CN113463063A - Preparation method of refractory metal material - Google Patents
Preparation method of refractory metal material Download PDFInfo
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- CN113463063A CN113463063A CN202110652785.0A CN202110652785A CN113463063A CN 113463063 A CN113463063 A CN 113463063A CN 202110652785 A CN202110652785 A CN 202110652785A CN 113463063 A CN113463063 A CN 113463063A
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- Prior art keywords
- gas
- reaction
- reaction chamber
- vapor deposition
- argon
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- 239000000463 material Substances 0.000 title claims abstract description 291
- 239000003870 refractory metal Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 596
- 238000000576 coating method Methods 0.000 claims abstract description 244
- 239000011248 coating agent Substances 0.000 claims abstract description 238
- 229910052751 metal Inorganic materials 0.000 claims abstract description 211
- 239000002184 metal Substances 0.000 claims abstract description 211
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 190
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 179
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 178
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 79
- 150000005309 metal halides Chemical class 0.000 claims abstract description 79
- 239000002131 composite material Substances 0.000 claims abstract description 58
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 836
- 238000006243 chemical reaction Methods 0.000 claims description 785
- 229910052786 argon Inorganic materials 0.000 claims description 418
- 238000000151 deposition Methods 0.000 claims description 264
- 238000007740 vapor deposition Methods 0.000 claims description 211
- 238000000034 method Methods 0.000 claims description 190
- 238000010438 heat treatment Methods 0.000 claims description 157
- 238000002156 mixing Methods 0.000 claims description 151
- 239000012535 impurity Substances 0.000 claims description 103
- 230000008569 process Effects 0.000 claims description 90
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 85
- 238000002309 gasification Methods 0.000 claims description 76
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 75
- 229910052715 tantalum Inorganic materials 0.000 claims description 74
- 229910052750 molybdenum Inorganic materials 0.000 claims description 71
- 239000011733 molybdenum Substances 0.000 claims description 71
- 230000002829 reductive effect Effects 0.000 claims description 71
- 229910052721 tungsten Inorganic materials 0.000 claims description 69
- 239000010937 tungsten Substances 0.000 claims description 69
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 68
- 239000010955 niobium Substances 0.000 claims description 66
- 238000011049 filling Methods 0.000 claims description 65
- 229910052758 niobium Inorganic materials 0.000 claims description 65
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 65
- 229910052702 rhenium Inorganic materials 0.000 claims description 61
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 61
- XZQYTGKSBZGQMO-UHFFFAOYSA-I rhenium pentachloride Chemical compound Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 claims description 51
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 50
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 49
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 45
- 238000001816 cooling Methods 0.000 claims description 44
- 238000005520 cutting process Methods 0.000 claims description 44
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims description 44
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 claims description 35
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 claims description 35
- 239000012153 distilled water Substances 0.000 claims description 33
- UKUWGTWCIFEMQK-UHFFFAOYSA-I pentafluororhenium Chemical compound F[Re](F)(F)(F)F UKUWGTWCIFEMQK-UHFFFAOYSA-I 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000004140 cleaning Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 32
- NBJFDNVXVFBQDX-UHFFFAOYSA-I molybdenum pentafluoride Chemical compound F[Mo](F)(F)(F)F NBJFDNVXVFBQDX-UHFFFAOYSA-I 0.000 claims description 32
- 239000012159 carrier gas Substances 0.000 claims description 30
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 30
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical group F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 claims description 30
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 229910052735 hafnium Inorganic materials 0.000 claims description 26
- 239000007769 metal material Substances 0.000 claims description 20
- QHEDSQMUHIMDOL-UHFFFAOYSA-J hafnium(4+);tetrafluoride Chemical compound F[Hf](F)(F)F QHEDSQMUHIMDOL-UHFFFAOYSA-J 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 230000008016 vaporization Effects 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 59
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 55
- 230000000704 physical effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 description 262
- 239000010410 layer Substances 0.000 description 106
- 238000012360 testing method Methods 0.000 description 70
- 239000012495 reaction gas Substances 0.000 description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 55
- 229910052799 carbon Inorganic materials 0.000 description 44
- 229910001220 stainless steel Inorganic materials 0.000 description 44
- 239000010935 stainless steel Substances 0.000 description 44
- 239000000853 adhesive Substances 0.000 description 38
- 230000001070 adhesive effect Effects 0.000 description 38
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 38
- 229910010271 silicon carbide Inorganic materials 0.000 description 38
- 230000000694 effects Effects 0.000 description 35
- 229920000049 Carbon (fiber) Polymers 0.000 description 33
- 239000004917 carbon fiber Substances 0.000 description 33
- 239000003153 chemical reaction reagent Substances 0.000 description 33
- 230000001276 controlling effect Effects 0.000 description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 33
- 230000008859 change Effects 0.000 description 30
- 238000005336 cracking Methods 0.000 description 29
- 239000000376 reactant Substances 0.000 description 29
- 238000005452 bending Methods 0.000 description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 23
- 239000000758 substrate Substances 0.000 description 21
- 238000001514 detection method Methods 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000011521 glass Substances 0.000 description 16
- 230000007547 defect Effects 0.000 description 15
- 238000006356 dehydrogenation reaction Methods 0.000 description 15
- 239000010408 film Substances 0.000 description 15
- 238000011056 performance test Methods 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 229910052581 Si3N4 Inorganic materials 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 10
- 229910052737 gold Inorganic materials 0.000 description 10
- 239000010931 gold Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000010587 phase diagram Methods 0.000 description 9
- 238000005234 chemical deposition Methods 0.000 description 8
- 229910004537 TaCl5 Inorganic materials 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 6
- -1 hydrogen Chemical class 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000003754 machining Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 229910019804 NbCl5 Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 229910003865 HfCl4 Inorganic materials 0.000 description 3
- 229910015221 MoCl5 Inorganic materials 0.000 description 3
- 229910003091 WCl6 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910004504 HfF4 Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910015227 MoCl3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 description 2
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 238000000918 plasma mass spectrometry Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 229910015253 MoF5 Inorganic materials 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 229910019787 NbF5 Inorganic materials 0.000 description 1
- 229910019594 ReF5 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 229910004546 TaF5 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AUTWRGZQAIMMQA-UHFFFAOYSA-N [Hf].[Nb] Chemical compound [Hf].[Nb] AUTWRGZQAIMMQA-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZSSVQAGPXAAOPV-UHFFFAOYSA-K molybdenum trichloride Chemical compound Cl[Mo](Cl)Cl ZSSVQAGPXAAOPV-UHFFFAOYSA-K 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- XGZGDYQRJKMWNM-UHFFFAOYSA-N tantalum tungsten Chemical compound [Ta][W][Ta] XGZGDYQRJKMWNM-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
- C23C16/14—Deposition of only one other metal element
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
-
- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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Abstract
The invention relates to a preparation method of a refractory metal material, which is characterized in that a refractory metal halide and a reducing gas are subjected to chemical vapor deposition to form a high-quality metal coating or composite material. The invention adopts carbon monoxide as reducing gas, solves the problems of hydrogen brittleness, poor binding force and the like generated in the preparation process of refractory metals, and the prepared product material has better physical properties and realizes industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of metal materials, and particularly relates to a preparation method for preparing a refractory metal material by a chemical vapor deposition process.
Background
The refractory metal with high melting point generally refers to metals and alloys with melting point above 2000 ℃, such as tantalum, tungsten, rhenium, niobium, molybdenum, hafnium, and alloys and metal compounds thereof, or composite materials composed of the above elementary metals, alloys and metal compounds. The refractory metal has good heat conductivity and electrical conductivity, low expansion coefficient, excellent high-temperature mechanical property, wear resistance, corrosion resistance and other properties, so that the refractory metal is widely applied to the fields of metallurgy, agriculture, aerospace, electronic chemical industry, semiconductor materials, electronic communication materials, medical implant materials and the like: tungsten and molybdenum are used for alloy steel, heat-resistant alloy and hard alloy of a handle, and tungsten is used as a filament material; niobium, tantalum are used in vacuum technology, radio industry (such as tantalum capacitors) and chemical industry; zirconium and its alloys are used as structural materials of atomic nuclear reactors because of their small thermal neutron capture cross-sections. Rhenium is widely used in various departments of modern industry, and is mainly applied to the fields of aerospace, electronic industry, petrochemical industry, nuclear industry and the like. Is used for manufacturing key parts of aeroengines, artificial satellites and rocket engines, guard plates of nuclear reactors and the like, and is chemically used as a catalyst. 70% of the global rhenium production is used to manufacture high temperature components of aircraft engines. Rhenium is important in military strategies because it can be used in high performance aircraft engines, as well as in rocket and satellite engines. The tantalum and tungsten alloy containing rhenium is considered as the most high temperature resistant performance and becomes an important material in the aspects of space navigation, rockets, missiles and the like. Hafnium has the characteristics of ductility, oxidation resistance, high temperature resistance and the like, is a good alloy material, and is applied to various alloys. For example, a hafnium-niobium alloy containing 10% hafnium can be used as a lunar rocket nozzle, while a tantalum-tungsten alloy containing 2% hafnium can be used as a spacecraft shield material due to its high creep strength.
Table 1 refractory metal physical properties
| Metal | Melting Point (. degree.C.) | Boiling point (. degree.C.) | Density (g/cm)3) |
| Ta tantalum | 2996 | 5425 | 16.65g |
| Tungsten W | 3410±20 | 5927 | 19.35 |
| Rhenium Re | 3180 | 5900 | 21.02 |
| Niobium Nb | 2468 | 4742 | 8.57 |
| Molybdenum Mo | 2620 | 5560 | 10.2 |
| Hafnium Hf | 2227 | 4602 | 13.31 |
The metal has the characteristics of high melting point and high hardness, and is generally difficult to machine and form by adopting casting and forging processes. Common fabrication methods include powder metallurgy, Physical Vapor Deposition (PVD) and Chemical Vapor Deposition (CVD). The powder metallurgy is limited by the size and the shape of the product, so that thin-wall products, products with complex shapes and large sizes cannot be prepared, and the structure purity obtained by the powder metallurgy is low, the crystal structure is uncontrollable and not compact. The physical vapor deposition method has low deposition efficiency, is generally only suitable for preparing films with simple shapes and ultrathin film thicknesses, and the prepared coating has high brittleness, poor bonding force between the film and a substrate, and easy falling and cracking. The chemical vapor deposition process has high deposition efficiency, and is suitable for parts with complicated shape. Therefore, the chemical vapor deposition process is widely used for preparing various metals or thin film materials of oxides, nitrides, carbides and the like of the metals, and has great significance and wide application prospect.
Chemical vapor deposition for preparing refractory metals generally uses metal halides as reactants, generally uses hydrogen as reducing gas, and involves chemical reaction systems of metal halides, hydrogen and inert gas, for example, tantalum and its alloys are deposited, the chemical reaction formula is as follows:
gasification reaction
TaCl5(s)→TaCl5(g)
Reduction reaction
TaCl5(g)+2.5H2(g)→Ta(s)+HCl(g)
Kinetic model of chemical vapor deposition tantalum: at a temperature above 1000 ℃ TaCl5Starting the conversion to TaCl under the action of hydrogen4，TaCl4Converted to elemental Ta, but not at high conversion, and the specific process can be expressed as:
TaCl5+H2→HCl+TaCl4+Ta
TaCl4+H2→HCl+Ta
TaCl4→Ta+Cl
there are also researchers believing that TaCl is present5The metal tantalum atoms are reduced step by step and finally reduced into the metal tantalum atoms, and the process can be expressed as follows: TaCl5→TaCl4→TaCl3→TaCl2→ Ta. The temperature at which further reduction of the intermediate tantalum chloride by hydrogen occurs varies depending on the hydrogen content of the reaction gas. Currently, the metallic tantalum successfully commercialized is the porous tantalum patented by the U.S. ZIMMER corporation, which deposits metallic tantalum to a thickness of about 120 μm on reticulated vitreous carbon by CVD.
Hydrogen is used as reducing gas, and hydrogen embrittlement (also called hydrogen induced cracking) of metal materials is easy to occur in the reaction process, particularly in a high-temperature environment. Hydrogen embrittlement is a hydrogen atom dissolved in metal and polymerizes into hydrogen molecules, causing stress concentration, exceeding the strength limit of the metal,fine cracks are formed inside the metal. Trace hydrogen (10-6Magnitude) can cause the material to be embrittled or even cracked under the action of internal residual or external stress, thereby reducing the mechanical property of the metal material and limiting the application range of the chemical vapor deposition process for preparing the metal material.
