy of the mechanical element to be manufactured can lead to a modification of the mechanical properties of the superalloy, and therefore lead to a degradation of the performance of the mechanical element obtained.
- preceramic polymers polymers which, after pyrolysis, are converted into ceramics.
- the "preceramic polymer” route is a synthesis method that makes it possible to manufacture homogeneous ceramics of high chemical purity. Due to a control of viscoelastic properties and composition at the atomic scale of the polymers, it is in particular possible to generate ceramics of the desired shape and composition.
- the best-known classes of ceramics obtained by this chemical route are the binary systems S13N4, SiC, BN and AIN, the ternary systems SiCN, SiCO and BCN, as well as the quaternary systems SiCNO, SiBCN, SiBCO, SiAlCN and SiAlCO.
- Figure 1 attached is a diagram illustrating a process for forming a coating using a pre-ceramic polymer. This process is broken down into five steps:
- the inorganic polymer P is preferably made up of the basic network of the ceramic, hence its name "preceramic".
- AFCOP Active-Filler-Controlled Pyrolysis of Preceramic Polymers
- P. Greil J. Am. Ceram. Soc. 1995. 78: p. 835-48.
- the polymer is partially loaded with particles of inert or active powder, to reduce shrinkage and to allow the production of quality ceramic parts.
- Active fillers or active fillers, such as Ti, Nb, Cr, Mo, B, MoSh incorporated into the polymer can reduce the shrinkage caused during the conversion of the polymer into ceramics, by reacting with the solid decomposition products and gas of the polymeric precursor and/or the pyrolysis atmosphere to form carbides, oxides, nitrides or silicides. This reaction can in fact occur with an expansion of the charged particles (“filler particles”), which neutralizes the shrinkage during densification, and leads to a ceramic composite as close as possible to its final shape.
- Also known from document FR 3 084 894 is a process for coating a refractory alloy part which consists in coating this part with the aid of a treatment composition comprising at least one type of preceramic polymer, a solvent and active fillers, then subjecting said coated part to a heat treatment making it possible to at least partially convert the preceramic polymer into ceramic and to form a coating, the latter being configured to protect the refractory alloy from oxidation.
- This method consists in using a low mass proportion of active filler, less than 35%.
- the analyzes of the protective coatings thus obtained showed that a discontinuous protective layer of a binary alloy resulting from the co-reactivity of this active charge with the refractory alloy part was obtained on the refractory alloy part, this discontinuous layer being covered with a layer of ceramic resulting from the conversion of the preceramic polymer.
- the reactivity of the active filler with respect to the substrate is limited because this filler is coated in the pre-ceramic polymer which obstructs inter-diffusion.
- An object of the invention is therefore to form a protective coating for a refractory alloy part, which is effective in protecting this part against oxidation.
- the invention relates to a process for coating a refractory alloy part, comprising the steps:
- a treatment composition comprising at least one type of preceramic polymer, a solvent and at least one active filler
- this heat treatment making it possible to at least partially convert the preceramic polymer to form a ceramic layer.
- said treatment composition comprises, relative to its total mass, a mass proportion of between 40% and 66% of at least one active filler, the active filler/preceramic polymer mass ratio is greater than or equal to 2, said active filler is chosen to form by solid or liquid diffusion, on the surface of said refractory alloy part, at least one alloy with a ternary minimum resulting from the co-reactivity of this active filler with the refractory alloy part and the polymer preceramic, this alloy with ternary minima forming a continuous layer between the surface of the refractory alloy part and the ceramic layer obtained by conversion and the heat treatment is carried out so as to form this continuous layer of alloy with ternary minima, which protects said part in refractory alloy from oxidation.
