CN111235511B - Preparation method of multi-element ceramic composite coating - Google Patents
Preparation method of multi-element ceramic composite coating Download PDFInfo
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- CN111235511B CN111235511B CN202010178922.7A CN202010178922A CN111235511B CN 111235511 B CN111235511 B CN 111235511B CN 202010178922 A CN202010178922 A CN 202010178922A CN 111235511 B CN111235511 B CN 111235511B
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- powder
- oxide
- silicon carbide
- aluminum
- coating
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- 239000002131 composite material Substances 0.000 title claims abstract description 252
- 238000000576 coating method Methods 0.000 title claims abstract description 205
- 239000011248 coating agent Substances 0.000 title claims abstract description 188
- 239000000919 ceramic Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 315
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 178
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 157
- 239000000463 material Substances 0.000 claims abstract description 123
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 85
- 238000007751 thermal spraying Methods 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 73
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 73
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 32
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 32
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 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 claims abstract description 27
- 229910001936 tantalum oxide Inorganic materials 0.000 claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 13
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005507 spraying Methods 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 7
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 6
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 71
- 239000011230 binding agent Substances 0.000 claims description 67
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 46
- 238000005488 sandblasting Methods 0.000 claims description 41
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 38
- 239000007921 spray Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 25
- 229910000601 superalloy Inorganic materials 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 239000010439 graphite Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 12
- 229910000943 NiAl Inorganic materials 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000007769 metal material Substances 0.000 claims description 6
- -1 NiCrAl Inorganic materials 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910001018 Cast iron Inorganic materials 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 229910015372 FeAl Inorganic materials 0.000 claims description 2
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- 244000137852 Petrea volubilis Species 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 25
- 238000000151 deposition Methods 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 60
- 239000002994 raw material Substances 0.000 description 37
- 238000002203 pretreatment Methods 0.000 description 27
- 229910021332 silicide Inorganic materials 0.000 description 25
- 238000007750 plasma spraying Methods 0.000 description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 21
- 238000007254 oxidation reaction Methods 0.000 description 20
- 229910026551 ZrC Inorganic materials 0.000 description 19
- 230000003647 oxidation Effects 0.000 description 19
- 229910052726 zirconium Inorganic materials 0.000 description 19
- 239000012071 phase Substances 0.000 description 17
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 15
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 15
- 238000002844 melting Methods 0.000 description 12
- 229910052758 niobium Inorganic materials 0.000 description 12
- 239000010955 niobium Substances 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 229910052580 B4C Inorganic materials 0.000 description 10
- 238000002679 ablation Methods 0.000 description 10
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 9
- 150000001247 metal acetylides Chemical class 0.000 description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 8
- 229910003470 tongbaite Inorganic materials 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 description 6
- 229910000816 inconels 718 Inorganic materials 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- WEAMLHXSIBDPGN-UHFFFAOYSA-N (4-hydroxy-3-methylphenyl) thiocyanate Chemical compound CC1=CC(SC#N)=CC=C1O WEAMLHXSIBDPGN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005524 ceramic coating Methods 0.000 description 3
- 229910021357 chromium silicide Inorganic materials 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 238000007581 slurry coating method Methods 0.000 description 3
- 229910021341 titanium silicide Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910021355 zirconium silicide Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004372 laser cladding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 2
- 239000003758 nuclear fuel Substances 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910003468 tantalcarbide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- TWRSDLOICOIGRH-UHFFFAOYSA-N [Si].[Si].[Hf] Chemical compound [Si].[Si].[Hf] TWRSDLOICOIGRH-UHFFFAOYSA-N 0.000 description 1
- VKTGMGGBYBQLGR-UHFFFAOYSA-N [Si].[V].[V].[V] Chemical compound [Si].[V].[V].[V] VKTGMGGBYBQLGR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 description 1
- 229910021342 tungsten silicide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Images
Classifications
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
Description
技术领域technical field
本发明的技术方案涉及碳化物、硅化物和氧化物对材料的镀覆，具体地说是多元陶瓷复合涂层的制备方法。The technical scheme of the present invention relates to the coating of carbides, silicides and oxides on materials, in particular to a preparation method of a multi-component ceramic composite coating.
背景技术Background technique
碳化物熔点高(可达3880℃)，硬度较高，且具有良好的导热、导电、耐磨损和耐腐蚀等综合性能，在机械、冶金、航空航天、核及军事等领域有重要的应用价值。其中，碳化钛是典型的过渡金属碳化物，且碳化钛是钛、锆、铬过渡金属碳化物中发展最广的材料，在机械、电子、化工、环境保护、聚变反应堆、国防工业等许多领域得到广泛的应用，尤其是被广泛用于结构材料的防护涂层。碳化锆作为一种难熔的金属碳化物，具有高熔点(3420℃)、高硬度(25.5GPa)、高热导和电导率以及高的化学稳定性等优良特性，广泛应用于发射器表面涂层、核燃料颗粒涂层、热光电辐射器涂层以及超高温耐火材料等领域。碳化铌具有高熔点(3610℃)、高硬度、高弹性模量、高耐磨性和热力学稳定等性能。因此在金属工件基体表面制备碳化铌涂层，可使其表面硬度大大提高，可达到HV2800以上，同时提高了工件的工作温度，从而延长其使用寿命，在机械、冶金、航空航天、核及军事等领域有重要的应用价值。碳化钽具有非常高的熔点(3985℃)，碳化钽涂层是一种重要的高强度、耐腐蚀和化学稳定性好的高温结构材料，它具有优异的高温力学性能、抗高速气流的冲刷性能、抗烧蚀性能，并与石墨、碳/碳复合材料具有良好的化学相容性及机械相容性。碳化钼具有高硬度、良好热稳定性和抗腐蚀特性，可在2000℃以上的中性或还原气氛用作高温材料，能耐冷氢氧化钾和氢氧化钠溶液的腐蚀，已经在各种耐高温、耐磨和耐化学腐蚀性的机械领域得到应用。碳化钨作为一种难熔的金属碳化物，具有高熔点(2870℃)、高硬度(2000HV)、高热导和电导率、以及高的化学稳定性等优良特性，广泛应用于发射器表面涂层、核燃料颗粒涂层、热光电辐射器涂层以及超高温耐火材料等领域，是用来制造硬质合金的主要原料，同时它的化学稳定性和热稳定性都比较好，在1000℃的工作环境中，依然具有很高的热硬度。碳化铬具有高温硬度高(HV1500～2100)、耐磨性能好、抗腐蚀性能好、密度低等优点，尤其是其热膨胀系数接近钢，与基体的部件匹配性好。碳化铬是目前高温(600～900℃)环境下应用最为广泛的涂层材料之一，广泛应用于冶金、航空、电力、核能等行业。碳化铬相可增加涂层的硬度，其在高温下能生成致密的氧化铬保护膜。碳化铬因具有良好的耐磨性和耐腐蚀性，广泛应用于零部件防护涂层。碳化铪具有非常高的熔点(3890℃)，是高熔点金属熔炼坩埚内衬的良好材料。碳化铪具有高硬度，可作硬质合金的添加剂，在切削工具和模具领域已得到广泛应用；还具有高弹性系数、良好的电热传导性、较小的热膨胀系数和较好的冲击性能，适用于火箭喷嘴材料，可用于火箭的鼻锥部位，在航天领域有重要应用，在喷管、耐高温内衬、电弧或电解用电极方面也有重要应用。碳化铪的固相稳定性好，耐化学腐蚀，具有适合于高温环境下使用的巨大潜力。另外，在碳纳米管阴极表面蒸镀碳化铪薄膜，可以很好地改善其场发射性能；在碳/碳复合材料中引入碳化铪可以提高其抗烧蚀能力。碳化铪具有许多优异的物理与化学性能，使得它在目前超高温材料中被非常广泛地应用。Carbide has high melting point (up to 3880°C), high hardness, and has good thermal conductivity, electrical conductivity, wear resistance and corrosion resistance and other comprehensive properties. It has important applications in the fields of machinery, metallurgy, aerospace, nuclear and military. value. Among them, titanium carbide is a typical transition metal carbide, and titanium carbide is the most widely developed material among titanium, zirconium, and chromium transition metal carbides. It is used in many fields such as machinery, electronics, chemical industry, environmental protection, fusion reactors, and defense industry. Widely used, especially for protective coatings of structural materials. As a refractory metal carbide, zirconium carbide has excellent properties such as high melting point (3420℃), high hardness (25.5GPa), high thermal and electrical conductivity, and high chemical stability, and is widely used in emitter surface coatings , nuclear fuel particle coating, thermal photoelectric radiator coating and ultra-high temperature refractory materials and other fields. Niobium carbide has properties such as high melting point (3610℃), high hardness, high elastic modulus, high wear resistance and thermodynamic stability. Therefore, the preparation of niobium carbide coating on the surface of the metal workpiece substrate can greatly improve the surface hardness, which can reach HV2800 or more, and at the same time increase the working temperature of the workpiece, thereby prolonging its service life. It is used in machinery, metallurgy, aerospace, nuclear and military. It has important application value in other fields. Tantalum carbide has a very high melting point (3985°C), and tantalum carbide coating is an important high-temperature structural material with high strength, corrosion resistance and chemical stability. It has excellent high-temperature mechanical properties and resistance to high-speed airflow. , ablation resistance, and good chemical and mechanical compatibility with graphite and carbon/carbon composites. Molybdenum carbide has high hardness, good thermal stability and anti-corrosion properties. It can be used as a high-temperature material in a neutral or reducing atmosphere above 2000 ° C. It is resistant to corrosion by cold potassium hydroxide and sodium hydroxide solutions. , wear-resistant and chemical-resistant mechanical fields are used. As a refractory metal carbide, tungsten carbide has excellent properties such as high melting point (2870°C), high hardness (2000HV), high thermal and electrical conductivity, and high chemical stability, and is widely used in emitter surface coatings , nuclear fuel particle coating, thermal photoelectric radiator coating and ultra-high temperature refractory materials, etc., are the main raw materials for making cemented carbide, and its chemical stability and thermal stability are relatively good, work at 1000 ℃ In the environment, it still has a high thermal hardness. Chromium carbide has the advantages of high high temperature hardness (HV1500~2100), good wear resistance, good corrosion resistance and low density, especially its thermal expansion coefficient is close to that of steel, and it has good matching with the components of the matrix. Chromium carbide is one of the most widely used coating materials in high temperature (600-900 ℃) environment, and is widely used in metallurgy, aviation, electric power, nuclear energy and other industries. The chromium carbide phase increases the hardness of the coating, which produces a dense protective chromium oxide film at high temperatures. Chromium carbide is widely used in protective coatings for parts due to its good wear resistance and corrosion resistance. Hafnium carbide has a very high melting point (3890°C) and is a good material for the lining of high melting point metal melting crucibles. Hafnium carbide has high hardness and can be used as an additive for cemented carbide, and has been widely used in the field of cutting tools and molds; it also has high elastic coefficient, good electrical and thermal conductivity, small thermal expansion coefficient and good impact performance, suitable for As a rocket nozzle material, it can be used in the nose cone of a rocket, and has important applications in the aerospace field, as well as in nozzles, high temperature resistant linings, arc or electrolysis electrodes. Hafnium carbide has good solid phase stability and chemical corrosion resistance, and has great potential for use in high temperature environments. In addition, vapor deposition of hafnium carbide film on the surface of carbon nanotube cathode can improve its field emission performance well; the introduction of hafnium carbide into carbon/carbon composite material can improve its ablation resistance. Hafnium carbide has many excellent physical and chemical properties, making it widely used in current ultra-high temperature materials.