Dehydrogenation treatments are often employed to reduce the risk of hydrogen embrittlement. The technical solutions of dehydrogenation treatment known to those skilled in the art include dehydrogenation by means of heating, dehydrogenation treatment by adding a reducing metal in the process, and prevention of diffusion of hydrogen atoms in the prepared metal material by adding a metal to form a second phase. However, these technical means cannot fundamentally solve the problem of hydrogen embrittlement. Therefore, a chemical vapor deposition reaction system is urgently needed to solve the problem of material cracking caused by hydrogen.
In addition, the metal deposition layer prepared in the prior art has insufficient bonding force with a substrate, poor stability on a microstructure, possible tissue defects, nonuniform tissues and difficulty in preparing a metal composite material with an extremely thick deposition layer, and the deposition layer is easy to fall off.
In view of the above, the present inventors provide a novel method for preparing refractory metal by using a chemical vapor deposition reaction system, aiming at the problems of hydrogen embrittlement, poor bonding between a substrate and a deposition layer, and the like, which are easily caused by the conventional chemical vapor deposition method.
Disclosure of Invention
Aiming at the hydrogen embrittlement phenomenon which is easy to occur in the process of preparing metal by CVD in the prior art and the insufficient binding force between a deposition layer and a substrate or between the deposition layer and the deposition layer, the invention provides a method for preparing a refractory metal material by a chemical vapor deposition process, which aims to solve the technical problems and realize the industrial production of products.
In order to achieve the aim, the solution of the invention is to take refractory metal halide as a reaction source, carry out reduction reaction with carbon monoxide in chemical vapor deposition equipment after gasification, and carry out deposition on the surface of a blank to prepare the required refractory metal material.
Further, before gasifying the refractory metal halide, the method also comprises the following steps:
(1) removing residual non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing a blank to be deposited into a reaction chamber of equipment;
(3) removing non-reaction required gas and impurities which enter the chemical vapor deposition equipment in the blank placing process and are not required by reaction;
(4) checking the tightness of the equipment, and setting the vacuum degree of the equipment and the reaction temperature of the reaction chamber.
Further, the refractory metal comprises any elementary metal of tantalum, tungsten, rhenium, niobium, molybdenum and hafnium or an alloy formed by combining the elementary metals with each other.
Further, the refractory metal halide comprises one or more of tantalum pentachloride, tantalum pentafluoride, tungsten hexachloride, tungsten hexafluoride, rhenium pentachloride, rhenium pentafluoride, niobium pentachloride, molybdenum pentafluoride, molybdenum pentachloride, hafnium tetrafluoride, and hafnium tetrachloride.
Further, the metal material comprises an alloy, a coating and a composite material.
Preferably, the vacuum degree in the step (4) is 6000-22000 Pa; the reaction temperature is 770-1300 ℃.
Further, the reaction chamber is an alumina reaction chamber.
Further, the refractory metal halide is gasified by a carrier gas and then introduced into the reaction chamber, wherein the carrier gas is argon.
Preferably, the refractory metal halide is tantalum pentachloride and tantalum pentafluoride, and the reaction temperature is 820-1300 ℃.
Preferably, the refractory metal halides are tungsten hexachloride and tungsten hexafluoride, and the reaction temperature is 850-.
Preferably, the refractory metal halides are rhenium pentachloride and rhenium pentafluoride, and the reaction temperature is 820-1300 ℃.
Preferably, the refractory metal halide is niobium pentafluoride and niobium pentachloride, and the reaction temperature is 800-1200 ℃.
Preferably, the refractory metal halide is molybdenum pentafluoride and molybdenum pentachloride, and the reaction temperature is 770-1200 ℃.
Preferably, the refractory metal halide is hafnium tetrafluoride or hafnium tetrachloride, and the reaction temperature is 800-1300 ℃.
Preferably, the refractory metal halide is tantalum pentachloride and tantalum pentafluoride, and the equipment vacuum degree is 12000-15000 Pa.
Preferably, the refractory metal halide is tungsten hexachloride and tungsten hexafluoride, and the vacuum degree of the equipment is controlled at 18000-22000 Pa.
Preferably, the refractory metal halides are rhenium pentachloride and rhenium pentafluoride, and the vacuum degree of the equipment is controlled to be 15000-20000 Pa.
Preferably, the refractory metal halide is niobium pentachloride or niobium pentafluoride, and the vacuum degree of the equipment is controlled to be 12000-15000 Pa.
Preferably, the refractory metal halide is molybdenum pentachloride and molybdenum pentafluoride, and the vacuum degree of the equipment is controlled at 6000-14000 Pa.
Preferably, the refractory metal halide is hafnium tetrafluoride or hafnium tetrachloride, and the vacuum degree of the equipment is controlled to be 11000 and 15500 Pa.
Preferably, the chemical vapor deposition equipment comprises a gasification chamber, wherein the gasification of the refractory metal halide is carried out in the gasification chamber, and the temperature of the gasification chamber is set to be 260-700 ℃.
Preferably, the refractory metal halide is tantalum pentachloride and tantalum pentafluoride, and the temperature of the gasification chamber is set to 300-600 ℃.
Preferably, the refractory metal halide is tungsten hexachloride and tungsten hexafluoride, and the temperature of the gasification chamber is set to 400-700 ℃.
Preferably, the refractory metal halides are rhenium pentachloride and rhenium pentafluoride, and the temperature of the gasification chamber is set to 260-520 ℃.
Preferably, the refractory metal halide is niobium pentachloride or niobium pentafluoride, and the temperature of the gasification chamber is set to be 300-500 ℃.
Preferably, the refractory metal halides are molybdenum pentachloride and molybdenum pentafluoride, and the temperature of the gasification chamber is set to be 350-550 ℃.
Preferably, the refractory metal halide is hafnium tetrafluoride or hafnium tetrachloride, and the temperature of the gasification chamber is set to 350-.
Preferably, the volume ratio of the refractory metal halide to the carbon monoxide is 1: 1-4.
Preferably, the volume ratio of one of tantalum pentachloride, tantalum pentafluoride, tungsten hexachloride, tungsten hexafluoride, niobium pentachloride, niobium pentafluoride, molybdenum pentachloride, molybdenum pentafluoride, hafnium tetrafluoride and hafnium tetrachloride is 1: 2.
Preferably, the volume ratio of rhenium pentachloride, rhenium pentafluoride gas and carbon monoxide is 1: 4.
Preferably, the volume ratio of the refractory metal halide to the carrier gas is 1: 1-5.
Preferably, the refractory metal halide has a gas flow rate of 1 to 9 cubic meters per hour, the carrier gas has a gas flow rate of 1 to 30 cubic meters per hour, and the carbon monoxide has a gas flow rate of 1 to 24 cubic meters per hour.
Further, the removal of the non-reactive desired gases and impurities remaining in the vapor deposition apparatus in the steps (1) and (3) employs the steps of: firstly, vacuumizing the vapor deposition equipment to 0-1000Pa vacuum state, keeping the vacuum state of 0-1000Pa for 5-20 minutes, checking that the vapor deposition equipment is sealed completely, then introducing carrier gas to be in a normal pressure state, filling the reaction chamber and all vacuum pipelines of the vapor deposition equipment with the carrier gas, opening an air valve to empty, continuing introducing the carrier gas for 5-20 minutes, and closing an exhaust valve.
Further, in the step (2), the blank body to be deposited is pretreated before being placed into a reaction chamber of the equipment, and the pretreatment comprises the following steps: after the deposited blank is cleaned by distilled water and decontaminated, the blank is dried for 3 to 15 hours at the temperature of between 105 and 200 ℃ until the blank is completely dried.
Further, the step (4) of checking the tightness of the device adopts the following steps: the sealing of the vapor deposition equipment is checked to be perfect by vacuumizing the vapor deposition equipment to a vacuum state of 0-1000Pa and maintaining the vacuum state of 0-1000Pa for 5-20 minutes.
The invention also provides a preparation method of the refractory metal tantalum material, which comprises the following steps:
(1) removing residual non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing the blank to be deposited into a reaction chamber of equipment after pretreatment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 820-1180 ℃;
(5) putting tantalum pentachloride or tantalum pentafluoride into a gasification chamber, heating to gasify the tantalum pentachloride or the tantalum pentafluoride, introducing gasified tantalum pentachloride or tantalum pentafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the tantalum pentachloride or tantalum pentafluoride gas, the carbon monoxide gas and the argon gas is 1: 2: 2, after fully mixing in a gas mixing tank, introducing the mixture into a reaction chamber to perform chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
The invention also provides a preparation method of the refractory metal tungsten material, which comprises the following steps:
(1) removing residual non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing the blank to be deposited into a reaction chamber of equipment after pretreatment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 850-1200 ℃;
(5) putting tungsten hexachloride or tungsten hexafluoride into a gasification chamber, heating and gasifying the tungsten hexachloride or tungsten hexafluoride gas, introducing the gasified tungsten hexachloride or tungsten hexafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the tungsten hexachloride or tungsten hexafluoride gas, the carbon monoxide gas and the argon gas is 1: 2: 3, after fully mixing in a gas mixing tank, introducing the mixture into a reaction chamber to perform chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
The invention also provides a preparation method of the refractory metal rhenium material, which comprises the following steps:
(1) removing residual non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing the blank to be deposited into a reaction chamber of equipment after pretreatment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 820-1200 ℃;
(5) putting rhenium pentachloride or rhenium pentafluoride into a gasification chamber, heating to gasify the rhenium pentachloride or rhenium pentafluoride, introducing gasified rhenium pentachloride or rhenium pentafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the rhenium pentachloride or rhenium pentafluoride, the carbon monoxide and the argon gas is 1: 4: 2, after fully mixing in a gas mixing tank, introducing the mixture into a reaction chamber to perform chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
The invention also provides a preparation method of the refractory metal niobium material, which comprises the following steps:
(1) removing residual non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing the blank to be deposited into a reaction chamber of equipment after pretreatment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 850-1180 ℃;
(5) putting niobium pentachloride or niobium pentafluoride into a gasification chamber, heating to gasify the niobium pentachloride or niobium pentafluoride, introducing the gasified niobium pentachloride or niobium pentafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the niobium pentachloride or niobium pentafluoride, the carbon monoxide gas and the argon gas is 1: 2: 2, fully mixing in a gas mixing tank, introducing into a reaction chamber, and performing chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
The invention also provides a preparation method of the refractory metal molybdenum material, which comprises the following steps:
(1) removing residual non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing the blank to be deposited into a reaction chamber of equipment after pretreatment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 850-1150 ℃;
(5) putting molybdenum pentachloride or molybdenum pentafluoride into a gasification chamber, heating to gasify the molybdenum pentachloride or molybdenum pentafluoride, introducing the gasified molybdenum pentachloride or molybdenum pentafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the molybdenum pentachloride or molybdenum pentafluoride, the carbon monoxide gas and the argon gas is 1: 2: 2, after fully mixing in a gas mixing tank, introducing the mixture into a reaction chamber to perform chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
The invention also provides a preparation method of the refractory metal hafnium material, which comprises the following steps:
(1) removing residual non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing the blank to be deposited into a reaction chamber of equipment after pretreatment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 850-1100 ℃;
(5) putting hafnium tetrafluoride or hafnium tetrachloride into a gasification chamber, heating to gasify the hafnium tetrafluoride or hafnium tetrachloride, introducing the gasified hafnium tetrafluoride or hafnium tetrachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of the hafnium tetrafluoride or hafnium tetrachloride, the carbon monoxide and the argon gas is 1: 2: 2, fully mixing in a gas mixing tank, introducing into a reaction chamber, and performing chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
From the collected literature data, the research on the chemical vapor deposition of reducing metal by hydrogen is relatively extensive, the research on the chemical vapor deposition of reducing refractory metal by carbon monoxide is very little, and the realization of industrial production is not developed at home.
After adopting above-mentioned scheme, the beneficial effect who obtains is:
(1) the invention is more suitable for industrial scale production.
(2) The invention can reduce the deposition temperature, can deposit metal at the temperature lower than 1000 ℃, has higher deposition rate and has practical production value.
(3) The average conversion rate of the metal halide is 42.15 percent, which is higher than that of a metal halide-hydrogen reaction system.
(4) In the invention, in the preparation of the refractory metal material by utilizing the chemical vapor deposition process, carbon monoxide is used as a reducing gas for the reaction gas of vapor deposition, a new reaction system is established, the hydrogen embrittlement phenomenon generated in the chemical deposition reaction process by using hydrogen as the reducing gas is avoided, the compact metal material can be prepared on a blank body by chemical vapor deposition, and the mechanical property of the material is obviously improved.