- said treatment composition comprises, relative to its total mass, a proportion by mass of between 45% and 60% of at least one active filler and in that the active filler/preceramic polymer mass ratio is between 2 and 3;
- said treatment composition comprises, relative to its total mass, a proportion by mass of between 55% and 60% of at least one active filler and in that the active filler/preceramic polymer mass ratio is between 2 and 2, 5;
- said at least one active filler is chosen from silicon powder, aluminum powder, iron powder, copper powder, cobalt powder, nickel powder, lanthanum powder, germanium powder , zirconium powder, chromium powder, titanium powder, hafnium powder, lanthanum powder and rhenium powder;
- the preceramic polymer is chosen from siloxanes, polysiloxanes with high ceramization yield which are converted into silica (S1O2) or into silicon oxycarbide (Si—O—C) by pyrolysis, polysilazanes or polycarbosilanes;
- the treatment composition further comprises so-called passive fillers, configured to modulate the thermal expansion coefficient of the alloy layer with a ternary minimum, so as to have a difference between the thermal expansion coefficient of the refractory alloy part and the coefficient of thermal expansion of the alloy layer with a ternary minima of less than 3.10 6 K 1 ;
- the method comprises at least a first consecutive coating step and a second coating step, and at least one heat treatment step carried out between two consecutive coating steps, the heat treatment step being a crosslinking step of the or preceramic polymers, configured to generate a network infusible polymer capable of withstanding the subsequent stages of pyrolysis, the second coating stage being applied to obtain a thicker layer of treatment composition;
- the treatment composition used during the second coating step has a viscosity lower than the viscosity of the treatment composition used during the first coating step
- the crosslinking step is carried out in the presence of air at a temperature greater than or equal to the highest crosslinking temperature among the different crosslinking temperatures of the different species of preceramic polymer of the treatment solution;
- the heat treatment step includes the steps of:
- the heat treatment step is carried out under a controlled atmosphere so as to avoid oxidation of the refractory alloy part, while having a partial pressure of oxygen sufficient to ensure the conversion of the preceramic polymer into oxycarbide ceramic or oxide ceramic ;
- the ceramic layer obtained by conversion is removed after the heat treatment, by mechanical or chemical action to leave only the minimum ternary alloy layer.
- the invention also relates to a part made of refractory alloy, in particular based on molybdenum.
- this part is obtained by the aforementioned coating process and it is coated with a continuous layer of at least one alloy with a ternary minimum resulting from the co-reactivity of the active charge with the refractory alloy part. and the preceramic polymer, and a ceramic layer, the continuous layer of at least one alloy to ternary minima being placed between the refractory alloy part and the ceramic layer.
- This part is, for example, a casting core of refractory alloy.
- FIG. 1 is a schematic representation of the stages of a coating by means of a preceramic polymer according to the prior art.
- FIG. 2 a state diagram of a preceramic polymer as a function of viscosity and temperature.
- FIG. 3 is a sectional view under a scanning electron microscope of a part obtained by a method according to the prior art.
- FIG. 4 is a diagram representing the different steps of the method according to the invention.
- FIG. 5 is a sectional view under a scanning electron microscope of a first part obtained by a process according to the invention.
- FIG. 6 is a detail view of figure 5.
- FIG. 7 is a sectional view under a scanning electron microscope of a second part obtained by a method according to the invention.
- the method in accordance with the invention can be applied to any type of refractory alloy part, in particular a refractory alloy based on molybdenum or a refractory alloy comprising molybdenum as the majority element, for example the titanium-zirconium-molybdenum alloy (TZM ), in order to protect this part from oxidation, especially in the presence of high temperatures (above 400°C) and air.
- a refractory alloy based on molybdenum or a refractory alloy comprising molybdenum as the majority element for example the titanium-zirconium-molybdenum alloy (TZM ), in order to protect this part from oxidation, especially in the presence of high temperatures (above 400°C) and air.
- ZM titanium-zirconium-molybdenum alloy
- Such a part is for example a mechanical part, such as for example a foundry core or a heating element of a furnace.
- the invention can be applied to a refractory alloy foundry core used for example to produce a superalloy turbomachine blade.
- the coating process according to the invention comprises steps:
- a treatment composition 2 comprising at least one type of preceramic polymer, a solvent and at least one active filler, this composition and the mass proportions of its various constituents being described later,
- part 1 coated with treatment composition 2 heat treatment of part 1 coated with treatment composition 2, so as to at least partially convert the preceramic polymer into ceramic and to form, around said part, a coating which protects it from oxidation.
- this heat treatment makes it possible to form by solid or liquid diffusion, on the surface of said refractory alloy part 1:
- this alloy with a ternary minimum forming a continuous layer 3 between the surface of the refractory alloy part 1 and the ceramic layer 4 obtained by conversion.
- Treatment composition 2 comprises, relative to its total mass, a proportion by mass of between 40% and 66% of at least one active filler, and the active filler/preceramic polymer mass ratio is greater than or equal to 2.