然而，碳化物陶瓷涂层的脆性大、抗热冲击性能和高温抗氧化性差，这些都在一定程度上限制了它的进一步应用。研究发现，陶瓷复合涂层可以降低单相难熔碳化物陶瓷涂层的脆性、提高其抗热冲击性能和高温抗氧化性，因此多元陶瓷复合涂层作为高温结构材料受到了人们的关注。硅化物(硅化锆、硅化钛、硅化铬、硅化铪、硅化铌、硅化钽、硅化钒和硅化钨等)具有低密度、良好的热稳定性及较强的抗氧化性能。在碳化物中加入硅化物，不仅可以降低碳化物涂层的脆性、提高其抗热冲击性能和高温抗氧化性，还可以使涂层获得裂纹自愈合能力。当涂层在高温恶劣环境服役过程中出现裂纹时，裂纹表面及附近的硅化物会迅速氧化生成二氧化硅(SiO2)及另一种氧化物，SiO2作为流动相可填封裂纹；另一方面，由于氧化反应的体积膨胀和硅化物自身较高的热膨胀系数会使裂纹处受到压应力，加速裂纹的愈合，从而使涂层具有较好的愈合能力【专利CN201410199003.2】。与相应的硼化物相比，硅化物具有更好的抗氧化性。However, the high brittleness, thermal shock resistance and high temperature oxidation resistance of carbide ceramic coatings limit its further application to a certain extent. It has been found that ceramic composite coatings can reduce the brittleness of single-phase refractory carbide ceramic coatings and improve their thermal shock resistance and high temperature oxidation resistance. Therefore, multi-component ceramic composite coatings have attracted attention as high-temperature structural materials. Silicides (zirconium silicide, titanium silicide, chromium silicide, hafnium silicide, niobium silicide, tantalum silicide, vanadium silicide and tungsten silicide, etc.) have low density, good thermal stability and strong oxidation resistance. Adding silicide to carbide can not only reduce the brittleness of the carbide coating, improve its thermal shock resistance and high temperature oxidation resistance, but also enable the coating to obtain crack self-healing ability. When cracks appear in the coating during service in high temperature and harsh environments, the silicides on the surface of the cracks and nearby will be rapidly oxidized to form silicon dioxide (SiO 2 ) and another oxide, and SiO 2 can be used as a mobile phase to seal the cracks; On the one hand, due to the volume expansion of the oxidation reaction and the high thermal expansion coefficient of the silicide itself, the cracks will be subjected to compressive stress, which will accelerate the healing of the cracks, so that the coating has better healing ability [Patent CN201410199003.2]. Compared with the corresponding borides, silicides have better oxidation resistance.
目前，制备多元陶瓷复合涂层的技术问题如下：At present, the technical problems of preparing multi-component ceramic composite coatings are as follows:
(1)化学气相沉积法的缺点是：1)所得涂层厚度太小，沉积效率低，生产效率低，制备较厚涂层困难；2)基体需要局部或某个表面沉积薄膜时很困难；3)参加沉积反应的反应源和反应后的余气多为有毒易燃易爆气体，操作起来比较危险，且污染环境；4)对设备要求比较严格，往往需要设备具有耐蚀性，导致制备成本很高。(1) The disadvantages of the chemical vapor deposition method are: 1) The thickness of the obtained coating is too small, the deposition efficiency is low, the production efficiency is low, and it is difficult to prepare a thicker coating; 2) It is difficult to deposit a film locally or on a certain surface of the substrate; 3) The reaction source participating in the deposition reaction and the residual gas after the reaction are mostly toxic, flammable and explosive gases, which are dangerous to operate and pollute the environment; 4) The equipment requirements are relatively strict, and the equipment is often required to have corrosion resistance, resulting in the preparation of High cost.
(2)物理气相沉积法的缺点是：1)沉积效率低，生产效率低；2)膜-基结合力弱，镀膜不耐磨，化学杂质难以去除；3)该方法设备复杂，一次投资大。(2) The disadvantages of the physical vapor deposition method are: 1) The deposition efficiency is low, and the production efficiency is low; 2) The film-base bonding force is weak, the coating is not wear-resistant, and the chemical impurities are difficult to remove; 3) This method is complicated in equipment and a large investment .
(3)激光熔覆法的缺点是：1)设备的一次性投资大，运行成本高，尤其是大面积熔覆时，由于光斑尺寸小而必须采取搭接工艺措施，增加了冶金缺陷产生的概率；2)激光熔覆陶瓷涂层过程中，容易产生开裂现象，使涂层质量降低。(3) The disadvantages of the laser cladding method are: 1) The one-time investment of the equipment is large, and the operating cost is high, especially in the case of large-area cladding, due to the small spot size, lap joint process measures must be taken, which increases the risk of metallurgical defects. Probability; 2) In the process of laser cladding ceramic coating, cracking is easy to occur, which reduces the quality of the coating.
(4)料浆涂刷法的缺点是：1)料浆涂敷方法不完善，难以使零件上涂层厚度均匀；2)涂层性能在很大程度上取决于操作者的技术熟练程度；在厚度相同和成分一样的情况下，料浆法涂层由于不致密，故抗破裂的能力较低；3)该方法制备的涂层与基体结合力差、抗热震性能差、烧结温度高、易引入杂质。(4) The disadvantages of the slurry coating method are: 1) The slurry coating method is not perfect, and it is difficult to make the thickness of the coating on the part uniform; 2) The performance of the coating depends to a large extent on the technical proficiency of the operator; In the case of the same thickness and the same composition, the slurry coating is not dense, so the ability to resist cracking is low; 3) The coating prepared by this method has poor adhesion to the substrate, poor thermal shock resistance, and high sintering temperature. , Easy to introduce impurities.
(5)包埋法的缺点是：包埋过程通常需将基体材料置于高温环境中保温(2000℃～3000℃)，因此存在对基体热损伤大且成本高的缺点；同时，由于不同元素沉积和扩散的速度不同，无法控制涂层厚度以及保证涂层中成分的均匀性；另外，受限于坩埚尺寸以及热源的影响，包埋技术难以满足在大尺寸零件上制备涂层。(5) The disadvantage of the embedding method is that the embedding process usually requires the matrix material to be kept in a high temperature environment (2000 ° C ~ 3000 ° C), so there are disadvantages of large thermal damage to the matrix and high cost; at the same time, due to different elements Different deposition and diffusion speeds make it impossible to control the thickness of the coating and ensure the uniformity of the composition in the coating; in addition, limited by the size of the crucible and the influence of the heat source, the embedding technology is difficult to prepare coatings on large-sized parts.
(6)热喷涂法是利用热源将喷涂材料加热至熔化或半熔化状态，并以较快的速度喷射沉积到经过预处理的基体表面形成涂层的方法。然而，热喷涂法直接喷涂多元陶瓷粉末制备多元陶瓷复合涂层的问题是：1)由于过渡族金属难熔化合物(碳化物、硅化物)熔点很高，粉末在热喷涂高温焰流中驻留时间短，可能造成熔化效果不理想，导致沉积效率低，涂层孔隙率高；2)在大气条件下或氧化性气氛下热喷涂碳化物、硅化物易氧化分解；3)碳化物和硅化物晶体中强的共价键键合力可能导致热喷涂工艺中沉积时颗粒间难以产生扩散烧结现象，使碳化物和硅化物颗粒间彼此孤立、无粘结，处于松散状态，涂层孔隙率高。(6) The thermal spraying method is a method of heating the spraying material to a molten or semi-melting state by using a heat source, and spraying and depositing it on the surface of the pretreated substrate at a relatively fast speed to form a coating. However, the problems of directly spraying multi-component ceramic powders to prepare multi-component ceramic composite coatings by thermal spraying are: 1) Due to the high melting point of transition metal refractory compounds (carbides, silicides), the powder resides in the high-temperature flame flow of thermal spraying Short time may cause unsatisfactory melting effect, resulting in low deposition efficiency and high coating porosity; 2) Thermally sprayed carbides and silicides are easily oxidatively decomposed under atmospheric conditions or oxidative atmospheres; 3) Carbides and silicides The strong covalent bonding force in the crystal may make it difficult to produce diffusion and sintering among the particles during deposition in the thermal spraying process, so that the carbide and silicide particles are isolated and unbonded from each other, in a loose state, and the coating porosity is high.
发明内容SUMMARY OF THE INVENTION
本发明的目的是针对当前技术中存在的不足，提供一种多元陶瓷复合涂层的制备方法。该方法采用热喷涂原位反应合成，只需将氧化物、碳化硅和铝粉混合而后进行热喷涂，在热喷涂过程中氧化物、碳化硅和铝反应原位生成碳化物、硅化物和氧化铝相，从而通过热喷涂原位反应得到多元陶瓷复合涂层(碳化物-硅化物-氧化铝复合涂层)。本发明克服了现有技术制备多元陶瓷复合涂层的工艺复杂、成本高、污染大、沉积效率低、涂层性能差和不适合在大规模工业生产中应用的缺陷。同时，本发明还克服了现有技术制备硼化物、碳化物陶瓷复合涂层过程中以碳化硼为原料导致的所得涂层中没有硅化物及碳化硅的存在而高温抗氧化性差的缺点。The purpose of the present invention is to provide a preparation method of a multi-component ceramic composite coating for the deficiencies existing in the current technology. The method adopts thermal spraying in situ reaction synthesis, only need to mix oxide, silicon carbide and aluminum powder and then thermal spray, in the thermal spraying process oxide, silicon carbide and aluminum react in situ to generate carbide, silicide and oxide aluminum phase, thereby obtaining a multi-component ceramic composite coating (carbide-silicide-alumina composite coating) by thermal spraying in-situ reaction. The invention overcomes the defects of complex process, high cost, large pollution, low deposition efficiency, poor coating performance and unsuitable application in large-scale industrial production of the prior art for preparing the multi-component ceramic composite coating. At the same time, the present invention also overcomes the shortcomings of poor high temperature oxidation resistance due to the absence of silicide and silicon carbide in the obtained coating caused by using boron carbide as a raw material in the process of preparing boride and carbide ceramic composite coatings in the prior art.