(5) The chemical deposition reaction of the invention adopts new reactants, optimizes the reaction temperature, the reaction gas flow and the proportional process parameters, is beneficial to stably forming metal deposition layers with consistent microstructures, and improves the binding force between the deposition layers and a matrix, so that the metal material with extremely thick deposition layers can be prepared. For example, the thickness of the tantalum or tungsten deposition layer prepared by the method can reach 10mm, the thickness of the rhenium deposition layer can reach 12mm, which are both higher than the thickness of the metal deposition layer obtained by the existing method, and meanwhile, the bonding force of the deposition layer and the substrate prepared by the method is greatly improved, for example, the tantalum coating can reach 158MPa, the bonding force of the tungsten deposition layer and the substrate reaches 166MPa, and the bonding force of the rhenium deposition layer and the substrate reaches 152MPa, thereby effectively solving the problems that the bonding force between the deposition layer and the substrate prepared by the existing method and between the deposition layer and the deposition layer are insufficient, the metal tantalum composite material with the extremely thick deposition layer is difficult to prepare, the deposition layer is easy to fall off, and the like.
(6) The purity of the metal material prepared by the invention reaches 99.999 percent, the porosity is 0, and the density is the same as the theoretical density of the metal.
(7) The product of the method has less corrosion to equipment, hydrogen is used as reducing gas, and the product contains HF and HCl and has strong corrosion to the equipment.
Drawings
FIG. 1 is a schematic structural diagram of a chemical vapor deposition apparatus system used in the present invention.
FIG. 2 shows example 1 (TaCl)5) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 3 shows example 1 (TaCl)5) The influence of the gas flow and the ratio on the thickness and adhesion of the deposited layer.
FIG. 4 shows example 5 (TaF)5) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 5 is a gold phase diagram (magnification 1000) of the tantalum metal surface of example 1.
FIG. 6 shows example 7 (WCl)6) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 7 shows example 7 (WCl)6) The influence of the gas flow and the ratio on the thickness and adhesion of the deposited layer.
FIG. 8 shows example 11 (WF)6) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 9 is a metallographic photograph (magnified 1000) of the surface of a tungsten metal fault in example 7.
FIG. 10 shows example 13 (Recl)5) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 11 shows example 13 (Recl)5) The influence of the gas flow and the ratio on the thickness and adhesion of the deposited layer.
FIG. 12 shows example 17 (ReF)5) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 13 is a gold phase diagram (magnification 1000) of the surface of a rhenium metal fault in example 13.
FIG. 14 shows example 19 (NbCl)5) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 15 is a drawing showingExample 19 (NbCl)5) The influence of the gas flow and the ratio on the thickness and adhesion of the deposited layer.
FIG. 16 shows example 23 (NbF)5) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 17 is a metallographic image (magnification 2000) of the surface of a fault of niobium metal in example 19.
FIG. 18 shows example 25 (MoCl)5) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 19 shows example 25 (MoCl)5) The influence of the gas flow and the ratio on the thickness and adhesion of the deposited layer.
FIG. 20 shows example 29 (MoF)5) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 21 is the gold phase diagram (magnification 500) of the surface of the molybdenum metal fault in example 25.
FIG. 22 shows example 31 (HfCl)4) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 23 shows example 31 (HfCl)4) The influence of the gas flow and the ratio on the thickness and adhesion of the deposited layer.
FIG. 24 shows example 35 (HfF)4) The effect of reaction temperature on deposition rate and adhesion of the deposited layer.
FIG. 25 is a metallographic image (magnification 2000) of the surface of a hafnium metal layer in example 31.
Detailed Description
The invention discloses a preparation method of a refractory metal material.
Metal halide (MX)n) A convenient source of inorganic material is provided for the deposition of metals, where M represents the metals tantalum, tungsten, rhenium, niobium, molybdenum, hafnium, X represents the halogens fluorine (F), chlorine (Cl), and n is the atomic number. Table 2 shows the physical and chemical properties of each metal halide employed in the present invention.
TABLE 2 physicochemical Properties of the Metal halides for deposition
| Melting Point (. degree.C.) | Boiling point (. degree.C.) | At room temperature (18-22 deg.C) | |
| TaF5 | 97 | 230 | Solid body |
| TaCl5 | 216 | 242 | Solid body |
| WF6 | 2.3 | 17.1 | Gas (es) |
| WCl6 | 275 | 347 | Solid body |
| ReF5 | 48 | 221.3 | Solid body |
| ReCl5 | 220 | 330 | Solid body |
| NbF5 | 73 | 236 | Solid body |
| NbCl5 | 204 | 250 | Solid body |
| MoF5 | 190 | 209 | |
| MoCl | |||
| 5 | 194 | 268 | Solid body |
| HfF4 | 310 | / | Solid body |
| HfCl4 | 320 | 317 (sublimation) | Solid body |
In the prior art, hydrogen is used as reducing gas for preparing a metal coating by chemical vapor deposition, and the method can cause hydrogen embrittlement, namely hydrogen induced cracking, of the film layer. At present, the performance of the film layer is stabilized by adding a dehydrogenation treatment step, so that the risk of hydrogen induced cracking is reduced. Through a large number of experiments, the inventor finds that the problem of hydrogen induced cracking can be fundamentally solved by considering carbon monoxide as reducing gas, the step of dehydrogenation treatment is reduced, and the physical properties of the prepared metal material are better than those of a product prepared by adopting a metal halide-hydrogen reaction system.
Chemical vapor deposition is a complex process involving the thermodynamics of chemical reactions and the kinetics of reactions as well as the effects of heat and mass transfer. On the one hand, the chemical reaction is controlled to occur in the reaction chamber, and on the other hand, the product is formed into crystal nucleus on the surface of the blank and grows up. That is to say, chemical reaction between chemical substances is possible but the reaction process cannot be guaranteed to occur efficiently, the invention continuously adjusts and optimizes process parameters to promote the reaction to proceed towards the direction of depositing metal, and considers the production cost and the industrial efficiency, thereby realizing the industrial scale production of products and further improving the material performance of the products.
A method of making a refractory metal material comprising the steps of:
(1) removing residual non-reaction required gas and impurities in the vapor deposition equipment;
(2) putting the blank to be deposited into a reaction chamber after pretreatment;
(3) removing non-reaction required gas and impurities entering the vapor deposition equipment in the blank body placing process;
(4) after the vapor deposition equipment is checked to be completely sealed, controlling the vacuum degree in the vapor deposition equipment to 6000-plus-one 22000Pa by a vacuum pump, and simultaneously heating the temperature in the reaction chamber to the required temperature within the range of 770-plus-1300 ℃;
(5) the metal halide is put into a gasification chamber for gasification, and then is introduced into a gas mixing tank after gasification, and simultaneously, carrier gas and reducing gas carbon monoxide with a certain volume ratio are introduced into the gas mixing tank. The ratio of the metal halide to the reducing gas is 1:1-4, and the ratio of the metal halide to the carrier gas is 1: 1-5. And after the three gases are fully mixed in the gas mixing tank, introducing the three gases into the reaction chamber to perform chemical vapor deposition reaction on the blank, and setting the reaction duration according to the thickness of the required metal coating or metal material. Preferably, the metal halide gas flow rate is 1 to 9 cubic meters per hour, the carbon monoxide gas flow rate is 1 to 24 cubic meters per hour, and the carrier gas flow rate is 1 to 30 cubic meters per hour.
(6) Cutting off the heating power supply, stopping heating, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing the carrier gas, stopping introducing the carrier gas after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared metal material.
The chemical vapor deposition equipment comprises a gasification chamber and a reaction chamber. As shown in fig. 1, the chemical vapor deposition apparatus 1 has a reaction chamber 11, a deposition workpiece 12 (e.g., a blank) is placed in the reaction chamber 11, and the reaction chamber 11 is provided with two vents, one of which is connected to an air inlet pipe 13 and the other is connected to a vacuum pipe 14. The reaction chamber 11 is further provided with a heating device (not shown) for heating the reaction chamber, and the outer end of the vacuum pipe 14 is connected to a vacuum pump 17. The gas inlet pipe 13 is connected to a gas mixing tank 16, and the gas mixing tank 16 is connected to at least one vent pipe 161, two in this embodiment, for respectively introducing the reducing gas and the inert carrier gas from the vent pipe 161. The gas mixing tank 16 is connected with a gasification chamber 15, the gasification chamber 15 can heat and gasify initial metal halide, and gasified metal halide gas enters the gas mixing tank 16 to be fully mixed with other gas. The flow rate of the reaction gas is regulated by a gas control device 18.
The solid reactant is activated in the gasification chamber by heat energy to be in a gas state, and is conveyed to the reaction chamber to react with carbon monoxide, so that the metal halide in a vapor state is converted into a metal deposition layer. The temperature at which the metal halide gas is gasified needs to be lower than the temperature at which the metal halide gas reacts with the carbon monoxide gas. In addition, the selection of the gasification temperature is not suitable to be too low, one is that if the gasification temperature is too low, condensation is easily caused by temperature reduction in the process of conveying through a pipeline, and the pipeline is blocked; secondly, the gas temperature is too low to affect the temperature of the reaction chamber in the furnace.
The reaction chamber for vapor deposition adopts an alumina reaction chamber. Compared with a common reaction chamber such as a quartz reaction chamber or a stainless reaction chamber, the stainless reaction chamber is corroded due to high corrosivity of reactant and product gas, and cannot be guaranteed to run stably for a long time, and the quartz reaction chamber is easy to damage under the condition of repeated lifting, heating and vibration, and cannot be guaranteed to run stably for a long time. In step 2, the blank to be deposited may be made of metal, carbon, ceramic, glass or fiber preform, semiconductor substrate, or the like. Including, for example, hard protective coatings for aerospace vehicle parts or engines; coatings for jewelry items; surface coatings for medical implant materials; barrier layers for military industry applications and for semiconductor components such as diffusion barrier layers between copper and silicon. Preferred metal blanks include stainless steel, aluminum, beryllium, chromium, cobalt, copper, gallium, gold, iron, lead, manganese, molybdenum, nickel, palladium, platinum, rhenium, rhodium, silver, strontium, tin, titanium, tantalum, zinc, zirconium, and alloys and compounds thereof, such as silicides, carbides, and the like. There is virtually no limitation on the type of blank that can be used in the present process, depending on the type of film being deposited and the intended use, and can be stable over a range of deposition temperatures.
The purpose of steps (1) - (3) is to increase the bonding force between the coating or composite material and the blank, and the pretreatment is carried out before the chemical vapor deposition.
In step (4), the chamber temperature needs to be high to ensure that the M-Cl chemical bond or M-F chemical bond of the metal halide participating in the deposition reaction is completely dissociated (where M represents the metal tantalum, tungsten, rhenium, niobium, molybdenum, hafnium), but the chamber temperature should not be too high, otherwise the chemical deposition reaction proceeds prematurely elsewhere before contacting the blank. Temperature affects the degree of ionization of the reactants. In general, the temperature of the reaction chamber directly controls the thermodynamic and kinetic processes of deposition, and has a major influence on the diffusion of reaction gases, the speed of chemical reaction efficiency, and nucleation and growth.
In addition, vacuum variations also have an effect on the deposition rate of the present invention. The deposition rate is increased along with the increase of the gas pressure of the reaction chamber; however, the degree of vacuum reaches a certain range, and the deposition rate changes slowly. The change of vacuum degree has no obvious change to the composition of the tantalum deposition layer, and has certain influence on the preferential growth.
In the step (5), the carrier gas may be an inert gas that does not chemically react with the reactant, such as argon or neon, or a mixed gas of argon and neon. In addition, metal materials can be deposited without a carrier gas. Controlling the delivery of the metal halide vapor directly into the reaction chamber can be accomplished by heating the solid metal halide within a temperature range, the temperature selection depending on the particular reactants. The temperature is selected to be sufficient to vaporize the reactants to provide a vapor pressure for transporting the metal halide vapor into the reaction chamber. Therefore, a carrier gas is not necessary.
Preferably, after the metal halide gas, the carbon monoxide and the carrier gas are fully mixed in the gas mixing tank, the mixture is introduced into the reaction chamber to perform chemical vapor deposition reaction, and the mixed gas inlet can ensure that the deposition is more uniform without excessive deposition or non-deposition.
The carbon monoxide gas and the metal halide gas are used for preparing the metal material, and compared with the hydrogen gas as the reducing gas, the carbon monoxide gas has the greatest advantage of not generating hydrogen embrittlement. The reaction temperature, vacuum degree, reaction gas flow and proportion in the preparation process have main influence on the proceeding speed of the deposition reaction and the structure and performance of the deposition layer. The ratio of carbon monoxide gas to metal halide gas and carrier gas affects the concentration of the reactants, and too low or too high a concentration of the reactants affects the deposition efficiency. The reaction gas has enough residence time on the surface of the blank to participate in the reaction, and the deposition rate is controlled by the adsorption and desorption processes of the reaction gas and the surface of the blank. When the gas flow is increased, the source substances participating in the reaction in unit time are increased, which is beneficial to the reaction towards the direction of the product, and the deposition rate is increased. However, when the gas flow exceeds a certain range, part of the gas can directly flow through the surface of the blank without participating in the reaction, thereby causing waste. The technological parameters such as the temperature of the reaction chamber, the vacuum degree of the equipment, the flow and proportion of the reaction gas, the gasification temperature of the metal halide, the deposition time and the heat treatment process in the chemical vapor deposition preparation process all influence the material performance of the prepared product, and the parameters are in a relationship of mutual restriction and mutual compensation, and need to be analyzed and adjusted in a unified way when the process is adjusted. It should be noted that, in the experimental process, the inventors found that in the metal halide-carbon monoxide reaction system, the reduction of the high valence metal to the simple substance metal is not completed in one step, an intermediate state exists, a side reaction occurs, and the conversion rate is affected by the process parameters.