- the mass proportion of solvent will be chosen to adjust the viscosity of the treatment composition and make it compatible with the printing process selected.
- the treatment composition 2 comprises a mass proportion of active filler(s) of between 45% and 60% and an active filler/preceramic polymer mass ratio of between 2 and 3.
- the solvent content is at adjust according to the chosen printing process (on the 10-40% range).
- the treatment composition 2 comprises a mass proportion of active filler(s) of between 55% and 60% and an active filler/preceramic polymer mass ratio of between 2 and 2.5.
- the preceramic polymer advantageously comprises polysiloxanes with high ceramization yield which are converted into silica (SiC) or into silicon oxycarbide (Si-OC) by pyrolysis but can also be chosen from polysilazanes or polycarbosilanes.
- high ceramization yield it is understood that the theoretical conversion rate to ceramic, to silicon dioxide S1O2 or to silicon oxycarbide Si-OC is at least 70% by mass, preferably at least 80% .
- the solvent is preferably organic and may comprise, for example, a solvent or a combination of solvents chosen from glycol ethers, terpineol, butanone, methyl ethyl ketone (MEK), acetone, benzene, xylene, toluene or other organic solvents.
- a solvent or a combination of solvents chosen from glycol ethers, terpineol, butanone, methyl ethyl ketone (MEK), acetone, benzene, xylene, toluene or other organic solvents.
- the active filler(s) used are chosen so that at least one of them reacts with the refractory alloy part and with the preceramic polymer during the heat treatment which will be described below.
- reaction with the preceramic polymer it is meant that the active charge and the refractory alloy part co-react with the solid and gaseous decomposition products of this preceramic polymer and/or with the atmosphere of the pyrolysis of the preceramic polymer which leads to the formation of ceramics.
- These elements interdiffuse on the surface of the refractory alloy part 1 by diffusion to form one or more alloys, at least one of which is a ternary minima alloy which is in the form of a continuous layer consisting of:
- This continuous layer 3 is formed directly in contact with the metal part made of refractory alloy 1 and is formed under the ceramic layer 4 formed.
- minimum ternary alloy is meant a ternary alloy composed of three different atomic elements, or any other alloy composed of more than three different atomic elements, for example a quaternary alloy or more.
- This continuous layer 3 of alloy with ternary minima is then able to generate a passivating oxide layer when it is subjected to oxidizing conditions.
- the layer continuous 3 of formed alloy is locally exposed to external conditions.
- this alloy with minimum ternary 3 generates a passivating oxide layer on the surface, capable of protecting part 1 against oxidation and the diffusion of external species.
- This healing effect therefore makes it possible to greatly increase the life of the refractory alloy part 1 .
- the active metallic fillers can advantageously contain one species or a combination of several of the species listed below: a silicon powder, an aluminum powder, an iron powder, a copper powder, a cobalt powder, a powder of nickel, lanthanum powder, germanium powder, zirconium powder, chromium powder, titanium powder, hafnium powder, lanthanum powder, rhenium powder.
- the particle size of the active fillers in the treatment composition 2 before the thermal conversion is preferably chosen so as to be less than 20 microns, more preferably less than 10 microns. If necessary, grinding of the active fillers can be carried out to lower the particle size below this threshold of 20 microns.
- the ternary minima alloys (layer 3) formed on the surface of part 1 by solid diffusion of the active filler(s) of composition 2 into this part 1 are thermodynamically stable compounds.
- the alloys capable of being formed are defined by the phase diagrams between its active charges and the part 1 to be coated.
- the excess preceramic polymer forms after pyrolysis a continuous ceramic layer on the surface of part 1.
- This generally porous ceramic layer can act as a thermal barrier for part 1 or even have an impact on the corrosion resistance of part 1 by modifying the wettability of part 1 thus coated with respect to of a molten metal in contact.
- the treatment composition 2 may contain as active filler a germanium powder and as preceramic polymer, a polysiloxane and a solvent, all while respecting the mass proportions and mass ratios in accordance with the aforementioned invention.
- part 1 is made of molybdenum or a molybdenum-based alloy comprising zirconium and titanium (TZM alloy), and it is coated with said composition 2 by coating, then it undergoes the heat treatment in accordance with the invention and which will be described later, then a continuous layer 3 of a ternary alloy of Mo(Si x Ge i. x ) 2 is formed on the surface of said part 1, this layer 3 being surmounted by the ceramic layer 4 formed by conversion of the preceramic polymer (SiC and/or SiOC phase depending on the partial pressure of oxygen during the heat treatment.