本发明解决该技术问题所采用的技术方案是：The technical scheme adopted by the present invention to solve the technical problem is:
一种多元陶瓷复合涂层的制备方法，该方法包括如下步骤：A preparation method of a multi-component ceramic composite coating, the method comprises the following steps:
第一步，制备用于热喷涂的氧化物/碳化硅/铝复合粉：The first step is to prepare oxide/silicon carbide/aluminum composite powder for thermal spraying:
将氧化物粉、碳化硅粉和铝粉混合成复合粉，再混合入粘结剂，由此配制成用于热喷涂的氧化物/碳化硅/铝复合粉；The oxide powder, silicon carbide powder and aluminum powder are mixed into composite powder, and then the binder is mixed into the oxide/silicon carbide/aluminum composite powder for thermal spraying;
其中，碳化硅粉为复合粉质量的5～30％，氧化物粉和铝粉之间的质量比例为60～90∶10～40；该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶0.1～2，所述氧化物为氧化锆、氧化钛、氧化铪、氧化钽、氧化铌、氧化钒、氧化铬、氧化钼或氧化钨中的任意x种，x＝1,2,3或4；Among them, the silicon carbide powder is 5-30% of the mass of the composite powder, and the mass ratio between the oxide powder and the aluminum powder is 60-90:10-40; Binder=100:0.1～2, the oxide is any x of zirconium oxide, titanium oxide, hafnium oxide, tantalum oxide, niobium oxide, vanadium oxide, chromium oxide, molybdenum oxide or tungsten oxide, x=1, 2, 3 or 4;
所述的粘结剂具体为聚乙烯醇或甲基纤维素；Described binder is specifically polyvinyl alcohol or methyl cellulose;
所述的氧化物粉和碳化硅粉的粒度为0.001微米～10微米；所述的铝粉粒度为0.1微米～10微米；The particle size of the oxide powder and the silicon carbide powder is 0.001 to 10 microns; the particle size of the aluminum powder is 0.1 to 10 microns;
第二步，对所需涂层的基体材料表面进行预处理，为以下两种方式之一：The second step is to pretreat the surface of the base material to be coated in one of the following two ways:
1)当基体材料为金属材料基体时，采用喷砂处理，随后在喷砂处理后的金属基体材料表面喷涂粘结层；1) When the base material is a metal base material, sandblasting is used, and then a bonding layer is sprayed on the surface of the sandblasted metal base material;
或者，2)当基体材料为无机非金属材料基体时，采用喷砂处理或砂纸打磨处理；Or, 2) When the matrix material is an inorganic non-metallic material matrix, sandblasting or sandpaper polishing is used;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用热喷涂的方法，将上述第一步中制备出的用于热喷涂的氧化物/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的基体材料表面，从而通过原位合成得到多元陶瓷复合涂层；Using the method of thermal spraying, the oxide/silicon carbide/aluminum composite powder for thermal spraying prepared in the above-mentioned first step is sprayed on the surface of the pretreated base material in the above-mentioned second step, thereby obtaining by in-situ synthesis. Multi-component ceramic composite coating;
所述的涂层的厚度为200-500微米；The thickness of the coating is 200-500 microns;
所述采用热喷涂的方法的工艺参数是：送粉气流量为0.3～0.6m3/h，电弧功率为30～40KW，喷枪距离为80～120mm。送粉气为氩气；The technological parameters of the thermal spraying method are: the flow rate of the powder feeding air is 0.3-0.6 m 3 /h, the arc power is 30-40 KW, and the distance of the spray gun is 80-120 mm. The powder feeding gas is argon;
所述的金属材料基体为钢、铸铁、铝合金、铜合金、钛合金、镁合金、镍基高温合金、镍铬合金、钴基高温合金或金属间化合物。The metal material base is steel, cast iron, aluminum alloy, copper alloy, titanium alloy, magnesium alloy, nickel-based superalloy, nickel-chromium alloy, cobalt-based superalloy or intermetallic compound.
所述的无机非金属材料基体为石墨、碳/碳复合材料、碳/碳化硅复合材料或碳化硅/碳化硅复合材料。The inorganic non-metallic material matrix is graphite, carbon/carbon composite material, carbon/silicon carbide composite material or silicon carbide/silicon carbide composite material.
所述粘结层材料是：NiAl、NiCrAl、FeAl、NiCrAlY、CoCrAlY、CoNiCrAlY、NiCoCrAlYTa或NiCrBSi。The bonding layer material is: NiAl, NiCrAl, FeAl, NiCrAlY, CoCrAlY, CoNiCrAlY, NiCoCrAlYTa or NiCrBSi.
上述多元陶瓷复合涂层的制备方法，所涉及的原料均从商购获得，所述的喷砂处理工艺、砂纸打磨工艺和喷涂粘结层的工艺均是本领域现有的熟知的工艺。For the preparation method of the above-mentioned multi-component ceramic composite coating, the raw materials involved are all obtained from commercial sources, and the sandblasting process, sandpaper polishing process and the process of spraying the adhesive layer are all well-known processes in the art.
上述多元陶瓷复合涂层的制备方法，当采用氧化物为氧化锆、氧化钛、氧化铪、氧化钽、氧化铌、氧化钒、氧化铬、氧化钼或氧化钨中的任意一种时，所制备的涂层主要是由碳化物和硅化物相构成，其中的碳化物和硅化物都是原位反应形成的，各相界面纯净，相间结合紧密，涂层内聚强度高；涂层中原位形成的硅化物不仅可以提高涂层的耐高温抗氧化性而且还可以使涂层获得裂纹自愈合能力；当所述原料氧化物粉为两种或两种以上氧化物同时使用时，所制备的涂层中原位生成的碳化物固溶，涂层内聚强度高，进一步提高涂层的硬度、耐磨抗蚀性和耐高温抗氧化性。The preparation method of the above-mentioned multi-component ceramic composite coating, when the oxide is any one of zirconium oxide, titanium oxide, hafnium oxide, tantalum oxide, niobium oxide, vanadium oxide, chromium oxide, molybdenum oxide or tungsten oxide, the prepared The coating is mainly composed of carbide and silicide phases, in which carbide and silicide are formed by in-situ reaction, the interface of each phase is pure, the interphase is closely combined, and the cohesive strength of the coating is high; the in-situ formation of the coating The silicide can not only improve the high temperature and oxidation resistance of the coating, but also make the coating obtain the self-healing ability of cracks; when the raw oxide powder is two or more oxides used at the same time, the prepared The carbides generated in-situ in the coating are solid-dissolved, and the cohesive strength of the coating is high, which further improves the hardness, wear and corrosion resistance and high temperature oxidation resistance of the coating.
本发明突出的实质性特点是：The outstanding substantive features of the present invention are:
当前技术中，如果想制备一种成分的涂层材料，那么就选择这种成分的材料作为热喷涂的原料(或称为喷涂喂料)，比如要想得到碳化锆-硅化锆-氧化铝复合涂层，那么选择碳化锆、硅化锆、氧化铝粉作为喷涂原料；然而，由于碳化物陶瓷相(熔点高)存在常规喷涂中难熔的特性和碳化物、硅化物在喷涂过程中可能被氧化的原因，导致直接喷涂碳化物、硅化物和氧化铝组成的复合粉制备多元陶瓷复合涂层存在困难。In the current technology, if you want to prepare a coating material of one composition, then the material of this composition is selected as the raw material for thermal spraying (or called spraying feed), for example, if you want to obtain a zirconium carbide-zirconium silicide-alumina composite coating layer, then choose zirconium carbide, zirconium silicide, and alumina powder as the spraying raw materials; however, due to the carbide ceramic phase (high melting point), there are refractory characteristics in conventional spraying and carbides and silicides may be oxidized during the spraying process. For this reason, it is difficult to prepare multi-component ceramic composite coatings by directly spraying composite powders composed of carbides, silicides and alumina.
而本发明的热喷涂原位反应是采用相对廉价的原料(比如本发明的氧化锆、碳化硅和铝)，利用氧化物(氧化锆、氧化钛、氧化铪、氧化钽、氧化铌、氧化钒、氧化铬、氧化钼或氧化钨)、碳化硅和铝间在热喷涂焰流的高温条件下发生反应，最终生成主相为碳化物、硅化物和氧化铝(如碳化锆、硅化锆和氧化铝)的多元陶瓷复合涂层。The thermal spraying in-situ reaction of the present invention uses relatively cheap raw materials (such as zirconia, silicon carbide and aluminum of the present invention), uses oxides (zirconia, titanium oxide, hafnium oxide, tantalum oxide, niobium oxide, vanadium oxide) , chromium oxide, molybdenum oxide or tungsten oxide), silicon carbide and aluminum react under the high temperature conditions of thermal spraying flame flow, and finally form the main phase of carbide, silicide and aluminum oxide (such as zirconium carbide, zirconium silicide and oxide Aluminium) multi-component ceramic composite coating.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
(1)本发明采用热喷涂氧化物(氧化锆、氧化钛、氧化铪、氧化钽、氧化铌、氧化钒、氧化铬、氧化钼或氧化钨)、碳化硅和铝组成的复合粉原位反应合成多元陶瓷复合涂层，选用的原料粉资源丰富、价格低廉，且采用了热喷涂的技术工艺，一次成形制备多元陶瓷复合涂层，制备工艺简单、成本低廉，提供了一种制备多元陶瓷复合涂层的新方法。(1) The present invention adopts the in-situ reaction of composite powder composed of thermally sprayed oxides (zirconia, titanium oxide, hafnium oxide, tantalum oxide, niobium oxide, vanadium oxide, chromium oxide, molybdenum oxide or tungsten oxide), silicon carbide and aluminum To synthesize the multi-component ceramic composite coating, the selected raw material powder is rich in resources and low in price, and the thermal spraying technology is adopted to prepare the multi-component ceramic composite coating by one-time forming. The preparation process is simple and the cost is low, and a method for preparing the multi-component ceramic composite coating is provided. A new approach to coating.
(2)采用本发明方法制备多元陶瓷复合涂层，克服了碳化物、硅化物颗粒间彼此孤立、无粘结处于松散状态的缺点，所制备出的多元陶瓷复合涂层中各相，即碳化物、硅化物和氧化铝都是原位反应形成的，各相界面纯净，相间结合紧密；当采用两种或两种以上氧化物作为原料时，所制备的涂层中原位生成的碳化物固溶，涂层内聚强度高。(2) The multi-component ceramic composite coating is prepared by the method of the present invention, which overcomes the shortcomings of the carbide and silicide particles being isolated from each other and in a loose state without bonding. Compounds, silicides and alumina are all formed by in-situ reactions, the interface of each phase is pure, and the phases are closely combined; when two or more oxides are used as raw materials, the carbides generated in-situ in the prepared coating will solidify. Soluble, the coating has high cohesive strength.
(3)本发明方法所制备出的多元陶瓷复合涂层成分均匀且具有较宽的元素配比调节空间，具有高的致密度、硬度、耐磨抗蚀性和耐高温抗氧化性；涂层中硅化物的存在不仅可以提高涂层的耐高温抗氧化性而且还可以使涂层获得裂纹自愈合能力；当采用两种或两种以上氧化物作为原料时，所制备的涂层中原位生成的碳化物固溶，可以起到固溶强化作用，进一步提高涂层的硬度、耐磨抗蚀性和耐高温抗氧化性；二元或多元固溶相可以起到固溶强化作用，进一步提高涂层的硬度、耐磨抗蚀性和耐高温抗氧化性；克服了现有技术制备多元陶瓷复合涂层工艺复杂、成本高、能耗大、污染大、效率低、涂层厚度低、涂层致密度低和涂层性能差的缺陷。(3) The multi-component ceramic composite coating prepared by the method of the present invention is uniform in composition, has a wide adjustment space for element ratio, and has high density, hardness, wear resistance and corrosion resistance, and high temperature and oxidation resistance; coating; The presence of silicide can not only improve the high temperature oxidation resistance of the coating, but also enable the coating to obtain crack self-healing ability; when two or more oxides are used as raw materials, the in-situ The formed carbide is solid solution, which can play a solid solution strengthening effect, and further improve the hardness, wear resistance and high temperature oxidation resistance of the coating; binary or multi-component solid solution phase can play a solid solution strengthening effect, further Improve the hardness, wear and corrosion resistance and high temperature and oxidation resistance of the coating; overcome the complex process, high cost, high energy consumption, large pollution, low efficiency, low coating thickness, Defects of low coating density and poor coating performance.