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples. In the industrial production, in consideration of economic cost, the embodiment uses argon as the inert gas for protection, and can also be popularized to other inert gases which do not participate in vapor deposition reaction. The following examples will assist the researcher in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Examples 1-6 are for the preparation of tantalum, examples 7-12 are for the preparation of tungsten, examples 13-18 are for the preparation of rhenium, examples 19-24 are for the preparation of niobium, examples 25-30 are for the preparation of molybdenum, examples 31-36 are for the preparation of hafnium. The starting materials and reagents used in the present invention are commercially available.
Preparation of tantalum (I), examples 1 to 6
The invention considers carbon monoxide as reducing gas, fundamentally solves the problem of hydrogen induced cracking, and simultaneously reduces the step of dehydrogenation treatment. The reaction equations involved in the invention are respectively:
2TaCl5+5CO→2Ta+5COCl
2TaF5+5CO→2Ta+5COF2
examples 1-6 were conducted using different bodies for chemical vapor deposition of tantalum metal, and examples 1-4 were conducted using tantalum pentachloride as a reactant, and examples 5 and 6 were conducted using tantalum pentafluoride as a reactant, using the same procedure. The chemical vapor deposition equipment is an alumina reaction chamber.
Example 1
The materials and reagents used were as follows: a silicon carbide ceramic disc blank (99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tantalum pentachloride (99.99%).
The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to an 800Pa vacuum state, keeping the 800Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating silicon carbide ceramic disc blanks by distilled water, drying for 6 hours at 150 ℃, and then putting the silicon carbide ceramic disc blanks into a reaction chamber to ensure that the surfaces to be deposited of the blanks are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to 800Pa vacuum state, keeping the 800Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to be in a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to 800Pa vacuum state, maintaining the 800Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 14000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1000 ℃;
(5) putting tantalum pentachloride into a gasification chamber, heating to 350 ℃, gasifying the tantalum pentachloride, introducing gasified tantalum pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of the tantalum pentachloride, the carbon monoxide and the argon gas is 1: 2: 2, the flow rates are respectively 4 cubic meters per hour, 8 cubic meters per hour and 8 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 50 hours; preparing a silicon carbide/metal tantalum coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared silicon carbide/metal tantalum coating material.
The product was tested after appropriate heat treatment. The thickness of the prepared silicon carbide/metal tantalum coating material tantalum coating is detected by using a metallographic microscope, and the detection result shows that the thickness of the coating is 520 mu m. The adhesion of the prepared tantalum coating of the silicon carbide/metal tantalum coating material is detected according to the ISO4624-2016 coating adhesion test standard, the adhesion of the metal tantalum coating and the silicon carbide substrate is 125MPa through the test, compared with the existing method, the adhesion of the coating is remarkably improved, and the adhesion of the coating is generally smaller than 100MPa through other chemical vapor deposition tantalum technical schemes. FIG. 5 shows a gold phase diagram of the tantalum metal surface, which is magnified 1000 times, and no cracking phenomenon is observed.
By using the process conditions of example 1, the deposition rate and the adhesion of the deposited layer were obtained at different temperatures by performing the chemical vapor deposition according to the above steps (1) to (6) while changing the temperature of the reaction chamber, i.e., the deposition temperature, as shown in table 3 and fig. 2. At 800 ℃, the deposition rate was very slow, with little tantalum deposition observed; the deposition rate increases with increasing reaction temperature. The temperature is changed from 850 ℃ to 1000 ℃, and the deposition rate is obviously improved; the speed of the temperature range of 1000-1300 ℃ rises relatively slowly, and when the temperature exceeds a certain range, the influence of the temperature on the deposition rate becomes slow and not obvious. The deposition rate can reach 12.6 mu m per hour.
As shown in fig. 2, at 800 ℃, no tantalum deposition resulted in untestable adhesion. The adhesive force of the coating is larger than 100Mpa within the range of 820-1300 ℃, and the overall trend is that the adhesive force is increased firstly and then decreased. The adhesive force of the coating rises along with the rise of the temperature within the range of 820-850 ℃; the adhesive force of the coating slowly decreases along with the temperature rise within the range of 850-1300 ℃. When the temperature is higher than 1200 ℃, the adhesive force of the coating is obviously reduced to be lower than 100 MPa. When the reaction temperature is 850 ℃, the maximum adhesion value can reach 127 MPa. The reaction temperature was observed by surface topography with no significant change in the composition of the tantalum deposition layer.
TABLE 3 Effect of reaction temperature on coating
The carbon monoxide gas flow rate was varied and the other parameters were kept constant, resulting in the results of table 4 and fig. 3. For convenience of illustration, the flow rate of the tantalum pentachloride gas in this embodiment is fixed to 4m3Other flow rates, with corresponding changes in deposition rate, may also be used. When the carbon monoxide gas flow is 4m3When the deposition rate is per hour, the volume ratio of the deposition rate to the tantalum pentachloride is 1:1, the thickness of the prepared coating is 122-139 mu m, and the average value of the calculated deposition rate is 2.6 mu m/hour. When the volume ratio of the two is adjusted to be 1:2, namely the carbon monoxide gas flow is 8m3When the deposition rate is per hour, the thickness of the prepared coating is 520-525 mu m, and the average value of the calculated deposition rate is 10.5 mu m/hour. . . When the volume ratio of the two is adjusted to 1:3, the CO gas flow rate continues to increase to 12m3When the thickness of the prepared coating reaches 531 mu m, the calculated average value of the deposition rate is 10.6 mu m/h, and partial gas directly flows through the surface of the blank without participating in the reaction, so that the efficiency of the reaction process is reduced. In this embodiment, the adhesion of the deposition layer is greater than 100MPa at different flow rates of the reaction gases, and the variation of the values is small.
TABLE 4 influence of the reaction gas ratio on the coating
When the volume ratio of the tantalum pentachloride to the carbon monoxide is not changed, the argon flow is respectively adjusted to be 4m3/h、8m3/h、12m3/h、20m3H, deposition rate and deposition layer adherenceThe force is increased to a certain extent. The flow rate of the carrier gas should not be too high, so as to avoid the waste of reactants. The change of the flow rate of the argon gas has no obvious influence on the deposition rate and the adhesion of the deposited layer. When the flow of argon is increased, the deposition rate and the adhesion of the deposition layer are slightly increased. However, the flow rate of the carrier gas should not be too large, so as to avoid the waste of reactants. The preferred flow rate of tantalum pentachloride is 2-6m3Other flow rates can be used, with the deposition rate varying accordingly. The preferred carbon monoxide flow rate is 2-18m3Adjusting within the range of/h. The preferred argon flow is in the range of 2 to 30m3Adjustment in the h range, example 2
The materials and reagents used were as follows: a quartz glass cylindrical body (silica content greater than 99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tantalum pentachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a vacuum state of 100Pa, keeping the vacuum state of 100Pa for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 5 minutes, closing an exhaust valve, and evacuating residual gases and impurities which are not required by reaction and are not required by the reaction in the vapor deposition equipment through the steps;
(2) cleaning a quartz glass cylindrical blank by distilled water, removing dirt, drying at 105 ℃ for 5 hours, and then putting into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the surfaces are not overlapped and blocked;
(3) vacuumizing to a 100Pa vacuum state, keeping the 100Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 5 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the blank through the steps;
(4) vacuumizing to a vacuum state of 100Pa, maintaining the vacuum state of 100Pa for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 12000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 820 ℃;
(5) putting tantalum pentachloride into a gasification chamber, heating to 500 ℃, gasifying the tantalum pentachloride, introducing gasified tantalum pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of the tantalum pentachloride, the carbon monoxide and the argon gas is 1: 2: 2, the flow rates are respectively 4 cubic meters per hour, 8 cubic meters per hour and 8 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 1 hour; preparing a glass/metal tantalum coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared glass/metal tantalum composite material.
After appropriate heat treatment, the test was carried out. The thickness of the prepared tantalum coating of the glass/metal tantalum coating material is detected by using a metallographic microscope, the detection result shows that the thickness of the coating is 10 mu m, the adhesion of the prepared tantalum coating of the glass/metal tantalum coating material is detected according to the adhesion test standard of ISO4624-2016 coatings, and the adhesion of the metal tantalum coating and a glass substrate is 133MPa through the test.
Example 3
The materials and reagents used were as follows: a carbon fiber cylindrical blank (the carbon content is more than 99.99 percent, and the porosity is 85 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tantalum pentachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual gases and impurities which are required by non-reaction and are not required by non-reaction in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a carbon fiber cylindrical blank by distilled water, drying the carbon fiber cylindrical blank for 10 hours at the temperature of 150 ℃, and then putting the carbon fiber cylindrical blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the carbon fiber cylindrical blank is not overlapped with the reaction gas outlet and is not blocked;
(3) vacuumizing to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating gas required by non-reaction and gas and impurities required by non-reaction which enter in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to 200Pa vacuum state, maintaining the 200Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is well sealed, controlling the vacuum degree in the vapor deposition equipment to 13500Pa by using a vacuum pump, and simultaneously heating the temperature in the reaction chamber to 1000 ℃;
(5) putting tantalum pentachloride into a gasification chamber, heating to 600 ℃, gasifying the tantalum pentachloride, introducing gasified tantalum pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of the tantalum pentachloride, the carbon monoxide and the argon gas is 1: 1.5: 3, the flow rates are respectively 2 cubic meters per hour, 3 cubic meters per hour and 6 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 500 hours; preparing a carbon fiber/metal tantalum composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared porous carbon/metal tantalum composite material.
After appropriate heat treatment, the test was carried out. The bending strength performance of the prepared material is tested according to GB/T232-. The elastic modulus of the prepared carbon fiber/metal tantalum composite material is 212GPa, the bending strength is 826Mpa, and compared with the prior method, the method overcomes hydrogen embrittlement and obviously improves the mechanical property of the material. The prepared carbon fiber/metal tantalum composite material is tested according to ISO/TR 26946-. The embodiment result shows that the technical scheme of the invention overcomes the defects of the existing method and can be suitable for preparing the high-performance metal tantalum composite material.
Example 4
The materials and reagents used were as follows: a 316L stainless steel cylindrical blank; high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tantalum pentachloride (99.99%). The implementation steps are as follows:
(1) vacuumizing the equipment to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities and non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning a 316L stainless steel cylindrical blank by distilled water, removing dirt, drying at 200 ℃ for 10 hours, and then putting into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blank is not overlapped and blocked;
(3) vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating gas required by non-reaction and gas and impurities required by non-reaction which enter in the process of placing a blank of the vapor deposition equipment into the blank through the steps;
(4) vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, controlling the vacuum degree in the vapor deposition equipment to 15000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 820 ℃;
(5) putting tantalum pentachloride into a gasification chamber, heating to 600 ℃, gasifying the tantalum pentachloride, introducing gasified tantalum pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of the tantalum pentachloride, the carbon monoxide and the argon gas is 1: 2: 5, the flow rates are respectively 3 cubic meters per hour, 6 cubic meters per hour and 15 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 1000 hours;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared metal tantalum material;
(7) and removing the 316L stainless steel cylindrical blank of the material obtained by deposition through machining, and finally obtaining the pure metal tantalum material with the thickness of 10 mm.
After proper heat treatment, the bending strength performance of the material is tested according to the standard GB/T232-. The elastic modulus performance of the prepared material is tested, the elastic modulus of the prepared metal tantalum material is 235GPa, the bending strength is 883Mpa, and compared with the existing method, the method overcomes hydrogen embrittlement and obviously improves the mechanical property of the material. The prepared metal tantalum material is tested according to ISO/TR26946-2011 porosity test standard, the test result shows that the porosity of the metal tantalum material is 0, and the metal tantalum material is 16.65g/cm calculated according to the method of mass/volume-density3The purity of the tantalum metal material is tested by using an inductively coupled high-frequency plasma mass spectrometry (TCP-IP) as same as the true density of the tantalum metal, and the test result shows that the tantalum metal materialThe purity was 99.999%. The embodiment result shows that the technical scheme of the invention overcomes the defects of the existing method and can be suitable for preparing high-purity and high-performance metal tantalum materials.