- the source of silicon for forming this ternary alloy comes from the products of the pyrolysis of the preceramic polymer.
- This layer of ternary alloy 3 is capable of forming a passivating layer of silica under oxidizing conditions, as mentioned above.
- treatment composition 2 may contain a cobalt powder as active filler and a polysiloxane and a solvent as preceramic polymer, all while respecting the aforementioned mass proportions and mass ratios in accordance with the invention.
- part 1 is made of molybdenum or a molybdenum-based alloy comprising zirconium and titanium (TZM alloy), and it is coated with said composition 2 by coating, then it undergoes the heat treatment in accordance with the invention and which will be described later, then a continuous layer 3 of a ternary alloy of C03M02S1 is formed on the surface of said part 1, this layer 3 being surmounted by the ceramic layer 4 formed by conversion of the preceramic polymer (S1O2 phase and/ or SiOC depending on the partial pressure of oxygen during the heat treatment.
- the source of silicon to form this ternary alloy comes from the products of the pyrolysis of the preceramic polymer.
- Cobalt-based coatings are used to protect parts against wear or corrosion by forming a passivating layer of chromium (III) oxide, Cr203.
- the treatment composition 2 may contain as active filler an aluminum powder and as preceramic polymer, a polysiloxane and a solvent, all while respecting the mass proportions and mass ratios in accordance with the invention. aforementioned.
- part 1 is made of molybdenum or a molybdenum-based alloy comprising zirconium and titanium (TZM alloy), and it is coated with said composition 2 by coating, then it undergoes the heat treatment in accordance with the invention and which will be described later, then a continuous layer 3 of a ternary alloy of Mo(Si x Ali- x ) 2 is formed on the surface of said part 1, this layer 3 being surmounted by the ceramic layer 4 formed by conversion preceramic polymer (S1O2 and/or SiOC phase depending on the partial pressure of oxygen during heat treatment.
- the source of silicon to form this ternary alloy comes from the products of the pyrolysis of the preceramic polymer.
- This layer of ternary alloy is able to form a passivating layer of silica and alumina under oxidizing conditions, as mentioned above, in ratios which depend on the respective contents of aluminum and silicon in the ternary alloy.
- passive fillers up to 30% by mass of the total mass.
- this mass percentage of passive filler(s) will be adapted according to the quantities of active filler(s) used, and the maximum will therefore, in certain cases, be less than 30% by mass.
- Passive loading prevents excessive shrinkage caused by ceramization during heat treatment after coating.
- the passive loads also make it possible to modulate the coefficient of thermal expansion of the layer 3 of alloy with a ternary minima, according to the properties of the part 1 covered, in particular so as to avoid the gradients of coefficients of thermal expansion at the interface between layer 3 and part 1.
- a difference in coefficient of thermal expansion of less than 3.10 6 K 1 between part 1 and layer 3 of minimum ternary alloy and a difference in coefficient of thermal expansion of less than 3.10 6 K 1 between the layer 3 of a minimum ternary alloy and the ceramic layer 4 make it possible to avoid delamination and cracking during heat treatments. Indeed, a sudden variation in the coefficient of thermal expansion can lead to delamination or detachment of the coating (that is to say of layer 3 or of layer 4) during significant thermal variations.
- the passive filler(s) comprise(s) ceramic fillers derived partly or totally from the composition of the ceramic cores conventionally used, for example zircon, alumina or silica, but also other oxides, for example aluminosilicates, calcite, magnesia, or other non-listed species or a mixture thereof.
- ceramic compositions can be found in US Patent 5,043,01.
- the shakeout of the foundry cores can be simplified.
- the ceramic layer 4 was obtained by using a composition 2 with passive fillers comprising ceramic fillers, as mentioned above, then it will be possible to dissolve this ceramic layer 4 using a basic solvent , as was done in the prior art for ceramic foundry cores.
- a basic solvent as was done in the prior art for ceramic foundry cores.
- passive fillers oxides zircon, zirconia, mullite, alumina or silica, but also other oxides, for example aluminosilicates, calcite, magnesia, or a mixture of those -here, carbides for example SiC or nitrides, for example S13N4.