(4)为了获得性能优异的多元陶瓷复合涂层，首先要进行原料体系的优化，本发明发明人团队经过多年的深入研究和近百次反复实验，才成功采用本发明方法制备多元陶瓷复合涂层，不仅制备工艺简单且获得的多元陶瓷复合涂层性能很好，获得了事先预料不到的技术效果和明显的经济效益。(4) In order to obtain a multi-component ceramic composite coating with excellent performance, the raw material system must be optimized first. After years of in-depth research and nearly a hundred repeated experiments, the inventor team of the present invention successfully used the method of the present invention to prepare the multi-component ceramic composite coating. Not only the preparation process is simple, but also the obtained multi-component ceramic composite coating has good performance, and obtains unexpected technical effects and obvious economic benefits.
将本发明制备的多元陶瓷复合涂层与相同工艺制备的硼化物、碳化物涂层的抗氧化性和抗烧蚀性相比较，本发明制备的多元陶瓷复合涂层比热喷涂碳化锆粉、硼化锆粉、硼化锆-碳化锆复合粉、碳化钛粉、锆/碳化硼复合粉和氧化锆/碳化硼/铝复合粉所得涂层的抗氧化性(1000℃，24h，质量增重率，％)最多提高40％；本发明制备的多元陶瓷复合涂层比热喷涂碳化锆粉、硼化锆粉、硼化锆-碳化锆复合粉、碳化钛粉、锆/碳化硼复合粉和氧化锆/碳化硼/铝复合粉所得涂层的抗烧蚀性(热通量4.02MW/m2，40s质量烧蚀率，％)最多提高6.68％。Comparing the oxidation resistance and ablation resistance of the multi-component ceramic composite coating prepared by the present invention with the boride and carbide coatings prepared by the same process, the multi-component ceramic composite coating prepared by the present invention is better than thermal spraying zirconium carbide powder, Oxidation resistance of coatings obtained by zirconium boride powder, zirconium boride-zirconium carbide composite powder, titanium carbide powder, zirconium/boron carbide composite powder and zirconia/boron carbide/aluminum composite powder (1000℃, 24h, mass gain ratio, %) by up to 40%; the multi-component ceramic composite coating prepared by the invention is thermally sprayed with zirconium carbide powder, zirconium boride powder, zirconium boride-zirconium carbide composite powder, titanium carbide powder, zirconium/boron carbide composite powder and The ablation resistance of the coating obtained by the zirconia/boron carbide/aluminum composite powder (heat flux 4.02MW/m 2 , 40s mass ablation rate, %) increased by up to 6.68%.
附图说明Description of drawings
下面结合附图和实施例对本发明进一步说明。The present invention will be further described below in conjunction with the accompanying drawings and embodiments.
图1为实施例4所制得的多元陶瓷复合涂层(碳化钛-硅化钛-氧化铝复合涂层)的XRD图谱。1 is the XRD pattern of the multi-component ceramic composite coating (titanium carbide-titanium silicide-alumina composite coating) prepared in Example 4.
图2为实施例4所制得的多元陶瓷复合涂层(碳化钛-硅化钛-氧化铝复合涂层)的SEM图。2 is a SEM image of the multi-component ceramic composite coating (titanium carbide-titanium silicide-alumina composite coating) prepared in Example 4.
图3为实施例8所制得的多元陶瓷复合涂层(碳化铬-硅化铬-氧化铝复合涂层)的XRD图谱。3 is the XRD pattern of the multi-component ceramic composite coating (chromium carbide-chromium silicide-alumina composite coating) prepared in Example 8.
图4为实施例8所制得的多元陶瓷复合涂层(碳化铬-硅化铬-氧化铝复合涂层)的SEM图。4 is a SEM image of the multi-component ceramic composite coating (chromium carbide-chromium silicide-alumina composite coating) prepared in Example 8.
图5为实施例11所制得的多元陶瓷复合涂层(碳化铌-硅化铌-氧化铝复合涂层)的XRD图谱。5 is the XRD pattern of the multi-component ceramic composite coating (niobium carbide-niobium silicide-alumina composite coating) prepared in Example 11.
图6为实施例11所制得的多元陶瓷复合涂层(碳化铌-硅化铌-氧化铝复合涂层)的SEM图。6 is a SEM image of the multi-component ceramic composite coating (niobium carbide-niobium silicide-alumina composite coating) prepared in Example 11.
具体实施方式Detailed ways
实施例1Example 1
第一步，制备用于热喷涂的氧化锆/碳化硅/铝复合粉：The first step is to prepare zirconia/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化锆粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化锆粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为5％，铝粉加氧化锆粉占上述氧化锆粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为95％，氧化锆粉和铝粉之间的质量比例为60∶40，再均匀混合入粘结剂(甲基纤维素，实施例2-10同)，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶0.1，由此配制成用于热喷涂的氧化锆/碳化硅/铝复合粉；The zirconia powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, the silicon carbide powder accounts for 5% of the total mass of the above-mentioned zirconia powder, silicon carbide powder and aluminum powder, and the aluminum powder plus zirconia powder accounts for the above-mentioned zirconia powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 95%, the mass ratio between the zirconia powder and the aluminum powder is 60:40, and then the binder (methyl cellulose, the same as in Example 2-10) is uniformly mixed, The amount of the binder is such that the weight ratio is the above-mentioned composite powder: binder=100:0.1, thereby preparing the zirconia/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为Inconel 718镍基高温合金，预处理方式采用喷砂处理，随后在喷砂处理后的镍基高温合金基体材料表面喷涂厚度为50微米的NiAl粘结底层；The base material is Inconel 718 nickel-based superalloy, and the pretreatment method is sandblasting, and then a NiAl bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the nickel-based superalloy base material after sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.36m3/h，电弧功率为30KW，喷枪距离为80mm，送粉气为氩气(以下实施例同)；将上述第一步中配制出的用于热喷涂的氧化锆/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的镍基高温合金基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。The atmospheric plasma spraying method was adopted, the flow rate of the powder feeding gas was 0.36m 3 /h, the arc power was 30KW, the distance of the spray gun was 80mm, and the powder feeding gas was argon (the same as in the following examples); The thermally sprayed zirconia/silicon carbide/aluminum composite powder was sprayed on the surface of the nickel-based superalloy base material pretreated in the second step above, thereby forming a multi-component ceramic composite coating with a thickness of 200 microns.
实施例2Example 2
第一步，制备用于热喷涂的氧化锆/碳化硅/铝复合粉：The first step is to prepare zirconia/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化锆粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化锆粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为10％，铝粉加氧化锆粉占上述氧化锆粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为90％，氧化锆粉和铝粉之间的质量比例为85∶15，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶1，由此配制成用于热喷涂的氧化锆/碳化硅/铝复合粉；The zirconia powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, the silicon carbide powder accounts for 10% of the total mass of the above-mentioned zirconia powder, silicon carbide powder and aluminum powder, and the aluminum powder plus zirconia powder accounts for the above-mentioned zirconia powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 90%, the mass ratio between the zirconia powder and the aluminum powder is 85:15, and then evenly mixed into the binder, the amount of the binder is 100%, and the weight ratio is the above composite powder. : Binder=100:1, which is formulated into zirconia/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的TC4钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结层；The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding layer with a thickness of 50 microns is sprayed on the surface of the sandblasted TC4 titanium alloy base material;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.4m3/h，电弧功率为35KW，喷枪距离为100mm，将上述第一步中配制出的用于热喷涂的氧化锆/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的TC4钛合金基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Using the atmospheric plasma spraying method, the powder feeding air flow rate is 0.4m 3 /h, the arc power is 35KW, and the spray gun distance is 100mm. The surface of the TC4 titanium alloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating with a thickness of 200 microns.
实施例3Example 3
第一步，制备用于热喷涂的氧化锆/碳化硅/铝复合粉：The first step is to prepare zirconia/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化锆粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化锆粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为30％，铝粉加氧化锆粉占上述氧化锆粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为70％，氧化锆粉和铝粉之间的质量比例为90∶10，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶2，由此配制成用于热喷涂的氧化锆/碳化硅/铝复合粉；The zirconia powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, silicon carbide powder accounts for 30% of the total mass of the above-mentioned zirconia powder, silicon carbide powder and aluminum powder, and aluminum powder plus zirconia powder accounts for the above-mentioned zirconia powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 70%, and the mass ratio between the zirconia powder and the aluminum powder is 90:10, and then evenly mixed into the binder, the amount of the binder is 70%, and the weight ratio is the above composite powder. : Binder = 100:2, which is formulated into zirconia/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为石墨，预处理方式采用喷砂处理；The base material is graphite, and the pretreatment method is sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用等离子喷涂方法，送粉气流量为0.6m3/h，电弧功率为40KW，喷枪距离为120mm，将上述第一步中配制出的用于热喷涂的氧化锆/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的石墨基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Using the plasma spraying method, the flow rate of powder feeding air is 0.6m 3 /h, the arc power is 40KW, and the distance of the spray gun is 120mm. The surface of the graphite base material pretreated in the second step above forms a multi-component ceramic composite coating with a thickness of 200 microns.
实施例4Example 4
第一步，制备用于热喷涂的氧化钛/碳化硅/铝复合粉：The first step is to prepare titanium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化钛粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化钛粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为5％，铝粉加氧化钛粉占上述氧化钛粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为95％，氧化钛粉和铝粉之间的质量比例为60∶40，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶0.1，由此配制成用于热喷涂的氧化钛/碳化硅/铝复合粉；The titanium oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, the silicon carbide powder accounts for 5% of the total mass of the above-mentioned titanium oxide powder, silicon carbide powder and aluminum powder, and the aluminum powder plus titanium oxide powder accounts for the above-mentioned titanium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 95%, the mass ratio between the titanium oxide powder and the aluminum powder is 60:40, and then evenly mixed into the binder, the amount of the binder is 100%, and the weight ratio is the above composite powder. : Binder = 100: 0.1, thus preparing titanium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为Inconel 718镍基高温合金，预处理方式采用喷砂处理，随后在喷砂处理后的镍基高温合金基体材料表面喷涂厚度为50微米的NiAl粘结底层；The base material is Inconel 718 nickel-based superalloy, and the pretreatment method is sandblasting, and then a NiAl bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the nickel-based superalloy base material after sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.5m3/h，电弧功率为32KW，喷枪距离为100mm，将上述第一步中配制出的用于热喷涂的氧化钛/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的镍基高温合金基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Atmospheric plasma spraying method is adopted, the powder feeding air flow is 0.5m 3 /h, the arc power is 32KW, and the distance of the spray gun is 100mm. The surface of the nickel-based superalloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating with a thickness of 200 microns.