Example 5
The materials and reagents used were as follows: a 316L stainless steel rivet; high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tantalum pentafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing chemical vapor deposition equipment to a 900Pa vacuum state, keeping the 900Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 12 minutes, closing an exhaust valve, and evacuating residual gases and impurities which are required by non-reaction and gases and impurities which are required by non-reaction in the vapor deposition equipment through the steps;
(2) cleaning 316L stainless steel rivet blanks by distilled water, removing dirt, drying at 120 ℃ for 7 hours, and then putting into a reaction chamber to ensure that the surfaces to be deposited of the blanks are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 900Pa vacuum state, keeping the 900Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 12 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber and the vacuum pipelines;
(4) vacuumizing to 900Pa vacuum state, maintaining the 900Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 12000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 850 ℃;
(5) putting tantalum pentafluoride into a gasification chamber, heating to 600 ℃, gasifying the tantalum pentafluoride, introducing gasified tantalum pentafluoride gas into a gas mixing tank, introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of tantalum pentafluoride, carbon monoxide and argon gas is 1: 1.5: 2, the flow rates are respectively 4 cubic meters per hour, 6 cubic meters per hour and 8 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 10 hours; preparing a stainless steel/metal tantalum coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared stainless steel/metal tantalum coating material.
After appropriate heat treatment, the test was carried out. The thickness of the prepared stainless steel/metal tantalum coating material tantalum coating is detected by using a metallographic microscope, the detection result shows that the thickness of the prepared stainless steel/metal tantalum coating material tantalum coating is 120 mu m, the adhesion of the prepared stainless steel/metal tantalum coating material tantalum coating is detected according to the ISO4624-2016 coating adhesion test standard, the adhesion of the metal tantalum coating and a stainless steel matrix is 158MPa through test, and the adhesion of the coating is remarkably improved compared with the existing method.
FIG. 4 is a graph of the deposition rate and the adhesion of the deposited layer for tantalum pentafluoride on a green body at various chamber temperatures as in example 5. At 800 ℃, the deposition rate was very slow, with little tantalum deposition observed; the deposition rate increases with increasing reaction temperature. The deposition rate is obviously improved within the range of 820-1000 ℃, the speed of the range of 1000-1200 ℃ is relatively slowly increased, and when the temperature exceeds a certain range, the influence of the temperature on the deposition rate is retarded and not obvious. The deposition rate can reach 13.9 μm per hour. The reaction temperature did not change significantly with respect to the composition of the tantalum deposition layer.
As shown in FIG. 4, the coating adhesion is greater than 100MPa within 820-1200 ℃, and the overall trend is that the coating adhesion increases first and then decreases. The adhesive force of the coating rises along with the rise of the temperature within the range of 820-850 ℃; the adhesive force of the coating slowly decreases along with the temperature rise within the range of 850-1200 ℃. When the temperature is higher than 1200 ℃, the adhesive force of the coating is obviously reduced to be lower than 100 MPa. When the reaction temperature is 850 ℃, the maximum adhesion value can reach 158 MPa.
Chemical vapor deposition was performed according to the above steps (1) to (6) with only changing the reaction gas ratio under the process parameters using the steps (1) to (6) of example 5. The preferred gas volume ratio of tantalum pentafluoride to carbon monoxide is 1:1-3 and the preferred gas volume ratio of tantalum pentafluoride to argon is 1: 1-5. The preferred tantalum pentafluoride flow rate is 2-6m3Other flow rates can be used, with the deposition rate varying accordingly. The preferred carbon monoxide flow rate is 2-18m3Adjusting within the range of/h. The preferred argon flow is in the range of 2 to 30m3The effect of adjusting the gas ratio and flow rate on the chemical deposition rate and the adhesion of the deposited layer in the/h range is observed and described in detail in the embodiment 1, which is not repeated here.
Example 6
The materials and reagents used were as follows: a porous carbon square blank (the carbon content is more than 99.999 percent, and the porosity is more than 96 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tantalum pentafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a porous carbon square blank by distilled water, drying the blank for 5 hours at 200 ℃, and then putting the blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the blank through the steps;
(4) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 15000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1180 ℃;
(5) putting tantalum pentafluoride into a gasification chamber, heating to 300 ℃, gasifying the tantalum pentafluoride, introducing gasified tantalum pentafluoride gas into a gas mixing tank, introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of tantalum pentafluoride, carbon monoxide and argon gas is 1: 1:2, the flow rates are respectively 2 cubic meters per hour, 2 cubic meters per hour and 4 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on a blank body for 100 hours; preparing a porous carbon/metal tantalum composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared porous carbon/metal tantalum composite material.
And carrying out performance test after proper heat treatment. The prepared porous carbon/metal tantalum composite material is tested according to ISO/TR26946-2011 porosity test standard, test results show that the porosity of the porous carbon/metal tantalum composite material is 85%, the bending strength performance of the prepared material is tested according to GB/T232-2010 metal material bending test method, the elastic modulus performance of the prepared material is tested according to GB/T22315-2008 metal material elastic modulus and Poisson ratio test method, and the test results show that the elastic modulus of the prepared porous carbon/metal tantalum composite material is 29GPa, the bending strength is 316MPa, and compared with the existing method, the hydrogen embrittlement is overcome, and the mechanical property of the material is obviously improved.
In the embodiments 1-6, all the tantalum metal is detected by adopting flame atomic absorption spectroscopy, the content of the tantalum metal is more than 99.999 percent, and the surface appearance of the coating is observed by adopting a scanning electron microscope without cracking. Preferably, the vacuum degree in the vapor deposition apparatus in the above embodiment is controlled within the range of 12000-15000Pa by a vacuum pump. The change of the vacuum degree also has influence on the deposition rate, and the deposition rate is increased along with the increase of the gas pressure of the reaction chamber; however, the degree of vacuum reaches a certain range, and the deposition rate changes slowly. The change of vacuum degree has no obvious change to the composition of the tantalum deposition layer, and has certain influence on the preferential growth. The test results of the above embodiments show that, compared with the existing method, the product prepared by the invention overcomes the defects of the prior art, remarkably improves the mechanical properties of the material, and can be suitable for preparing high-performance metal tantalum coating or tantalum composite material in industrialized production.
Preparation of tungsten (II), example 7-example 12
In the prior art, chemical vapor deposition of tungsten generally uses hydrogen as a reducing gas:
WCl6+3H2→W+6HCl
WF6+3H2→W+6HF
this process can cause hydrogen embrittlement of the film, i.e., hydrogen induced cracking. The prior art generally adds a dehydrogenation step to stabilize the properties of the film layer, thereby reducing the risk of hydrogen induced cracking. The invention considers carbon monoxide as reducing gas, fundamentally solves the problem of hydrogen induced cracking, and simultaneously reduces the step of dehydrogenation treatment. The reaction equation involved in the invention is as follows:
WCl6+3CO→W+3COCl2
WF6+3CO→W+3COF2
examples 7-12 tungsten metal was deposited by chemical vapor deposition using different blanks, wherein examples 7-10 used tungsten hexachloride as the reactant and example 11 performed the same procedure as example 12 using tungsten hexafluoride as the reactant. The chemical vapor deposition equipment is an alumina reaction chamber.
Example 7
The materials and reagents used were as follows: a graphite cylindrical blank (99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tungsten hexachloride (99.99%). The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 15 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a cylindrical graphite blank by distilled water, drying the cylindrical graphite blank for 15 hours at 150 ℃, and then putting the cylindrical graphite blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the blank through the steps;
(4) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 22000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1000 ℃;
(5) putting tungsten hexachloride into a gasification chamber, heating to 700 ℃, gasifying the tungsten hexachloride, introducing the gasified tungsten hexachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the tungsten hexachloride, the carbon monoxide gas and the argon gas is 1: 2: 3, the flow rates are respectively 1 cubic meter/h, 2 cubic meters/h and 3 cubic meters/h, after fully mixing in a gas mixing tank, the mixture is introduced into a reaction chamber to carry out chemical vapor deposition reaction on the blank for 100 hours; preparing a graphite/metal tungsten coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared silicon carbide/metal tungsten coating material.
And carrying out performance test after proper heat treatment. The thickness of the prepared graphite/metal tungsten coating material tungsten coating is detected by using a metallographic microscope, and the detection result shows that the thickness of the coating is 271 μm. The adhesion of the prepared graphite/metal tungsten coating material tungsten coating is detected according to the ISO4624-2016 coating adhesion test standard, and the adhesion of the metal tungsten coating and the graphite matrix is 152MPa through the test, so that compared with the existing method, the adhesion of the coating is remarkably improved, and the adhesion of the coating is generally less than 100MPa through other chemical vapor deposition tungsten technical schemes. FIG. 9 shows a gold phase diagram of the surface of a tungsten metal fault, which is magnified 1000 times, and no cracking phenomenon is observed.
Chemical vapor deposition was performed according to the above steps (1) - (6) with only the change in chamber temperature using the process conditions of example 7, and the results of table 5 and fig. 6 were obtained, reflecting the effect of different deposition temperatures on deposition rate and adhesion of the deposited layer. As shown in fig. 6, at 800 ℃, the deposition rate was very slow, and almost no tungsten deposition was observed; the deposition rate increases with increasing reaction temperature. In the range of higher than 900 ℃ to 1000 ℃, the deposition rate is obviously improved, the speed of the range of 1000 ℃ to 1250 ℃ is relatively slowly increased, and when the temperature exceeds a certain range, the influence of the temperature on the deposition rate becomes slow and not obvious. The deposition rate can reach 3.37 mu m per hour.
As shown in fig. 6, at 800 ℃, adhesion could not be tested since the deposition rate was very slow and little tungsten deposition was observed; the adhesive force of the coating is more than 100Mpa within the range of 850-1250 ℃, and the general trend of the adhesive force of the coating is a trend of increasing firstly and then decreasing along with the temperature. It can be seen from FIG. 6 that when the reaction temperature is in the range of 850 ℃ to 1000 ℃, the adhesion is significantly increased; the adhesive force of the coating is reduced within the range of 1000-1250 ℃, and is reduced to 110MPa at 1250 ℃. When the temperature is higher than 1250 ℃, the adhesive force of the coating is obviously reduced to be lower than 100 MPa. When the reaction temperature is 900 ℃, the maximum adhesion value can reach 162 MPa. In comprehensive consideration, the reaction temperature is preferably in the range of 850-1250 ℃.
TABLE 5 Effect of reaction temperature on coating
Differences in the flow rates and ratios of the reactant gases also have an effect on chemical vapor deposition. The chemical vapor deposition was carried out by changing only the reaction gas ratio in the above steps (1) to (6). For convenience of illustration, the flow rate of the tungsten hexachloride gas in this example was fixed to 4m3Other flow rates, with corresponding changes in deposition rate, may also be used. The carbon monoxide gas flow rate was changed while the other parameters were kept constant, and the results of table 6 and fig. 7 were obtained. When the carbon monoxide gas flow is 4m3When the deposition rate is/h, namely the ratio of the tungsten hexachloride gas to the carbon monoxide is 1:1, the calculated average deposition rate of the prepared coating with the thickness of 119-138 mu m is about 1.3 mu m/h; the CO gas flow is increased to 8m3The ratio of tungsten hexachloride gas to carbon monoxide is 1:2, the amount of source substances participating in the reaction in unit time is increased, the reaction is favorably carried out towards the direction of a product, the deposition rate is increased, the thickness of the prepared coating is 521-525 mu m, and the calculated average deposition rate is about 3.15 mu m/h; increasing the carbon monoxide gas flow to 12m3When the deposition time is/h, namely the ratio of the tungsten hexachloride gas to the carbon monoxide is 1:3, the film thickness is 530um after deposition, the adhesion force is 159MPa, and the deposition rate is calculated to be about 5.3 mu m/h. If the flow of the CO gas is continuously increased, part of the gas does not participate in the reaction and directly flows through the surface of the blank, so that the efficiency of the reaction process is reduced.
TABLE 6 influence of the reaction gas ratio on the coating
Keeping the volume ratio of tungsten hexachloride to carbon monoxide unchanged, and adjusting the argon flow to 4m3/h、8m3/h、12m3/h、20m3H, deposition rateThe rate and the adhesion of the deposition layer are increased to a certain extent. The flow rate of the carrier gas should not be too high, so as to avoid the waste of reactants. The ratio of reactant gas to flow rate is related to the concentration of the reactants. The concentration of the reactant is too low or too high, which affects the deposition efficiency, greatly affects the deposition rate and has certain influence on the adhesive force of the deposition layer. In order to ensure that the tungsten halide is reacted sufficiently, the CO is ensured to be excessive due to the production cost of enterprises. In this embodiment, the adhesion to the deposition layer is greater than 100MPa at different flow rates of the reaction gases, and the influence of the change of the value is small. The preferred flow rate of tungsten hexachloride is between 1 and 9m3Other flow rates can be used, with the deposition rate varying accordingly. The preferred carbon monoxide flow rate is 2-18m3Adjusting within the range of/h. The preferred argon flow is in the range of 3 to 27m3Adjusting within the range of/h.