- the coating of part 1 can be carried out according to a process comprising one or more coating steps, which can themselves be carried out by the same method or by different methods.
- the choice of the coating method depends in particular on the viscosity of the treatment composition 2, the size and the complexity of the geometry of the part 1 to be coated and its surface condition.
- the thickness of the desired layer influences the choice of the coating method.
- the coating is preferably carried out by centrifugation, by dipping or by spraying. Centrifugal deposition makes it possible to obtain a thin homogeneous layer on a flat surface of a part 1.
- the thickness of the deposited layer can also be adjusted by modifying the speed of rotation of the part 1.
- the coating step is advantageously carried out by dipping, the part 1 being dipped in a bath of treatment composition 2, so as to cover the entire surface of the part 1 with a layer of composition treatment 2.
- the spraying is carried out using a spraying device which locally projects the treatment composition 2 onto an area of the part to be treated 1, so as to cover said area with a layer of treatment composition 2.
- the spraying is advantageously applies to parts having complex geometries, in particular when it is not necessary or when it is desired to avoid producing a coating over the entire surface of the part 1.
- the treatment composition 2 can also be deposited by various printing processes which facilitate the covering of the complex parts 1 at reduced costs.
- These printing processes are for example chosen from among electrophoresis, centrifugal deposition, sputtering deposition and suspension plasma spraying (these last three techniques being respectively known in English by the names of "S pin coating”, “ Spray coati ng”and “Suspension plasma spraying”).
- the process in accordance with the invention is carried out so as to have an overall thickness of the alloy layer 3 and of the ceramic layer 4 of less than 5 ⁇ m, so as to guarantee that the ceramic layer 4 remains intact. . Above this thickness and all the more so above 50 ⁇ m, phenomena of cracking and delamination of the ceramic layer 4 may occur.
- the layer 3 of alloy with a ternary minima obtained is continuous. Consequently, it is possible to have an overall layer (layers 3 and 4) with a thickness greater than the aforementioned thickness of 50 ⁇ m, since in this case, the cracking of layer 4 is not critical, the alloy layer 3 ensuring the protection of the part 1 against oxidation. Multiple layers.
- the viscosity of treatment composition 2 is advantageously reduced with each coating iteration in order to fill the porosity of the previous layer.
- a crosslinking step (heat treatment) of the coating can advantageously be carried out.
- part 1 is heated in the presence of air to a crosslinking temperature (from 100°C to 200°C) of the preceramic polymer(s) contained in treatment composition 2.
- the crosslinking will be carried out at the highest crosslinking temperature among the crosslinking temperatures of the species present.
- the coating of a part 1 is carried out with as many coating passes as necessary to obtain a desired coating.
- preceramic polymers into ceramics are complex approaches.
- factors can vary and modify the composition, microstructure, density, ceramic yield and properties of ceramics made from preceramic polymers. Among these factors, mention may be made of: the rheology, the ceramic yield, the reactivity and the degree of crosslinking of the precursor, the pyrolysis atmosphere (inert/reactive/vacuum) during shaping and/or during ceramization, the gas pressure during ceramization, the heating speed, the heating temperature, the duration of the stage.
- the preceramic polymer of the treatment composition 2 is converted by a ceramic heat treatment.
- Part 1, covered with composition 2, is placed in an enclosure 5 which is brought to a temperature required for the treatment.
- this enclosure 5 is hermetic and contains a gas that is inert with respect to the part 1 or the treatment composition 2.
- the heat treatment of the preceramic polymer is preferably carried out in a non-oxidizing atmosphere for the part 1, but whose partial pressure of oxygen is sufficient to convert the preceramic polymer into ceramic, in particular into oxycarbide ceramic or oxide ceramic.
- the partial pressure range of oxygen can be between 10 15 bar and 10 30 bar for a pyrolysis treatment carried out at 1350°C.
- the heat treatment may comprise several steps, namely a crosslinking step, a conversion step and a structuring step.
- a crosslinking step is preferably carried out after the coating step and prior to any other heat treatment step.
- the cross-linking step makes it possible in particular to vaporize the solvent and to cause the cross-linking of the pre-ceramic polymer.
- This crosslinking step generates a low content of organic groups which improves the ceramic yield and avoids excessively sudden variations in density and volume during the conversion.
- This treatment is carried out at a first temperature, preferably between 100° C. and 400° C., more preferably at a temperature of around 200° C.