图1为本实施例制得的多元陶瓷复合涂层的XRD图谱，由该XRD图谱可以看出，该多元陶瓷复合涂层主要是由碳化钛、硅化钛和氧化铝相构成，其次还有碳化硅相存在。可以看出，以氧化钛/碳化硅/铝复合粉为原料，采用等离子喷涂方法可以成功制备出主要成分为碳化钛、硅化钛和氧化铝的多元陶瓷复合涂层。Fig. 1 is the XRD pattern of the multi-component ceramic composite coating prepared in the present embodiment. It can be seen from the XRD pattern that the multi-component ceramic composite coating is mainly composed of titanium carbide, titanium silicide and alumina phases, followed by carbonization. The silicon phase is present. It can be seen that the multi-component ceramic composite coating whose main components are titanium carbide, titanium silicide and aluminum oxide can be successfully prepared by plasma spraying using titanium oxide/silicon carbide/aluminum composite powder as raw materials.
图2为本实施例制得的多元陶瓷复合涂层的SEM图。可以看出，多元陶瓷复合涂层厚度达到200微米以上，涂层致密度高，涂层与基体结合良好。FIG. 2 is an SEM image of the multi-component ceramic composite coating prepared in this example. It can be seen that the thickness of the multi-component ceramic composite coating reaches more than 200 microns, the coating density is high, and the coating is well combined with the substrate.
实施例5Example 5
第一步，制备用于热喷涂的氧化钛/碳化硅/铝复合粉：The first step is to prepare titanium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化钛粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化钛粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为10％，铝粉加氧化钛粉占上述氧化钛粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为90％，氧化钛粉和铝粉之间的质量比例为85∶15，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶1，由此配制成用于热喷涂的氧化钛/碳化硅/铝复合粉；The titanium oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, the silicon carbide powder accounts for 10% of the total mass of the above-mentioned titanium oxide powder, silicon carbide powder and aluminum powder, and the aluminum powder plus titanium oxide powder accounts for the above-mentioned titanium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 90%, the mass ratio between the titanium oxide powder and the aluminum powder is 85:15, and then evenly mixed into the binder, the amount of the binder is 100%, and the weight ratio is the above-mentioned composite powder. : Binder=100:1, thus preparing titanium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为1Cr18Ni9Ti钢，预处理方式采用喷砂处理，随后在喷砂处理后的1Cr18Ni9Ti钢基体材料表面喷涂厚度为50微米的NiCrAlY粘结层；The base material is 1Cr18Ni9Ti steel, and the pretreatment method is sandblasting, and then a NiCrAlY bonding layer with a thickness of 50 microns is sprayed on the surface of the sandblasted 1Cr18Ni9Ti steel base material;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.5m3/h，电弧功率为36KW，喷枪距离为110mm，将上述第一步中配制出的用于热喷涂的氧化钛/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的1Cr18Ni9Ti钢基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Atmospheric plasma spraying method was used, the powder feeding air flow was 0.5m 3 /h, the arc power was 36KW, and the spray gun distance was 110mm. The surface of the 1Cr18Ni9Ti steel base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating with a thickness of 200 microns.
实施例6Example 6
第一步，制备用于热喷涂的氧化钛/碳化硅/铝复合粉：The first step is to prepare titanium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化钛粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化钛粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为30％，铝粉加氧化钛粉占上述氧化钛粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为70％，氧化钛粉和铝粉之间的质量比例为90∶10，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶2，由此配制成用于热喷涂的氧化钛/碳化硅/铝复合粉；The titanium oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, silicon carbide powder accounts for 30% of the total mass of the above-mentioned titanium oxide powder, silicon carbide powder and aluminum powder, and aluminum powder plus titanium oxide powder accounts for the above-mentioned titanium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 70%, the mass ratio between the titanium oxide powder and the aluminum powder is 90:10, and then evenly mixed into the binder, the amount of the binder is , and the weight ratio is the above composite powder. : Binder = 100: 2, thereby preparing titanium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为石墨，预处理方式采用喷砂处理；The base material is graphite, and the pretreatment method is sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用等离子喷涂方法，送粉气流量为0.6m3/h，电弧功率为40KW，喷枪距离为120mm，将上述第一步中配制出的用于热喷涂的氧化钛/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的石墨基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Using the plasma spraying method, the powder feeding air flow rate is 0.6m 3 /h, the arc power is 40KW, and the spray gun distance is 120mm. The surface of the graphite base material pretreated in the second step above forms a multi-component ceramic composite coating with a thickness of 200 microns.
实施例7Example 7
第一步，制备用于热喷涂的氧化铬/碳化硅/铝复合粉：The first step is to prepare chromium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化铬粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化铬粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为5％，铝粉加氧化铬粉占上述氧化铬粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为95％，氧化铬粉和铝粉之间的质量比例为60∶40，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶0.1，由此配制成用于热喷涂的氧化铬/碳化硅/铝复合粉；Chromium oxide powder with a particle size range of 0.001 micron to 10 microns, silicon carbide powder with a particle size range of 0.001 micron to 10 microns, and aluminum powder with a particle size range of 0.1 micron to 10 microns are uniformly mixed into composite powder, Among them, silicon carbide powder accounts for 5% of the total mass of the above-mentioned chromium oxide powder, silicon carbide powder and aluminum powder, and aluminum powder plus chromium oxide powder accounts for the above-mentioned chromium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 95%, the mass ratio between the chromium oxide powder and the aluminum powder is 60:40, and then evenly mixed into the binder, the amount of the binder is 100%, and the weight ratio is the above-mentioned composite powder. : Binder=100: 0.1, which is formulated into chromium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为Inconel 718镍基高温合金，预处理方式采用喷砂处理，随后在喷砂处理后的镍基高温合金基体材料表面喷涂厚度为50微米的NiAl粘结底层；The base material is Inconel 718 nickel-based superalloy, and the pretreatment method is sandblasting, and then a NiAl bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the nickel-based superalloy base material after sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.4m3/h，电弧功率为33KW，喷枪距离为90mm，将上述第一步中配制出的用于热喷涂的氧化铬/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的镍基高温合金基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Atmospheric plasma spraying method was adopted, the powder feeding air flow was 0.4m 3 /h, the arc power was 33KW, and the spray gun distance was 90mm. The surface of the nickel-based superalloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating with a thickness of 200 microns.
实施例8Example 8
第一步，制备用于热喷涂的氧化铬/碳化硅/铝复合粉：The first step is to prepare chromium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化铬粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化铬粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为20％，铝粉加氧化铬粉占上述氧化铬粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为80％，氧化铬粉和铝粉之间的质量比例为78∶22，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶1，由此配制成用于热喷涂的氧化铬/碳化硅/铝复合粉；Chromium oxide powder with a particle size range of 0.001 micron to 10 microns, silicon carbide powder with a particle size range of 0.001 micron to 10 microns, and aluminum powder with a particle size range of 0.1 micron to 10 microns are uniformly mixed into composite powder, Among them, the silicon carbide powder accounts for 20% of the total mass of the above-mentioned chromium oxide powder, silicon carbide powder and aluminum powder, and the aluminum powder plus chromium oxide powder accounts for the above-mentioned chromium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three kinds of raw material powders is 80%, the mass ratio between the chromium oxide powder and the aluminum powder is 78:22, and then evenly mixed into the binder, the amount of the binder is 100%, and the weight ratio is the above-mentioned composite powder. : Binder=100:1, which is formulated into chromium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结层；The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding layer with a thickness of 50 microns is sprayed on the surface of the sandblasted titanium alloy base material;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.5m3/h，电弧功率为38KW，喷枪距离为110，将上述第一步中配制出的用于热喷涂的氧化铬/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的钛合金基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Using the atmospheric plasma spraying method, the powder feeding air flow rate is 0.5m 3 /h, the arc power is 38KW, and the spray gun distance is 110. The chromium oxide/silicon carbide/aluminum composite powder for thermal spraying prepared in the first step above was prepared The surface of the titanium alloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating with a thickness of 200 microns.
图3为本实施例制得的多元陶瓷复合涂层的XRD图谱，由该XRD图谱可以看出，该多元陶瓷复合涂层主要是由碳化铬、硅化铬和氧化铝相构成，其次还有氧化铬和碳化硅相存在。可以看出，以氧化铬/碳化硅/铝复合粉为原料，采用等离子喷涂方法可以成功制备出主要成分为碳化铬、硅化铬和氧化铝的多元陶瓷复合涂层。Fig. 3 is the XRD pattern of the multi-component ceramic composite coating prepared in the present embodiment. It can be seen from the XRD pattern that the multi-component ceramic composite coating is mainly composed of chromium carbide, chromium silicide and aluminum oxide phases, followed by oxidation Chromium and silicon carbide phases are present. It can be seen that the multi-component ceramic composite coating whose main components are chromium carbide, chromium silicide and aluminum oxide can be successfully prepared by plasma spraying using chromium oxide/silicon carbide/aluminum composite powder as raw materials.
图4为本实施例制得的多元陶瓷复合涂层的SEM图。可以看出，多元陶瓷复合涂层厚度达到200微米以上，涂层致密度高，涂层与基体结合良好。FIG. 4 is an SEM image of the multi-component ceramic composite coating prepared in this example. It can be seen that the thickness of the multi-component ceramic composite coating reaches more than 200 microns, the coating density is high, and the coating is well combined with the substrate.
实施例9Example 9
第一步，制备用于热喷涂的氧化铬/碳化硅/铝复合粉：The first step is to prepare chromium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化铬粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化铬粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为30％，铝粉加氧化铬粉占上述氧化铬粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为70％，氧化铬粉和铝粉之间的质量比例为90∶10，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶2，由此配制成用于热喷涂的氧化铬/碳化硅/铝复合粉；Chromium oxide powder with a particle size range of 0.001 micron to 10 microns, silicon carbide powder with a particle size range of 0.001 micron to 10 microns, and aluminum powder with a particle size range of 0.1 micron to 10 microns are uniformly mixed into composite powder, Among them, silicon carbide powder accounts for 30% of the total mass of the above-mentioned chromium oxide powder, silicon carbide powder and aluminum powder, and aluminum powder plus chromium oxide powder accounts for the above-mentioned chromium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 70%, the mass ratio between the chromium oxide powder and the aluminum powder is 90:10, and then evenly mixed into the binder, the amount of the binder is 70%, and the weight ratio is the above-mentioned composite powder. : Binder = 100:2, which is formulated into chromium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为石墨，预处理方式采用喷砂处理；The base material is graphite, and the pretreatment method is sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用等离子喷涂方法，送粉气流量为0.6m3/h，电弧功率为40KW，喷枪距离为120mm，将上述第一步中配制出的用于热喷涂的氧化铬/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的石墨基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Using the plasma spraying method, the powder feeding air flow rate is 0.6m 3 /h, the arc power is 40KW, and the spray gun distance is 120mm. The surface of the graphite base material pretreated in the second step above forms a multi-component ceramic composite coating with a thickness of 200 microns.