Example 8
The materials and reagents used were as follows: a silicon nitride cylindrical blank (the silicon nitride content is more than 99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tungsten hexachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a 300Pa vacuum state, keeping the 300Pa vacuum state for 5 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities and non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning a silicon nitride cylindrical blank by distilled water, removing dirt, drying at 105 ℃ for 15 hours, and then putting the silicon nitride cylindrical blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the surface to be deposited of the blank is not overlapped with the reaction gas outlet and is not blocked;
(3) vacuumizing to a 300Pa vacuum state, keeping the 300Pa vacuum state for 5 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber and the vacuum pipelines;
(4) vacuumizing to 300Pa vacuum state, keeping 300Pa vacuum state for 5 minutes, controlling the vacuum degree in the vapor deposition equipment to 20000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 900 ℃;
(5) putting tungsten hexachloride into a gasification chamber, heating to 700 ℃, gasifying the tungsten hexachloride, introducing the gasified tungsten hexachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the tungsten hexachloride, the carbon monoxide gas and the argon gas is 1: 2: 3, the flow rates are respectively 6 cubic meters per hour, 12 cubic meters per hour and 18 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 1 hour; preparing a silicon nitride/metal tungsten coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the silicon nitride/metal tungsten composite material which is prepared.
And carrying out performance test after proper heat treatment. The thickness of the prepared silicon nitride/metal tungsten coating material tungsten coating is detected by using a metallographic microscope, the detection result shows that the thickness of the coating is 8 mu m, the adhesion of the prepared silicon nitride/metal tungsten coating material tungsten coating is detected according to the ISO4624-2016 coating adhesion test standard, and the adhesion of the metal tungsten coating and the silicon nitride substrate is 138MPa through the test.
Example 9
The materials and reagents used were as follows: a carbon fiber cylindrical blank (the carbon content is more than 99.99 percent, and the porosity is 85 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tungsten hexachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 8 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 12 minutes, closing an exhaust valve, and evacuating residual gases and impurities which are required by non-reaction and are not required by non-reaction in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a carbon fiber cylindrical blank by distilled water, drying the carbon fiber cylindrical blank at 120 ℃ for 12 hours, and then putting the carbon fiber cylindrical blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the carbon fiber cylindrical blank is not overlapped with the reaction gas outlet and is not blocked;
(3) vacuumizing to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 8 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 12 minutes, closing an exhaust valve, and evacuating gas required by non-reaction and gas and impurities required by non-reaction which enter in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to a vacuum state of 200Pa, maintaining the vacuum state of 200Pa for 8 minutes, controlling the vacuum degree in the vapor deposition equipment to 21000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 980 ℃;
(5) putting tungsten hexachloride into a gasification chamber, heating to 500 ℃ to gasify the tungsten hexachloride, introducing the gasified tungsten hexachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the tungsten hexachloride, the carbon monoxide gas and the argon gas is 1: 1.5: 2, the flow rates are respectively 6 cubic meters per hour, 9 cubic meters per hour and 12 cubic meters per hour, after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to carry out chemical vapor deposition reaction on a blank body, and the reaction time is 500 hours; preparing a carbon fiber/metal tungsten composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared porous carbon/metal tungsten composite material.
And carrying out performance test after proper heat treatment. The bending strength performance of the material is tested according to the standard GB/T232-. The elastic modulus of the prepared carbon fiber/metal tungsten composite material is 462GPa, the bending strength is 1721Mpa, and compared with the prior method, the method overcomes hydrogen embrittlement and obviously improves the mechanical property of the material. The prepared carbon fiber/metal tungsten composite material is tested according to ISO/TR 26946-. The embodiment result shows that the technical scheme of the invention overcomes the defects of the existing method and can be suitable for preparing the high-performance metal tungsten composite material.
Example 10
The materials and reagents used were as follows: a cylindrical graphite blank; high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tungsten hexachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 15 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities and non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a graphite cylindrical blank by distilled water, drying the blank for 15 hours at 150 ℃, and then putting the blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blank is not overlapped with the reaction gas outlet and is not blocked;
(3) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the blank through the steps;
(4) vacuumizing to a 500Pa vacuum state, maintaining the 500Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 22000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1250 ℃;
(5) putting tungsten hexachloride into a gasification chamber, heating to 700 ℃, gasifying the tungsten hexachloride, introducing the gasified tungsten hexachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the tungsten hexachloride, the carbon monoxide gas and the argon gas is 1: 2: 3, the flow rates are respectively 9 cubic meters per hour, 18 cubic meters per hour and 27 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 1000 hours;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared metal tungsten material;
(7) and removing the graphite cylindrical blank of the material obtained by deposition through machining, and finally obtaining the pure metal tungsten material with the thickness of 10 mm.
And carrying out performance test after proper heat treatment. The bending strength performance of the prepared material is tested according to the GB/T232-. The elastic modulus of the prepared metal tungsten material is 538GPa, the bending strength is 1897Mpa, and compared with the existing method, the method overcomes hydrogen embrittlement and obviously improves the mechanical property of the material. The prepared metal tungsten material is tested according to ISO/TR26946-2011 porosity test standard, and the test result shows that the porosity of the metal tungsten material is 0The metal tungsten material is calculated by a method of mass/volume-density, and is 19.35g/cm3The purity of the material is tested by using an inductively coupled high-frequency plasma mass spectrometry (TCP-IP) which is the same as the true density of tungsten metal, and the test result shows that the purity of the metal tungsten material is 99.999 percent. The embodiment result shows that the technical scheme of the invention overcomes the defects of the existing method and can be suitable for preparing high-purity and high-performance metal tungsten materials.
Example 11
The materials and reagents used were as follows: a 316L stainless steel disk blank; high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tungsten hexafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing chemical vapor deposition equipment to a 400Pa vacuum state, keeping the 400Pa vacuum state for 5 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual gases and impurities which are required by non-reaction and gases and impurities which are required by non-reaction in the vapor deposition equipment through the steps;
(2) cleaning 316L stainless steel disc blanks by distilled water, removing dirt, drying at 105 ℃ for 10 hours, and then putting into a reaction chamber to ensure that the surfaces to be deposited of the blanks are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 400Pa vacuum state, keeping the 400Pa vacuum state for 5 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber and the vacuum pipelines;
(4) vacuumizing to a 400Pa vacuum state, keeping the 400Pa vacuum state for 5 minutes, controlling the vacuum degree in the vapor deposition equipment to 18000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 950 ℃;
(5) putting tungsten hexafluoride into a gasification chamber, heating to 400 ℃ to gasify the tungsten hexafluoride, introducing the gasified tungsten hexachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the tungsten hexafluoride gas, the carbon monoxide gas and the argon gas is 1: 1.5: 2, the flow rates are respectively 4 cubic meters per hour, 6 cubic meters per hour and 8 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 10 hours; preparing a stainless steel/metal tungsten coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared stainless steel/metal tungsten coating material.
And carrying out performance test after proper heat treatment. The thickness of the prepared stainless steel/metal tungsten coating material tungsten coating is detected by using a metallographic microscope, the detection result shows that the thickness of the prepared stainless steel/metal tungsten coating material tungsten coating is 129 mu m, the adhesion of the prepared stainless steel/metal tungsten coating material tungsten coating is detected according to the ISO 4624-one 2016 coating adhesion test standard, the adhesion of the metal tungsten coating and a stainless steel substrate is 166MPa through test, and the adhesion of the coating is remarkably improved compared with the existing method.
FIG. 8 is a graph of the effect of different deposition temperatures on deposition rate and adhesion of the deposited layer in tungsten hexafluoride production of tungsten on a green body according to example 11. At 800 ℃, the deposition rate was very slow, with little tungsten deposition observed; the deposition rate increases with increasing reaction temperature. The temperature is increased from 820 ℃ to 1000 ℃, the deposition rate is obviously improved, the speed is relatively slowly increased from 1000 ℃ to 1200 ℃, and when the temperature exceeds a certain range, the influence of the temperature on the deposition rate becomes slow and is not obvious.
The adhesion of the coating is more than 100MPa at the temperature of 820-1200 ℃. When the temperature was greater than 820 ℃, deposition of tungsten was initially observed and adhesion was significantly improved. When the reaction temperature is 850 ℃, the maximum adhesion value can reach 159 MPa. The reaction temperature is in the range of 850-1200 ℃, the adhesive force of the coating is gradually reduced along with the temperature rise, and when the temperature is higher than 1200 ℃, the adhesive force of the coating is obviously reduced to be less than 100 MPa.
The observation of the surface morphology shows that the reaction temperature has no obvious change on the composition of the tungsten deposition layer, but has certain influence on the preferred growth; the grain size of the tungsten deposition layer increases with the increase of the temperature, and when the temperature is higher than 1250 ℃, the phenomenon of coarse grains is caused.
Chemical vapor deposition was carried out according to the above steps (1) to (6) with the preferred gas volume ratio of tungsten hexafluoride to carbon monoxide being 1:1 to 3 and the preferred gas volume ratio of tungsten hexafluoride to argon being 1:1 to 3, with only the reaction gas ratios being varied using the process parameters of example 11. Preferably, the flow rate of tungsten hexafluoride is between 1 and 9m3Other flow rates can be used, with the deposition rate varying accordingly. Preferably, the carbon monoxide flow is 2-18m3Adjusting within the range of/h. Preferably, the flow rate of argon is 3-27m3The effect of adjusting the gas ratio and flow rate on the chemical deposition rate and the adhesion of the deposited layer in the/h range is observed, and is described in detail in the embodiment 7, which is not repeated here.
Example 12
The materials and reagents used were as follows: a porous carbon cylindrical blank (the carbon content is more than 99.999 percent, and the porosity is more than 96 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity tungsten hexafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 5 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a porous carbon cylindrical blank by distilled water, drying the blank for 10 hours at 150 ℃, and then putting the blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 5 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the blank through the steps;
(4) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 5 minutes, controlling the vacuum degree in the vapor deposition equipment to 19000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1250 ℃;
(5) putting tungsten hexafluoride into a gasification chamber, heating to 400 ℃ to gasify the tungsten hexafluoride, introducing the gasified tungsten hexafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the tungsten hexafluoride gas to the carbon monoxide gas to the argon gas is 1: 1:1, the flow rates are respectively 9 cubic meters per hour, 9 cubic meters per hour and 9 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on a blank body for 100 hours; preparing a porous carbon/metal tungsten composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared porous carbon/metal tungsten composite material.
And carrying out performance test after proper heat treatment. The prepared porous carbon/metal tungsten composite material is tested according to ISO/TR 26946-. The bending strength performance of the material is tested according to the standard GB/T232-. The test result shows that the elastic modulus of the prepared porous carbon/metal tungsten composite material is 55GPa, the bending strength is 531MPa, and compared with the existing method, the method overcomes hydrogen embrittlement and obviously improves the mechanical property of the material.
In examples 7 to 12, the metal tungsten is detected by flame atomic absorption spectroscopy, the content of the metal tungsten is more than 99.999 percent, and the surface appearance of the coating is observed by a scanning electron microscope without cracking. Preferably, the vacuum degree in the vapor deposition equipment is controlled at 18000-22000Pa by the vacuum pump in the above embodiment, and the change of the vacuum degree also has influence on the deposition rate of the invention. The deposition rate is increased along with the increase of the gas pressure of the reaction chamber; however, the degree of vacuum reaches a certain range, and the deposition rate changes slowly. The change of vacuum degree has no obvious change to the composition of the deposition layer, but has certain influence on the preferential growth. The test results of the above embodiments show that, compared with the existing method, the product prepared by the invention overcomes the defects of the prior art, remarkably improves the mechanical properties of the material, and can be suitable for preparing high-performance metal tantalum coating or tantalum composite material in industrialized production.
Preparation of (Tri) rhenium, examples 13-18
In the prior art, chemical vapor deposition of rhenium uses hydrogen as the reducing gas:
2ReCl5+5H2→2Re+10HCl
2ReF5+5H2→2Re+10HF
combining literature and experimental practical conditions to obtain one of the kinetic models of chemical vapor deposition of rhenium: at a temperature above 1000 ℃ in ReCl5Starting the conversion to Recl under the action of hydrogen3，ReCl3Conversion to elemental Re, but not high, a specific process can be expressed as:
ReCl5+H2——→ReCl3+2HCl
2ReCl3+3H2——→2Re+6HCl
the invention considers carbon monoxide as reducing gas, fundamentally solves the problem of hydrogen induced cracking, and simultaneously reduces the step of dehydrogenation treatment. The chemical reaction equation related to the invention is as follows:
2ReCl5+5CO→2Re+5COCl2
2ReF5+5CO→2Re+5COF2
examples 13-18 chemical vapor deposition of rhenium metal was carried out using different bodies, where examples 13-16 used rhenium pentachloride as the reactant and example 17 performed the same procedure as example 18 using rhenium pentafluoride as the reactant. The chemical vapor deposition equipment is an alumina reaction chamber.