- the crosslinking can be induced by ultraviolet radiation.
- a conversion step is carried out in order to convert the polymer into a ceramic. This conversion leads to the decomposition and removal of organic moieties (such as methyl, ethyl, phenyl or vinyl) and Si-H or Si-NHx groups during processing.
- organic moieties such as methyl, ethyl, phenyl or vinyl
- the conversion step is preferably carried out at a second temperature higher than the first, for example between 600°C and 800°C. After the conversion step an amorphous structure is obtained.
- a structuring step is carried out, at a third temperature, higher than the second and chosen to define the final crystalline structure, the microstructure and the properties of the coating.
- the structuring step is carried out at a temperature between 1000°C and 1350°C.
- Different treatment techniques can be used to carry out one or more steps of the aforementioned heat treatment.
- Pyrolysis for example induced by a laser, is advantageously used for parts 1 having a low melting temperature, and to generate ceramic deposits with specific compositions.
- Treatment with an ion beam is advantageously used in order to control the breaking of chemical bonds and the crosslinking of the preceramic polymer.
- the heat treatment of the part 1 in refractory alloy (whether in molybdenum or molybdenum alloy), coated with composition 2, is parameterized and carried out so as to ensure the conversion into ceramic 4 of all or part of the polymer preceramic contained in the treatment composition 2 and to allow co-reactivity of the decomposition products of the preceramic polymer with the active filler and with the part 1.
- the layer 4 is potentially less adherent than Layer 3 and may delaminate over time or wear faster than Layer 3.
- a treatment composition 2 was prepared comprising, relative to its total mass:
- SILRES MK® polysiloxane preceramic polymer, with a theoretical conversion rate in ceramic into silicon dioxide Si02 or into silicon oxycarbide Si-O-C of 80% by mass
- the active filler/preceramic polymer mass ratio is equal to 44.5/18.5, i.e. 2.4, i.e. greater than or equal to 2.
- the dissolution of the preceramic polymer in the Terpineol solvent is carried out at 60° C., with magnetic stirring, in a beaker for at least 30 minutes.
- the aluminum powder is then added and stirring is maintained for at least 12 hours.
- the treatment composition 2 is then cooled and stabilized between 19° C. and 21° C. during the soaking phase and also kept under magnetic stirring.
- Molybdenum or molybdenum alloy part 1 is introduced into treatment composition 2 at a speed of 10 mm/min, maintained for 30 seconds in the formulation, then taken out at a speed of 10 mm/min.
- treatment composition 2 When the part has completely emerged from treatment composition 2, it is dried in hot air (between 150° C. and 220° C.) until the solvent has evaporated. A total of six successive dippings with intermediate hot air drying were carried out to obtain a perfectly continuous coating with a thickness of 40 to 50 microns.
- the part is then subjected to a crosslinking heat treatment in air for 1 hour, at a temperature between 170°C and 230°C, for example at 200°C.
- any cracks in a first layer of the coating will be filled with an additional layer of coating, thus achieving a crack-free coating.
- the heat treatment must lead to the partial or total conversion of the SILRES MK® into ceramic but also allow the reactivity of the solid and gaseous silica decomposition products of the SILRES with part 1 and the active aluminum filler.
- the heat treatment plateau time must be sufficient to then allow interdiffusion in the molybdenum or molybdenum base support to form a continuous layer of ternary molybdenum-silicon-aluminum alloy.
- the heat treatments can optionally be carried out during the same thermal cycle in an alumina tube furnace under argon flushing at a flow rate of 35 to 40 L/h.
- the thermal cycle imposed on the coated part is carried out in an alumina tube furnace and includes temperature rise and fall ramps of 200°C/h and a 15-hour plateau at 900°C under argon of 35L/h.
- a zirconium oxygen monitor is placed upstream of the part relative to the argon flow to prevent oxidation of the molybdenum part during heat treatment.
- FIG. 5 shows a sectional view, obtained by scanning electron microscope (SEM), of a molybdenum rod 1 coated with the composition of the example cited above, after heat treatment. The solution results in a metal/ceramic multilayer coating.
- the ceramic part 4 consists of a layer of less than 50 microns of heterogeneous compositions: the matrix consists of silicon oxycarbide (Si-O-C) resulting from the conversion of the preceramic polymer into ceramic.