实施例10Example 10
第一步，制备用于热喷涂的氧化铌/碳化硅/铝复合粉：The first step is to prepare niobium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化铌粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化铌粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为5％，铝粉加氧化铌粉占上述氧化铌粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为95％，氧化铌粉和铝粉之间的质量比例为60∶40，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶0.1，由此配制成用于热喷涂的氧化铌/碳化硅/铝复合粉；The niobium oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, the silicon carbide powder accounts for 5% of the total mass of the above-mentioned niobium oxide powder, silicon carbide powder and aluminum powder, and the aluminum powder plus niobium oxide powder accounts for the above-mentioned niobium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 95%, the mass ratio between the niobium oxide powder and the aluminum powder is 60:40, and then evenly mixed into the binder, the amount of the binder is 100%, and the weight ratio is the above composite powder. : Binder=100: 0.1, which is formulated into niobium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为Inconel 718镍基高温合金，预处理方式采用喷砂处理，随后在喷砂处理后的镍基高温合金基体材料表面喷涂厚度为50微米的NiAl粘结底层；The base material is Inconel 718 nickel-based superalloy, and the pretreatment method is sandblasting, and then a NiAl bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the nickel-based superalloy base material after sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.6m3/h，电弧功率为40KW，喷枪距离为120mm，将上述第一步中配制出的用于热喷涂的氧化铌/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的镍基高温合金基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Using the atmospheric plasma spraying method, the powder feeding air flow rate is 0.6m3 /h, the arc power is 40KW, and the spray gun distance is 120mm. The niobium oxide/silicon carbide/aluminum composite powder for thermal spraying prepared in the first step above was The surface of the nickel-based superalloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating with a thickness of 200 microns.
实施例11Example 11
第一步，制备用于热喷涂的氧化铌/碳化硅/铝复合粉：The first step is to prepare niobium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化铌粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化铌粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为13％，铝粉加氧化铌粉占上述氧化铌粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为87％，氧化铌粉和铝粉之间的质量比例为75∶25，再均匀混合入粘结剂(聚乙烯醇，以下实施例同)，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶1，由此配制成用于热喷涂的氧化铌/碳化硅/铝复合粉；The niobium oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, silicon carbide powder accounts for 13% of the total mass of the above-mentioned niobium oxide powder, silicon carbide powder and aluminum powder, and aluminum powder plus niobium oxide powder accounts for the above-mentioned niobium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 87%, the mass ratio between the niobium oxide powder and the aluminum powder is 75:25, and then uniformly mixed into a binder (polyvinyl alcohol, the same in the following examples), the bonding agent The dosage of the agent is that the weight ratio is the above-mentioned composite powder: the binder=100:1, thereby preparing the niobium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结层；The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding layer with a thickness of 50 microns is sprayed on the surface of the sandblasted titanium alloy base material;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.5m3/h，电弧功率为37KW，喷枪距离为110mm，将上述第一步中配制出的用于热喷涂的氧化铌/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的钛合金基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Using the atmospheric plasma spraying method, the powder feeding air flow is 0.5m 3 /h, the arc power is 37KW, and the spray gun distance is 110mm. The niobium oxide/silicon carbide/aluminum composite powder for thermal spraying prepared in the first step above The surface of the titanium alloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating with a thickness of 200 microns.
图5为本实施例制得的多元陶瓷复合涂层的XRD图谱，由该XRD图谱可以看出，该多元陶瓷复合涂层主要是由碳化铌、硅化铌和氧化铝相构成，其次还有氧化铌和碳化硅相存在。可以看出，以氧化铌/碳化硅/铝复合粉为原料，采用等离子喷涂方法可以成功制备出主要成分为碳化铌、硅化铌和氧化铝的多元陶瓷复合涂层。Fig. 5 is the XRD pattern of the multi-component ceramic composite coating prepared in the present embodiment. It can be seen from the XRD pattern that the multi-component ceramic composite coating is mainly composed of niobium carbide, niobium silicide and alumina phases, followed by oxides Niobium and silicon carbide phases are present. It can be seen that the multi-component ceramic composite coating whose main components are niobium carbide, niobium silicide and alumina can be successfully prepared by plasma spraying using niobium oxide/silicon carbide/aluminum composite powder as raw materials.
图6为本实施例制得的多元陶瓷复合涂层的SEM图。可以看出，多元陶瓷复合涂层厚度达到200微米以上，涂层致密度高，涂层与基体结合良好。FIG. 6 is an SEM image of the multi-component ceramic composite coating prepared in this example. It can be seen that the thickness of the multi-component ceramic composite coating reaches more than 200 microns, the coating density is high, and the coating is well combined with the substrate.
实施例12Example 12
第一步，制备用于热喷涂的氧化铌/碳化硅/铝复合粉：The first step is to prepare niobium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化铌粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化铌粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为30％，铝粉加氧化铌粉占上述氧化铌粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为70％，氧化铌粉和铝粉之间的质量比例为90∶10，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶2，由此配制成用于热喷涂的氧化铌/碳化硅/铝复合粉；The niobium oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, the silicon carbide powder accounts for 30% of the total mass of the above-mentioned niobium oxide powder, silicon carbide powder and aluminum powder, and the aluminum powder plus niobium oxide powder accounts for the above-mentioned niobium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 70%, the mass ratio between the niobium oxide powder and the aluminum powder is 90:10, and then evenly mixed into the binder, the amount of the binder is 1, and the weight ratio is the above-mentioned composite powder. : Binder = 100:2, which is formulated into niobium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为石墨，预处理方式采用喷砂处理；The base material is graphite, and the pretreatment method is sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用等离子喷涂方法，送粉气流量为0.3m3/h，电弧功率为30KW，喷枪距离为80mm，将上述第一步中配制出的用于热喷涂的氧化铌/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的石墨基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Using the plasma spraying method, the flow rate of the powder feeding air is 0.3m 3 /h, the arc power is 30KW, and the distance of the spray gun is 80mm. The surface of the graphite base material pretreated in the second step above forms a multi-component ceramic composite coating with a thickness of 200 microns.
实施例13Example 13
第一步，制备用于热喷涂的氧化铪/碳化硅/铝复合粉：The first step is to prepare the hafnium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化铪粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化铪粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为5％，铝粉加氧化铪粉占上述氧化铪粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为95％，氧化铪粉和铝粉之间的质量比例为60∶40，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶0.1，由此配制成用于热喷涂的氧化铪/碳化硅/铝复合粉；The hafnium oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, the silicon carbide powder accounts for 5% of the total mass of the above-mentioned hafnium oxide powder, silicon carbide powder and aluminum powder, and the aluminum powder plus hafnium oxide powder accounts for the above-mentioned hafnium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three kinds of raw material powders is 95%, the mass ratio between the hafnium oxide powder and the aluminum powder is 60:40, and then evenly mixed into the binder, the amount of the binder is , and the weight ratio is the above-mentioned composite powder. : Binder=100: 0.1, which is formulated into hafnium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为Inconel 718镍基高温合金，预处理方式采用喷砂处理，随后在喷砂处理后的镍基高温合金基体材料表面喷涂厚度为50微米的NiAl粘结底层；The base material is Inconel 718 nickel-based superalloy, and the pretreatment method is sandblasting, and then a NiAl bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the nickel-based superalloy base material after sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.6m3/h，电弧功率为40KW，喷枪距离为120mm，将上述第一步中配制出的用于热喷涂的氧化铪/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的镍基高温合金基体材料表面，从而形成多元陶瓷复合涂层。制备出的多元陶瓷复合涂层厚度达到200微米，涂层致密度高，涂层与基体结合良好。Atmospheric plasma spraying method was adopted, the powder feeding air flow was 0.6m 3 /h, the arc power was 40KW, and the spray gun distance was 120mm. The surface of the nickel-based superalloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating. The thickness of the prepared multi-component ceramic composite coating reaches 200 microns, the coating density is high, and the coating is well combined with the substrate.
实施例14Example 14
第一步，制备用于热喷涂的氧化铪/碳化硅/铝复合粉：The first step is to prepare the hafnium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化铪粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化铪粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为20％，铝粉加氧化铪粉占上述氧化铪粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为80％，氧化铪粉和铝粉之间的质量比例为75∶25，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶1，由此配制成用于热喷涂的氧化铪/碳化硅/铝复合粉；The hafnium oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, silicon carbide powder accounts for 20% of the total mass of the above-mentioned hafnium oxide powder, silicon carbide powder and aluminum powder, and aluminum powder plus hafnium oxide powder accounts for the above-mentioned hafnium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three kinds of raw material powders is 80%, the mass ratio between the hafnium oxide powder and the aluminum powder is 75:25, and then evenly mixed into the binder, the amount of the binder is 100%, and the weight ratio is the above-mentioned composite powder. : Binder = 100:1, which is formulated into hafnium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结层；The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding layer with a thickness of 50 microns is sprayed on the surface of the sandblasted titanium alloy base material;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.3m3/h，电弧功率为30KW，喷枪距离为80mm，将上述第一步中配制出的用于热喷涂的氧化铪/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的钛合金基体材料表面，从而形成多元陶瓷复合涂层。制备出的多元陶瓷复合涂层厚度达到200微米，涂层致密度高，涂层与基体结合良好。Atmospheric plasma spraying method was adopted, the powder feeding air flow was 0.3m 3 /h, the arc power was 30KW, and the spray gun distance was 80mm. The hafnium oxide/silicon carbide/aluminum composite powder for thermal spraying prepared in the first step was The surface of the titanium alloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating. The thickness of the prepared multi-component ceramic composite coating reaches 200 microns, the coating density is high, and the coating is well combined with the substrate.
实施例15Example 15
第一步，制备用于热喷涂的氧化铪/碳化硅/铝复合粉：The first step is to prepare the hafnium oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化铪粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化铪粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为30％，铝粉加氧化铪粉占上述氧化铪粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为70％，氧化铪粉和铝粉之间的质量比例为90∶10，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶2，由此配制成用于热喷涂的氧化铪/碳化硅/铝复合粉；The hafnium oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, silicon carbide powder accounts for 30% of the total mass of the above-mentioned hafnium oxide powder, silicon carbide powder and aluminum powder, and aluminum powder plus hafnium oxide powder accounts for the above-mentioned hafnium oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three kinds of raw material powders is 70%, the mass ratio between the hafnium oxide powder and the aluminum powder is 90:10, and then evenly mixed into the binder, the amount of the binder is 100%, and the weight ratio is the above-mentioned composite powder. : Binder=100: 2, which is formulated into hafnium oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为石墨，预处理方式采用喷砂处理；The base material is graphite, and the pretreatment method is sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用等离子喷涂方法，送粉气流量为0.4m3/h，电弧功率为34KW，喷枪距离为90mm，将上述第一步中配制出的用于热喷涂的氧化铪/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的石墨基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Using the plasma spraying method, the powder feeding air flow rate is 0.4m 3 /h, the arc power is 34KW, and the spray gun distance is 90mm. The surface of the graphite base material pretreated in the second step above forms a multi-component ceramic composite coating with a thickness of 200 microns.