Example 13
The materials and reagents used were as follows: metallic molybdenum square billet (density 1.8 g/cm)3Purity 99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity rhenium pentachloride (99.99%). The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to an 800Pa vacuum state, keeping the 800Pa vacuum state for 20 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 20 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a square molybdenum blank by distilled water, drying the square molybdenum blank for 5 hours at 150 ℃, and then putting the square molybdenum blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to 800Pa vacuum state, keeping the 800Pa vacuum state for 20 minutes, checking that the vapor deposition equipment is sealed completely, then introducing argon to be filled to normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 20 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber and the vacuum pipelines;
(4) vacuumizing to 800Pa vacuum state, maintaining the 800Pa vacuum state for 20 minutes, controlling the vacuum degree in the vapor deposition equipment to 20000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 950 ℃;
(5) putting rhenium pentachloride into a gasification chamber, heating to 500 ℃, gasifying the rhenium pentachloride, introducing gasified rhenium pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the rhenium pentachloride to the carbon monoxide to the argon gas is 1: 4: 2, the flow rates are respectively 1 cubic meter/h, 4 cubic meters/h and 2 cubic meters/h, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on a blank body for 100 hours; preparing a metal rhenium coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared molybdenum/rhenium metal coating material.
And carrying out performance test after proper heat treatment. The thickness of the prepared rhenium metal coating is detected by using a metallographic microscope, and the detection result shows that the thickness of the coating is 980 mu m. The adhesion of the prepared metal rhenium coating is detected according to the adhesion test standard of ISO4624-2016 coating, the adhesion of the metal rhenium coating and the substrate is 170MPa through test, compared with the existing method, the adhesion of the coating is obviously improved, and the adhesion of the coating is generally less than 100MPa through other chemical vapor deposition rhenium technical schemes. The gold phase diagram of the rhenium metal fault surface is shown in fig. 13, the magnification is 1000 times, and no cracking phenomenon is observed.
Chemical vapor deposition was performed according to the above steps (1) to (6) while changing only the chamber temperature under the process conditions using example 13, and the results of table 7 and fig. 10 were obtained, reflecting the effect of different deposition temperatures on the deposition rate and the adhesion of the deposited layer. At 800 ℃, the deposition rate was very slow, with little rhenium deposition observed; the deposition rate increases with increasing reaction temperature. The deposition rate is obviously improved within the range of 850 ℃ to 1000 ℃, the speed of the range of 1000-1300 ℃ is relatively slowly increased, and when the temperature exceeds a certain range, the influence of the temperature on the deposition rate is retarded and not obvious. The deposition rate can reach 12.02 mu m per hour.
As shown in FIG. 10, the coating adhesion is greater than 100MPa in the range of 820-1300 ℃, and the general trend of the coating adhesion is that the coating adhesion increases firstly and then decreases with the increase of the temperature. At 800 ℃, the adhesion cannot be tested because the deposition rate is very slow and little rhenium deposition is observed; when the reaction temperature is higher than 800 ℃ to 1000 ℃, rhenium deposition is observed, and the adhesive force is obviously changed; the adhesive force of the coating is reduced within the range of 1000-1300 ℃, and is reduced to 113MPa at 1300 ℃. When the temperature is higher than 1300 ℃, the adhesive force of the coating is obviously reduced to be less than 100 MPa. When the reaction temperature is 850 ℃, the maximum adhesion value can reach 170 Pa. In comprehensive consideration, the reaction temperature is preferably within the range of 820-1300 ℃.
TABLE 7 Effect of reaction temperature on coating
Using the process conditions of example 13, chemical vapor deposition was carried out in accordance with the above-described steps (1) to (6) while changing only the reaction gas ratio, and for convenience of explanation, the flow rate of rhenium pentachloride was fixed to 4m3Other flow rates, with corresponding changes in deposition rate, may also be used. The results are shown in table 8 and fig. 11. When the carbon monoxide gas flow is 4m3And/h, namely when the volume ratio of rhenium pentachloride to carbon monoxide is 1:1, the thickness of the prepared coating is 120-136 mu m. The CO gas flow is increased to 8m3And/h is that when the volume ratio of the two is 1:2, the thickness of the prepared coating is 513-520 mu m. The CO gas flow rate continues to increase to 12m3When the volume ratio of the two is 1:3, the thickness of the prepared coating is 529 mu m, and partial gas directly flows through the surface of the green body without participating in the reaction, so that the efficiency of the reaction process is reduced. Keeping the volume ratio of rhenium pentachloride to carbon monoxide unchanged, and adjusting the argon flow to 4m3/h、8m3/h、12m3/h、20m3The deposition rate and the adhesion of the deposited layer fluctuate within a certain range. But a carrier gasToo large a flow rate, but rather reduces the deposition rate. In this embodiment, the adhesion to the deposition layer is greater than 100MPa at different flow rates of the reaction gases, and the influence of the change of the value is small.
TABLE 8 influence of the reaction gas ratio on the coating
Example 14
The materials and reagents used were as follows: an alumina cylindrical blank (the alumina content is more than 99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity rhenium pentachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 15 minutes, closing an exhaust valve, and evacuating residual gases and impurities which are required by non-reaction and are not required by non-reaction in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating an aluminum oxide cylindrical blank by distilled water, drying the aluminum oxide cylindrical blank for 5 hours at 105 ℃, and then putting the aluminum oxide cylindrical blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the surfaces are not overlapped and blocked;
(3) vacuumizing to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating gas required by non-reaction and gas and impurities required by non-reaction which enter in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to a vacuum state of 200Pa, maintaining the vacuum state of 200Pa for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 18000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 800 ℃;
(5) putting rhenium pentachloride into a gasification chamber, heating to 450 ℃, gasifying the rhenium pentachloride, introducing gasified rhenium pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the rhenium pentachloride to the carbon monoxide to the argon gas is 1: 3: 2, the flow rates are respectively 3 cubic meters per hour, 9 cubic meters per hour and 6 cubic meters per hour, after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to carry out chemical vapor deposition reaction on a blank body, and the reaction time is 1 hour; preparing an aluminum oxide/metal rhenium coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the silicon nitride/metal rhenium composite material which is prepared.
And carrying out performance test after proper heat treatment. The thickness of the rhenium coating of the prepared aluminum oxide/metal rhenium coating material is detected by using a metallographic microscope, the detection result shows that the thickness of the coating is 9 mu m, the adhesion of the rhenium coating of the prepared aluminum oxide/metal rhenium coating material is detected according to the adhesion test standard of ISO4624-2016 coatings, and the adhesion of the rhenium coating of the prepared aluminum oxide/metal rhenium coating material to a silicon nitride substrate is 165 MPa.
Example 15
The materials and reagents used were as follows: a silicon carbide fiber cylindrical blank (the carbon content is more than 99.99 percent, and the porosity is 85 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity rhenium pentachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a vacuum state of 100Pa, keeping the vacuum state of 100Pa for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 12 minutes, closing an exhaust valve, and evacuating residual gases and impurities which are not required by reaction and are not required by the reaction in the vapor deposition equipment through the steps;
(2) cleaning a silicon carbide fiber cylindrical blank by distilled water, removing dirt, drying at 150 ℃ for 4 hours, and then putting the silicon carbide fiber cylindrical blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the surfaces are not overlapped and blocked;
(3) vacuumizing to a 100Pa vacuum state, keeping the 100Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 12 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber and the vacuum pipelines;
(4) vacuumizing to a vacuum state of 100Pa, maintaining the vacuum state of 100Pa for 12 minutes, controlling the vacuum degree in the vapor deposition equipment to 19500Pa by a vacuum pump after the vapor deposition equipment is checked to be completely sealed, and simultaneously heating the temperature in the reaction chamber to 1000 ℃;
(5) putting rhenium pentachloride into a gasification chamber, heating to 380 ℃, gasifying the rhenium pentachloride, introducing gasified rhenium pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the rhenium pentachloride to the carbon monoxide to the argon gas is 1: 2: 2, the flow rates are respectively 2 cubic meters per hour, 4 cubic meters per hour and 4 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 500 hours; preparing a silicon carbide fiber/metal rhenium composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the silicon carbide/metal rhenium composite material which is prepared.
And carrying out performance test after proper heat treatment. The bending strength performance of the prepared material is tested according to the bending test standard of GB/T232-. The prepared carbon fiber/metal rhenium composite material is tested according to ISO/TR 26946-. The embodiment result shows that the technical scheme of the invention overcomes the defects of the existing method and can be suitable for preparing the high-performance metal rhenium composite material.
Example 16
The materials and reagents used were as follows: molybdenum metal square blanks (99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity rhenium pentachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a 800Pa vacuum state, keeping the 800Pa vacuum state for 20 minutes, checking that the vapor deposition equipment is sealed completely, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 20 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities and non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning a square molybdenum blank by distilled water, removing dirt, drying at 120 ℃ for 5 hours, and putting the square molybdenum blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the surfaces are not overlapped and blocked;
(3) vacuumizing to 800Pa vacuum state, keeping the 800Pa vacuum state for 20 minutes, checking that the vapor deposition equipment is sealed completely, then introducing argon to be filled to normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 20 minutes, closing an exhaust valve, and evacuating the gas required by non-reaction and the gas and impurities required by non-reaction which enter in the process of placing the blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to 800Pa vacuum state, maintaining the 800Pa vacuum state for 20 minutes, controlling the vacuum degree in the vapor deposition equipment to 20000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1100 ℃;
(5) putting rhenium pentachloride into a gasification chamber, heating to 520 ℃, gasifying, introducing gasified rhenium pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the rhenium pentachloride to the carbon monoxide to the argon gas is 1: 4: 2, the flow rates are respectively 3 cubic meters per hour, 12 cubic meters per hour and 6 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 1200 hours;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared metal rhenium material;
(7) and removing the metal molybdenum cylindrical blank of the material obtained by deposition through machining, and finally obtaining the pure metal rhenium material with the thickness of 12 mm.
And carrying out performance test after proper heat treatment. The bending strength performance of the prepared material is tested according to the bending test standard of GB/T232-. The prepared metal rhenium material is tested according to ISO/TR26946-3The purity of the material is tested by flame atomic absorption spectroscopy, and the test result shows that the purity of the metal rhenium material is 99.999 percent, which is the same as the true density of rhenium metal. The results of the examples show that the technical scheme of the invention overcomes the existing methodThe method is not enough, and can be suitable for preparing high-purity and high-performance metal rhenium materials.
Example 17
The chemical vapor deposition equipment is an alumina reaction chamber.
The materials and reagents used were as follows: a metallic titanium disc blank (99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity rhenium pentafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing chemical vapor deposition equipment to a 600Pa vacuum state, keeping the 600Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 15 minutes, closing an exhaust valve, and evacuating residual gases and impurities which are required by non-reaction and gases and impurities which are required by non-reaction in the vapor deposition equipment through the steps;
(2) cleaning a metallic titanium disc blank by distilled water, removing dirt, drying at 105 ℃ for 3 hours, and then putting into a reaction chamber to ensure that the surface to be deposited of the blank faces the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to 600Pa vacuum state, keeping the 600Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to be in a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber and the vacuum pipelines;
(4) vacuumizing to 600Pa vacuum state, maintaining the 600Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 15000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 900 ℃;
(5) putting rhenium pentafluoride into a gasification chamber, heating to 500 ℃ to gasify the rhenium pentafluoride, introducing gasified rhenium pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the rhenium pentafluoride, the carbon monoxide and the argon gas is 1: 3: 2, the flow rates are respectively 2 cubic meters per hour, 6 cubic meters per hour and 4 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 10 hours; preparing a metallic titanium/metallic rhenium coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared stainless steel/metal rhenium coating material.
And carrying out performance test after proper heat treatment. The thickness of the prepared rhenium coating of the metallic titanium/metallic rhenium coating material is detected by using a metallographic microscope, the detection result shows that the thickness of the prepared rhenium coating of the metallic titanium/metallic rhenium coating material is 115 mu m, the adhesion of the prepared rhenium coating of the stainless steel/metallic rhenium coating material is detected according to the adhesion test standard of ISO 4624-.