- the layer also includes inclusions of aluminum (residue of the active filler of the formulation which has not reacted because it is too far from the rod), free carbon (decomposition product of the preceramic polymer), silica (idem) and possibly polysiloxane if the conversion of the initial preceramic polymer is not complete.
- a treatment composition 2 was also prepared comprising, relative to its total mass:
- SILRES MK® polysiloxane preceramic polymer, with a theoretical conversion rate in ceramic into silicon dioxide Si02 or into silicon oxycarbide Si-O-C of 80% by mass
- the mass ratio of active filler/preceramic polymer greater than 2 (here 58/25, ie 2.32).
- Molybdenum or molybdenum alloy part 1 is introduced into treatment composition 2 at a speed of 10 mm/min, maintained for 30 seconds in the formulation, then taken out at a speed of 10 mm/min.
- FIG. 7 shows a sectional view, obtained by scanning electron microscope (SEM), of a coated molybdenum rod 1, after four successive dippings with intermediate hot air drying followed by a heat treatment identical to that of example 1.
- the ceramic part 4 consisting of silicon oxycarbide (Si—O—C) with a thickness of less than 40 ⁇ m was removed by mechanical action (sandblasting).
- Layer 3 of the coating is composed of three main alloy phases (listed from rod 1 outwards):
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US5043014A (en) | 1988-02-10 | 1991-08-27 | Societe Nationale D'etude Et De Construction De Moteurs D'aviation "S.N.E.C.M.A." | Thermoplastic paste for the production of foundry mold cores and a process for the production of such cores using said paste |
JPH0623476A (ja) * | 1992-07-10 | 1994-02-01 | Ahresty Corp | 崩壊性置中子用塗型剤 |
FR3084894A1 (fr) | 2018-08-07 | 2020-02-14 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Revetement ceramique pour noyau de fonderie |
WO2020085716A1 (fr) * | 2018-10-24 | 2020-04-30 | 주식회사 포스코 | Composition de solution de traitement de surface contenant du chrome trivalent et un composé inorganique, et procédé de fabrication de tôle d'acier galvanisée par immersion à chaud traitée en surface avec une telle composition |
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2021
- 2021-06-01 FR FR2105756A patent/FR3123365B1/fr active Active
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2022
- 2022-05-30 WO PCT/FR2022/051021 patent/WO2022254139A1/fr active Application Filing
- 2022-05-30 CN CN202280039876.XA patent/CN117412824A/zh active Pending
- 2022-05-30 EP EP22733698.9A patent/EP4347153A1/fr active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5043014A (en) | 1988-02-10 | 1991-08-27 | Societe Nationale D'etude Et De Construction De Moteurs D'aviation "S.N.E.C.M.A." | Thermoplastic paste for the production of foundry mold cores and a process for the production of such cores using said paste |
JPH0623476A (ja) * | 1992-07-10 | 1994-02-01 | Ahresty Corp | 崩壊性置中子用塗型剤 |
FR3084894A1 (fr) | 2018-08-07 | 2020-02-14 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Revetement ceramique pour noyau de fonderie |
WO2020085716A1 (fr) * | 2018-10-24 | 2020-04-30 | 주식회사 포스코 | Composition de solution de traitement de surface contenant du chrome trivalent et un composé inorganique, et procédé de fabrication de tôle d'acier galvanisée par immersion à chaud traitée en surface avec une telle composition |
Non-Patent Citations (2)
Title |
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GREIL P: "ACTIVE-FILLER-CONTROLLED PYROLYSIS OF PRECERAMIC POLYMERS", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, BLACKWELL PUBLISHING, MALDEN, MA, US, vol. 78, no. 4, 1 April 1995 (1995-04-01), pages 835 - 848, XP000707875, ISSN: 0002-7820, DOI: 10.1111/J.1151-2916.1995.TB08404.X * |
P. GREIL: "Active-Filler-Controlled Pyrolysis of Preceramic Polymers", J. AM. CERAM. SOC., vol. 78, 1995, pages 835 - 48, XP000707875, DOI: 10.1111/j.1151-2916.1995.tb08404.x |
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Publication number | Publication date |
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FR3123365A1 (fr) | 2022-12-02 |
FR3123365B1 (fr) | 2024-05-31 |
EP4347153A1 (fr) | 2024-04-10 |
CN117412824A (zh) | 2024-01-16 |
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