实施例16Example 16
第一步，制备用于热喷涂的氧化钽/碳化硅/铝复合粉：The first step is to prepare tantalum oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化钽粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化钽粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为5％，铝粉加氧化钽粉占上述氧化钽粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为95％，氧化钽粉和铝粉之间的质量比例为60∶40，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶0.1，由此配制成用于热喷涂的氧化钽/碳化硅/铝复合粉；The tantalum oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, the silicon carbide powder accounts for 5% of the total mass of the above-mentioned tantalum oxide powder, silicon carbide powder and aluminum powder, and the aluminum powder plus tantalum oxide powder accounts for the above-mentioned tantalum oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 95%, the mass ratio between the tantalum oxide powder and the aluminum powder is 60:40, and then evenly mixed into the binder, the amount of the binder is 100%, and the weight ratio is the above composite powder. : Binder=100: 0.1, which is formulated into tantalum oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为Inconel 718镍基高温合金，预处理方式采用喷砂处理，随后在喷砂处理后的镍基高温合金基体材料表面喷涂厚度为50微米的NiAl粘结底层；The base material is Inconel 718 nickel-based superalloy, and the pretreatment method is sandblasting, and then a NiAl bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the nickel-based superalloy base material after sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.5m3/h，电弧功率为33KW，喷枪距离为110mm，将上述第一步中配制出的用于热喷涂的氧化钽/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的镍基高温合金基体材料表面，从而形成多元陶瓷复合涂层。制备出的多元陶瓷复合涂层厚度达到200微米，涂层致密度高，涂层与基体结合良好。Atmospheric plasma spraying method was adopted, the powder feeding air flow was 0.5m 3 /h, the arc power was 33KW, and the spray gun distance was 110mm. The surface of the nickel-based superalloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating. The thickness of the prepared multi-component ceramic composite coating reaches 200 microns, the coating density is high, and the coating is well combined with the substrate.
实施例17Example 17
第一步，制备用于热喷涂的氧化钽/碳化硅/铝复合粉：The first step is to prepare tantalum oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化钽粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化钽粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为20％，铝粉加氧化钽粉占上述氧化钽粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为80％，氧化钽粉和铝粉之间的质量比例为75∶25，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶1，由此配制成用于热喷涂的氧化钽/碳化硅/铝复合粉；The tantalum oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, silicon carbide powder accounts for 20% of the total mass of the above-mentioned tantalum oxide powder, silicon carbide powder and aluminum powder, and aluminum powder plus tantalum oxide powder accounts for the above-mentioned tantalum oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 80%, the mass ratio between the tantalum oxide powder and the aluminum powder is 75:25, and then evenly mixed into the binder, the amount of the binder is 100%, and the weight ratio is the above composite powder. : Binder=100:1, which is formulated into tantalum oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结层；The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding layer with a thickness of 50 microns is sprayed on the surface of the sandblasted titanium alloy base material;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.5m3/h，电弧功率为38KW，喷枪距离为120mm，将上述第一步中配制出的用于热喷涂的氧化钽/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的钛合金基体材料表面，从而形成多元陶瓷复合涂层。制备出的多元陶瓷复合涂层厚度达到200微米，涂层致密度高，涂层与基体结合良好。Atmospheric plasma spraying method is adopted, the powder feeding air flow is 0.5m 3 /h, the arc power is 38KW, and the distance of the spray gun is 120mm. The surface of the titanium alloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating. The thickness of the prepared multi-component ceramic composite coating reaches 200 microns, the coating density is high, and the coating is well combined with the substrate.
实施例18Example 18
第一步，制备用于热喷涂的氧化钽/碳化硅/铝复合粉：The first step is to prepare tantalum oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化钽粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述氧化钽粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为30％，铝粉加氧化钽粉占上述氧化钽粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为70％，氧化钽粉和铝粉之间的质量比例为90∶10，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶2，由此配制成用于热喷涂的氧化钽/碳化硅/铝复合粉；The tantalum oxide powder with a particle size range of 0.001 microns to 10 microns, silicon carbide powder with a particle size range of 0.001 microns to 10 microns, and aluminum powders with a particle size range of 0.1 microns to 10 microns are uniformly mixed into composite powder. Among them, silicon carbide powder accounts for 30% of the total mass of the above-mentioned tantalum oxide powder, silicon carbide powder and aluminum powder, and aluminum powder plus tantalum oxide powder accounts for the above-mentioned tantalum oxide powder, silicon carbide powder and aluminum powder. The mass percentage of the total mass of the three raw material powders is 70%, the mass ratio between the tantalum oxide powder and the aluminum powder is 90:10, and then evenly mixed into the binder, the amount of the binder is 100%, and the weight ratio is the above composite powder. : Binder = 100: 2, which is formulated into tantalum oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为石墨，预处理方式采用喷砂处理；The base material is graphite, and the pretreatment method is sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用等离子喷涂方法，送粉气流量为0.5m3/h，电弧功率为40KW，喷枪距离为120mm，将上述第一步中配制出的用于热喷涂的氧化钽/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的石墨基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Using the plasma spraying method, the powder feeding air flow rate is 0.5m 3 /h, the arc power is 40KW, and the distance of the spray gun is 120mm. The surface of the graphite base material pretreated in the second step above forms a multi-component ceramic composite coating with a thickness of 200 microns.
实施例19Example 19
第一步，制备用于热喷涂的氧化物/碳化硅/铝复合粉：The first step is to prepare oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化物粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述所有原料粉总质量的质量百分比为5％，铝粉加氧化物粉占上述所有原料粉总质量的质量百分比为95％，氧化物粉和铝粉之间的质量比例为60∶40，其中氧化物包括氧化铌、氧化钛、氧化铬、氧化锆四种氧化物粉各占25％，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶0.1，由此配制成用于热喷涂的氧化物/碳化硅/铝复合粉；The oxide powder with a particle size range of 0.001 μm to 10 μm, silicon carbide powder with a particle size range of 0.001 μm to 10 μm and aluminum powder with a particle size range of 0.1 μm to 10 μm are uniformly mixed into composite powder, Among them, the mass percentage of silicon carbide powder in the total mass of all the above-mentioned raw material powders is 5%, the mass percentage of aluminum powder plus oxide powder in the total mass of all the above-mentioned raw material powders is 95%, and the mass ratio between oxide powder and aluminum powder is 95%. It is 60:40, wherein the oxides include niobium oxide, titanium oxide, chromium oxide, and zirconium oxide four oxide powders each accounting for 25%, and then evenly mixed into the binder, the amount of the binder is, the weight ratio is the above compound. Powder: binder = 100: 0.1, which is formulated into oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为镍基高温合金，预处理方式采用喷砂处理，随后在喷砂处理后的镍基高温合金基体材料表面喷涂厚度为50微米的NiAl粘结底层；The base material is a nickel-based superalloy, and the pretreatment method is sandblasting, and then a NiAl bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the nickel-based superalloy base material after sandblasting;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.3m3/h，电弧功率为30KW，喷枪距离为80mm，将上述第一步中配制出的用于热喷涂的氧化物/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的镍基高温合金基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Atmospheric plasma spraying method was adopted, the powder feeding air flow was 0.3m 3 /h, the arc power was 30KW, and the spray gun distance was 80mm. The surface of the nickel-based superalloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating with a thickness of 200 microns.
实施例20Example 20
第一步，制备用于热喷涂的氧化物/碳化硅/铝复合粉：The first step is to prepare oxide/silicon carbide/aluminum composite powder for thermal spraying:
将粒度范围在0.001微米～10微米之间的氧化物粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述所有原料粉总质量的质量百分比为13％，铝粉加氧化物粉占上述所有原料粉总质量的质量百分比为87％，氧化物粉和铝粉之间的质量比例为75∶25，其中氧化物包括氧化铌、氧化钛、氧化铬、氧化锆四种氧化物粉各占25％，再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶1，由此配制成用于热喷涂的氧化物/碳化硅/铝复合粉；The oxide powder with a particle size range of 0.001 μm to 10 μm, silicon carbide powder with a particle size range of 0.001 μm to 10 μm and aluminum powder with a particle size range of 0.1 μm to 10 μm are uniformly mixed into composite powder, Among them, the mass percentage of silicon carbide powder in the total mass of all the above-mentioned raw material powders is 13%, the mass percentage of aluminum powder plus oxide powder in the total mass of all the above-mentioned raw material powders is 87%, and the mass ratio between oxide powder and aluminum powder is 87%. It is 75:25, wherein the oxides include niobium oxide, titanium oxide, chromium oxide, and zirconium oxide four oxide powders each accounting for 25%, and then evenly mixed into a binder, the binder dosage is, the weight ratio is the above compound. powder:binder=100:1, which is formulated into oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料预处理：The second step, the base material pretreatment:
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结层；The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding layer with a thickness of 50 microns is sprayed on the surface of the sandblasted titanium alloy base material;
第三步，多元陶瓷复合涂层的制备：The third step, the preparation of multi-component ceramic composite coating:
采用大气等离子喷涂方法，送粉气流量为0.6m3/h，电弧功率为40KW，喷枪距离为120mm，将上述第一步中配制出的用于热喷涂的氧化物/碳化硅/铝复合粉喷涂在上述第二步中经过预处理的钛合金基体材料表面，从而形成厚度为200微米的多元陶瓷复合涂层。Using the atmospheric plasma spraying method, the powder feeding air flow rate is 0.6m 3 /h, the arc power is 40KW, and the spray gun distance is 120mm. The oxide/silicon carbide/aluminum composite powder for thermal spraying prepared in the first step above The surface of the titanium alloy base material pretreated in the second step above is sprayed to form a multi-component ceramic composite coating with a thickness of 200 microns.
实施例21Example 21
第一步，制备用于热喷涂的多元氧化物/碳化硅/铝复合粉：将粒度范围在0.001微米～10微米之间的多元氧化物粉、粒度范围在0.001微米～10微米之间的碳化硅粉和粒度范围在0.1微米～10微米之间的铝粉均匀混合成复合粉，其中，碳化硅粉占上述多元氧化物粉、碳化物粉和铝粉这三种原料粉总质量的质量百分比为15％，铝粉加多元氧化物粉占上述多元氧化物粉、碳化硅粉和铝粉这三种原料粉总质量的质量百分比为85％，多元氧化物粉和铝粉之间的质量比例为68∶32，氧化物粉ZrO2、TiO2、Nb2O5和V2O5占多元氧化物粉总的质量比例是25:25:25:25；再均匀混合入粘结剂，该粘结剂用量是，重量比为上述复合粉∶粘结剂＝100∶0.1，由此配制成用于热喷涂的多元氧化物/碳化硅/铝复合粉；The first step is to prepare the multi-component oxide/silicon carbide/aluminum composite powder for thermal spraying: carbonize the multi-component oxide powder with a particle size range of 0.001 μm to 10 μm and a particle size range of 0.001 μm to 10 μm. Silicon powder and aluminum powder with a particle size range of 0.1 micrometers to 10 micrometers are uniformly mixed into composite powder, wherein silicon carbide powder accounts for the mass percentage of the total mass of the above-mentioned three kinds of raw material powders: multi-element oxide powder, carbide powder and aluminum powder. It is 15%, the mass percentage of aluminum powder and multi-component oxide powder in the total mass of the above-mentioned multi-component oxide powder, silicon carbide powder and aluminum powder is 85%, and the mass ratio between multi-component oxide powder and aluminum powder is 85%. It is 68:32, and the mass ratio of oxide powder ZrO 2 , TiO 2 , Nb 2 O 5 and V 2 O 5 to the total multi-component oxide powder is 25:25:25:25; The amount of the binder is such that the weight ratio is the above-mentioned composite powder: the binder=100:0.1, thereby preparing the multi-component oxide/silicon carbide/aluminum composite powder for thermal spraying;
第二步，基体材料表面预处理：The second step, the surface pretreatment of the base material:
基体材料为1Cr18Ni9Ti钢，预处理方式采用喷砂处理，随后在喷砂处理后的1Cr18Ni9Ti钢基体材料表面喷涂厚度为50微米的NiCrAlY粘结底层；The base material is 1Cr18Ni9Ti steel, and the pretreatment method is sandblasting, and then a NiCrAlY bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the sandblasted 1Cr18Ni9Ti steel base material;
第三步，高熵陶瓷-氧化铝复合涂层的制备：The third step, the preparation of high-entropy ceramic-alumina composite coating:
采用热喷涂的方法，将上述第一步中制备出的用于热喷涂的多元复合粉喷涂在上述第二步中经过预处理的1Cr18Ni9Ti钢基体材料表面，从而原位合成厚度为300微米的多元陶瓷复合涂层。Using the method of thermal spraying, the multi-component composite powder for thermal spraying prepared in the above-mentioned first step was sprayed on the surface of the 1Cr18Ni9Ti steel base material pretreated in the above-mentioned second step, so that the multi-component composite powder with a thickness of 300 microns was synthesized in situ. Ceramic composite coating.
上述多元陶瓷复合涂层的制备方法，所述采用热喷涂的方法的工艺参数是：送粉气流量为0.5m3/h，电弧功率为35kW，喷枪距离为110mm。For the preparation method of the multi-component ceramic composite coating, the process parameters of the thermal spraying method are: the flow rate of the powder feeding air is 0.5m 3 /h, the arc power is 35kW, and the distance of the spray gun is 110mm.
上述实施例中，所涉及的原料均从商购获得，所述的喷砂处理工艺、砂纸打磨工艺和喷涂粘结层的工艺均是本领域现有的熟知的工艺。In the above embodiments, the raw materials involved are obtained from commercial sources, and the sandblasting process, the sandpaper polishing process and the process of spraying the adhesive layer are all well-known processes in the art.
将本发明制备的多元陶瓷复合涂层与相同工艺制备的硼化物、碳化物涂层的抗氧化性和抗烧蚀性相比较，热喷涂碳化锆粉、硼化锆粉、硼化锆-碳化锆复合粉、碳化钛粉、锆/碳化硼复合粉和氧化锆/碳化硼/铝复合粉所得涂层的抗氧化性(1000℃，24h，质量增重率，％)分别为58、56、47、65、38和36，而本发明实施例4涂层(碳化钛-硅化钛-氧化铝复合涂层)、实施例8涂层(碳化铬-硅化铬-氧化铝复合涂层)和实施例11涂层(碳化铌-硅化铌-氧化铝复合涂层)的抗氧化性分别为30、25和31；热喷涂碳化锆粉、硼化锆粉、硼化锆-碳化锆复合粉、碳化钛粉、锆/碳化硼复合粉和氧化锆/碳化硼/铝复合粉所得涂层的抗烧蚀性(热通量4.02MW/m2，40s质量烧蚀率，％)分别为8.16、7.81、6.33、10.15、4.99和4.74，而本发明实施例4涂层(碳化钛-硅化钛-氧化铝复合涂层)、实施例8涂层(碳化铬-硅化铬-氧化铝复合涂层)和实施例11涂层(碳化铌-硅化铌-氧化铝复合涂层)的抗烧蚀性分别为3.59、3.47和3.62。可以看出，采用本发明方法制备出的多元陶瓷复合涂层比相应的硼化物、碳化物涂层具有更优异的性能(包括抗氧化性和抗烧蚀性)。Comparing the oxidation resistance and ablation resistance of the multi-component ceramic composite coating prepared by the present invention with the boride and carbide coatings prepared by the same process, thermal spraying of zirconium carbide powder, zirconium boride powder, zirconium boride-carbide The oxidation resistance (1000℃, 24h, mass weight gain rate, %) of the coatings obtained by zirconium composite powder, titanium carbide powder, zirconium/boron carbide composite powder and zirconia/boron carbide/aluminum composite powder were 58, 56, 47, 65, 38, and 36, while Example 4 coatings of the present invention (titanium carbide-titanium silicide-alumina composite coating), Example 8 coatings (chromium carbide-chromium silicide-alumina composite coating) and implementation The oxidation resistance of the coating of Example 11 (niobium carbide-niobium silicide-alumina composite coating) is 30, 25 and 31 respectively; thermal spraying of zirconium carbide powder, zirconium boride powder, zirconium boride-zirconium carbide composite powder, The ablation resistance of the coatings obtained by titanium powder, zirconium/boron carbide composite powder and zirconia/boron carbide/aluminum composite powder (heat flux 4.02MW/m 2 , 40s mass ablation rate, %) were 8.16 and 7.81, respectively , 6.33, 10.15, 4.99 and 4.74, while the coating of Example 4 of the present invention (titanium carbide-titanium silicide-alumina composite coating), the coating of Example 8 (chromium carbide-chromium silicide-alumina composite coating) and The ablation resistance of the coating of Example 11 (niobium carbide-niobium silicide-alumina composite coating) was 3.59, 3.47 and 3.62, respectively. It can be seen that the multi-component ceramic composite coating prepared by the method of the present invention has more excellent properties (including oxidation resistance and ablation resistance) than the corresponding boride and carbide coatings.
对比例1Comparative Example 1
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的TC4钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结底层；将碳化锆粉喷涂在上述经过预处理的TC4钛合金基体材料表面，热喷涂工艺参数是：送粉气流量为0.3m3/h，电弧功率为35KW，喷枪距离为100mm，送粉气为氩气；从而合成厚度为300微米的碳化锆涂层。The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the sandblasted TC4 titanium alloy base material; the zirconium carbide powder is sprayed on the above-mentioned pretreated On the surface of the TC4 titanium alloy base material, the thermal spraying process parameters are: the flow rate of the powder feeding gas is 0.3m 3 /h, the arc power is 35KW, the distance of the spray gun is 100mm, and the powder feeding gas is argon gas; thus the zirconium carbide with a thickness of 300 microns is synthesized coating.
对比例2Comparative Example 2
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的TC4钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结底层；将硼化锆粉喷涂在上述经过预处理的TC4钛合金基体材料表面，热喷涂工艺参数是：送粉气流量为0.3m3/h，电弧功率为35KW，喷枪距离为100mm，送粉气为氩气；从而合成厚度为300微米的硼化锆涂层。The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the sandblasted TC4 titanium alloy base material; the zirconium boride powder is sprayed on the pretreated surface. On the surface of the TC4 titanium alloy base material, the thermal spraying process parameters are: the powder feeding gas flow rate is 0.3m 3 /h, the arc power is 35KW, the spray gun distance is 100mm, and the powder feeding gas is argon gas; thus, boron with a thickness of 300 microns is synthesized. Zirconium coating.
对比例3Comparative Example 3
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的TC4钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结底层；将硼化锆-碳化锆粉喷涂在上述经过预处理的TC4钛合金基体材料表面，热喷涂工艺参数是：送粉气流量为0.3m3/h，电弧功率为35KW，喷枪距离为100mm，送粉气为氩气；从而合成厚度为300微米的硼化锆-碳化锆涂层。The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the sandblasted TC4 titanium alloy base material; the zirconium boride-zirconium carbide powder is sprayed on the above On the surface of the pretreated TC4 titanium alloy base material, the thermal spraying process parameters are: the flow rate of the powder feeding gas is 0.3m 3 /h, the arc power is 35KW, the distance of the spray gun is 100mm, and the powder feeding gas is argon gas; thus the composite thickness is 300 Micron zirconium boride-zirconium carbide coating.
对比例4Comparative Example 4
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的TC4钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结底层；将碳化钛粉喷涂在上述经过预处理的TC4钛合金基体材料表面，热喷涂工艺参数是：送粉气流量为0.3m3/h，电弧功率为35KW，喷枪距离为100mm，送粉气为氩气；从而合成厚度为300微米的碳化钛涂层。The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the sandblasted TC4 titanium alloy base material; the titanium carbide powder is sprayed on the above-mentioned pretreated On the surface of the TC4 titanium alloy base material, the thermal spraying process parameters are: the flow rate of the powder feeding gas is 0.3m 3 /h, the arc power is 35KW, the distance of the spray gun is 100mm, and the powder feeding gas is argon gas; thus, titanium carbide with a thickness of 300 microns is synthesized coating.
对比例5Comparative Example 5
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的TC4钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结底层；将锆/碳化硼复合粉喷涂在上述经过预处理的TC4钛合金基体材料表面，热喷涂工艺参数是：送粉气流量为0.3m3/h，电弧功率为35KW，喷枪距离为100mm，送粉气为氩气；从而合成厚度为300微米的硼化锆-碳化锆复合涂层。The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the sandblasted TC4 titanium alloy base material; On the surface of the pretreated TC4 titanium alloy base material, the thermal spraying process parameters are: the flow rate of the powder feeding gas is 0.3m 3 /h, the arc power is 35KW, the distance of the spray gun is 100mm, and the powder feeding gas is argon gas; thus the composite thickness is 300 microns zirconium boride-zirconium carbide composite coating.
对比例6Comparative Example 6
基体材料为TC4钛合金，预处理方式采用喷砂处理，随后在喷砂处理后的TC4钛合金基体材料表面喷涂厚度为50微米的NiCrAlY粘结底层；将氧化锆/碳化硼/铝复合粉喷涂在上述经过预处理的TC4钛合金基体材料表面，热喷涂工艺参数是：送粉气流量为0.3m3/h，电弧功率为35KW，喷枪距离为100mm，送粉气为氩气；从而合成厚度为300微米的硼化锆-碳化锆-氧化铝复合涂层。The base material is TC4 titanium alloy, and the pretreatment method is sandblasting, and then a NiCrAlY bonding bottom layer with a thickness of 50 microns is sprayed on the surface of the sandblasted TC4 titanium alloy base material; the zirconia/boron carbide/aluminum composite powder is sprayed On the surface of the above-mentioned pretreated TC4 titanium alloy base material, the thermal spraying process parameters are: the flow rate of the powder feeding gas is 0.3m 3 /h, the arc power is 35KW, the distance of the spray gun is 100mm, and the powder feeding gas is argon gas; thus the composite thickness is It is a 300-micron zirconium boride-zirconium carbide-alumina composite coating.
本发明未尽事宜为公知技术。Matters not addressed in the present invention are known in the art.
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