Using the process conditions of example 17, chemical vapor deposition was performed according to the above steps (1) to (6) while changing only the chamber temperature, resulting in variations in deposition rate and adhesion of the deposited layer at different deposition temperatures, as shown in fig. 12. At 800 ℃, the deposition rate was very slow, with little rhenium deposition observed; the deposition rate increases with increasing reaction temperature. When the temperature is increased from 820 ℃ to 850 ℃, the deposition rate is obviously improved, the speed is relatively slowly increased in the range of 850-1200 ℃, and when the temperature exceeds a certain range, the influence of the temperature on the deposition rate is retarded and not obvious. The adhesion of the deposited layer measured at different deposition temperatures is also shown in fig. 12. At 800 c, adhesion could not be tested because there was no deposited layer. The adhesive force is obviously improved at 820-850 ℃. The adhesive force of the coating is reduced within the range of 850-1200 ℃, and when the temperature is higher than 1200 ℃, the adhesive force of the coating is obviously reduced to be less than 100 MPa. In general terms, the reaction temperature is preferably in the range of820-1200 ℃. Chemical vapor deposition was carried out according to the above-described steps (1) to (6) with the preferred gas volume ratio of rhenium pentafluoride to carbon monoxide being 1:1 to 4 and the preferred gas volume ratio of rhenium pentafluoride to argon being 1:1 to 5, using the process parameters of example 17, with only the reaction gas ratios being varied. Preferred rhenium pentafluoride flow rates are in the range of 1 to 4m3H, preferred carbon monoxide flow rates are from 1 to 12m3H is used as the reference value. At a rhenium pentafluoride flux of 2m3For example, when the volume ratio of rhenium pentafluoride to carbon monoxide is 1:1, the average deposition rate is 6.2 μm/h; when the volume ratio of the two is 1:1.5, the average value of the deposition rate can reach 9.6 mu m/h; when the volume ratio of the two is 1:3, the average value of the deposition rate is 11.2 mu m/h; when the volume ratio of the two is 1:4, the average value of the deposition rate is 11.7 μm/h. The preferred flow rate of argon is 1m3/h-20m3Adjusting within a/h range, observing the influence of the gas proportion and the flow on the chemical deposition rate and the adhesive force of the deposition layer, wherein the deposition rate and the adhesive force of the deposition layer fluctuate within a certain range. The effect of the ratio of the reaction gases and the flow rate is described in detail in example 13 and will not be repeated here.
Example 18
The reaction chamber in the chemical vapor deposition equipment adopts an alumina reaction chamber.
The materials and reagents used were as follows: a porous carbon cylindrical blank (the carbon content is more than 99.999 percent, and the porosity is more than 96 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity rhenium pentafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 15 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a porous carbon cylindrical blank by distilled water, drying the blank for 5 hours at 180 ℃, and then putting the blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the blank through the steps;
(4) vacuumizing to a 500Pa vacuum state, maintaining the 500Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 17000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1100 ℃;
(5) putting rhenium pentafluoride into a gasification chamber, heating to 500 ℃ to gasify the rhenium pentafluoride, introducing gasified rhenium pentafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the rhenium pentafluoride, the carbon monoxide and the argon gas is 1: 1:1, the flow rates are respectively 3 cubic meters per hour, 3 cubic meters per hour and 3 cubic meters per hour, after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to carry out chemical vapor deposition reaction on a blank body, and the reaction time is 100 hours; preparing a porous carbon/metal rhenium composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared porous carbon/metal rhenium composite material.
And carrying out performance test after proper heat treatment. The prepared porous carbon/metal rhenium composite material is tested according to ISO/TR 26946-.
In the examples 13 to 18, the metal rhenium is detected by adopting flame atomic absorption spectroscopy, the content is over 99.999 percent, and the surface appearance of the coating is observed by adopting a scanning electron microscope without cracking. Preferably, in the above examples 13-18, the vacuum degree in the vapor deposition apparatus is controlled by the vacuum pump to the vacuum degree of 15000-20000Pa, and the variation of the vacuum degree also has an influence on the deposition rate of the present invention. The deposition rate is increased along with the increase of the gas pressure of the reaction chamber; however, the degree of vacuum reaches a certain range, and the deposition rate changes slowly. The change of vacuum degree has no obvious change to the composition of the deposition layer, but has certain influence on the preferential growth. The test results of the above embodiments show that, compared with the existing method, the product prepared by the invention overcomes the defects of the prior art, remarkably improves the mechanical properties of the material, and can be suitable for preparing high-performance metal tantalum coating or tantalum composite material in industrialized production.
Preparation of (tetra) niobium, examples 19 to 24
In the prior art, hydrogen is used as a reducing gas in the chemical vapor deposition of niobium, and the reaction equation is as follows:
gasification reaction
NbCl5(s)—→NbCl5(g)
Reduction reaction
2NbCl5+5H2—→2Nb+10HCl
Combining literature and experimental practical conditions to obtain one of the kinetic models of chemical vapor deposition niobium: at a temperature above 1000 ℃ NbCl5Starting the conversion to NbCl under the action of hydrogen4，NbCl4The conversion rate is not high, and the specific process can be expressed as follows:
2NbCl5+H2—→2NbCl4+2HCl
2NbCl4+4H2—→2Nb+8HCl
the temperature at which the further reduction of the intermediate niobium chloride by hydrogen takes place varies depending on the hydrogen content of the reaction gas. The invention considers carbon monoxide as reducing gas, fundamentally solves the problem of hydrogen induced cracking, and simultaneously reduces the step of dehydrogenation treatment. The reaction equations involved in the invention are respectively:
2NbCl5+5CO→2Nb+5COCl2
2NbF5+5CO→2Nb+5COF2
examples 19-24 chemical vapor deposition of niobium metal was carried out using different blanks and the same procedure was followed, with examples 19-22 using niobium pentachloride as the reactant and examples 23 and 24 using niobium pentafluoride as the reactant. The chemical vapor deposition equipment is an alumina reaction chamber.
Example 19
The materials and reagents used were as follows: a silicon carbide ceramic disc blank (99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity niobium pentachloride (99.99%). The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to an 800Pa vacuum state, keeping the 800Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating silicon carbide ceramic disc blanks by distilled water, drying for 6 hours at 150 ℃, and then putting the silicon carbide ceramic disc blanks into a reaction chamber to ensure that the surfaces to be deposited of the blanks are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to 800Pa vacuum state, keeping the 800Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to be in a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber and the vacuum pipelines;
(4) vacuumizing to 800Pa vacuum state, maintaining the 800Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 14000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1000 ℃;
(5) putting niobium pentachloride into a gasification chamber, heating to 350 ℃, gasifying the niobium pentachloride, introducing the gasified niobium pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the niobium pentachloride gas to the carbon monoxide gas to the argon gas is 1: 2: 2, the flow rates are respectively 4 cubic meters per hour, 8 cubic meters per hour and 8 cubic meters per hour, after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to carry out chemical vapor deposition reaction on a blank body, and the reaction time is 50 hours; preparing a silicon carbide/metal niobium coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the silicon carbide/metal niobium coating material which is prepared.
The product was tested after appropriate heat treatment. The thickness of the niobium coating of the prepared silicon carbide/niobium metal coating material is detected by using a metallographic microscope, and the detection result shows that the thickness of the coating is 523 mu m. The adhesion of the prepared silicon carbide/metal niobium coating material niobium coating is detected according to the ISO4624-2016 coating adhesion test standard, the adhesion of the metal niobium coating and the silicon carbide substrate is 137MPa through the test, compared with the existing method, the adhesion of the coating is obviously improved, and the adhesion of the coating is generally less than 100MPa through other chemical vapor deposition niobium technical schemes. FIG. 17 shows a gold phase diagram of the surface of a niobium metal layer, at 2000 times magnification, no cracking was observed.
Using the process parameters of example 19, only the chamber temperature, i.e., the deposition temperature, was varied according to the above steps (1) - (6) to obtain the deposition rates and the adhesion variations of the deposited layers at different deposition temperatures, as shown in table 9 and fig. 14.
It can be seen from fig. 14 that at 750 ℃, the deposition rate is very slow, and niobium deposition is hardly observed; the deposition rate increases with increasing reaction temperature. The deposition rate is in a slow increasing trend within the range of 800-850 ℃; in the range of 850-1000 ℃, the deposition rate is obviously improved, the speed in the range of 1000-1200 ℃ is relatively slowly increased, and when the temperature exceeds a certain range, the influence of the temperature on the deposition rate becomes slow and is not obvious. The deposition rate can reach 11.76 mu m/h.
As shown in FIG. 14, the coating adhesion is greater than 100MPa within the range of 800-1200 ℃, the general trend of the coating adhesion is increased along with the increase of the temperature, and the coating adhesion is increased firstly and then decreased within a certain temperature range. When the temperature is 750 ℃, the adhesion cannot be tested because the deposition rate is very slow and niobium deposition is hardly observed; within the range of 800-850 ℃, niobium deposition is observed, and the adhesive force is obviously changed; within the range of 850-1200 ℃, the adhesive force of the coating is in a descending trend, and the descending is slow and not obvious. When the temperature is higher than 1200 ℃, the adhesive force of the coating is obviously reduced to be lower than 100 MPa.
The observation of the surface morphology shows that the reaction temperature has no obvious change on the composition of the niobium deposition layer and has certain influence on the preferred growth; the grain size of the niobium deposition layer increases with the increase of the temperature, and when the temperature is higher than 1200 ℃, the grain coarsening phenomenon is caused. In comprehensive consideration, the preferable range of the reaction temperature is 800-1200 ℃.
TABLE 9 Effect of reaction temperature on coating
Using the process conditions of example 19, only by varying the reaction gas ratio according to the above-mentioned steps (1) to (6), it was found that the effect on the chemical vapor deposition results was also exerted, namelyTo facilitate explanation, the flow rate of niobium pentachloride was fixed to 4m3Other flow rates, with corresponding changes in deposition rate, may also be used. The results are shown in Table 10 and FIG. 15.
From FIG. 15, when the volume ratio of rhenium pentachloride to carbon monoxide is 1:1, the thickness of the prepared coating is 111-123 μm, and the average value of the calculated deposition rate is 2.4 μm/h; when the volume ratio of the two is 1:2, the thickness of the prepared coating is 523-528 mu m, and the average value of the calculated deposition rate is 10.5 mu m/h; when the volume ratio of the two is 1:3, the coating thickness is 535 μm, and the average calculated deposition rate is 10.7 μm/h. Keeping the volume ratio of rhenium pentachloride to carbon monoxide unchanged, and adjusting the argon flow to 4m3/h、8m3/h、12m3/h、20m3The deposition rate and the adhesion of the deposited layer fluctuate within a certain range. However, the flow rate of the carrier gas is too large, which in turn reduces the deposition rate. In this embodiment, the adhesion to the deposition layer is greater than 100MPa at different flow rates of the reaction gases, and the influence of the change of the value is small.
TABLE 10 influence of the reaction gas ratio on the coating
Example 20
The materials and reagents used were as follows: a quartz glass cylindrical body (silica content greater than 99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity niobium pentachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a vacuum state of 100Pa, keeping the vacuum state of 100Pa for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 5 minutes, closing an exhaust valve, and evacuating residual gases and impurities which are not required by reaction and are not required by the reaction in the vapor deposition equipment through the steps;
(2) cleaning a quartz glass cylindrical blank by distilled water, removing dirt, drying at 105 ℃ for 5 hours, and then putting into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the surfaces are not overlapped and blocked;
(3) vacuumizing to a 100Pa vacuum state, keeping the 100Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 5 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the blank through the steps;
(4) vacuumizing to a vacuum state of 100Pa, maintaining the vacuum state of 100Pa for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 12000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 820 ℃;
(5) putting niobium pentachloride into a gasification chamber, heating to 500 ℃ to gasify the niobium pentachloride, introducing gasified niobium pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the niobium pentachloride gas to the carbon monoxide gas to the argon gas is 1: 2: 3, the flow rates are respectively 2 cubic meter/h, 4 cubic meter/h and 6 cubic meter/h, after fully mixing in a gas mixing tank, the mixture is introduced into a reaction chamber to carry out chemical vapor deposition reaction on the blank body for 1 hour; preparing a glass/metal niobium coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared glass/metal niobium composite material.
After appropriate heat treatment, the test was carried out. The thickness of the prepared niobium coating of the glass/metal niobium coating material is detected by using a metallographic microscope, the detection result shows that the thickness of the coating is 10 mu m, the adhesion of the prepared niobium coating of the glass/metal niobium coating material is detected according to the adhesion test standard of ISO4624-2016 coating, and the adhesion of the metal niobium coating and a glass substrate is 116MPa through the test.
Example 21
The materials and reagents used were as follows: a carbon fiber cylindrical blank (the carbon content is more than 99.99 percent, and the porosity is 85 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity niobium pentachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual gases and impurities which are required by non-reaction and are not required by non-reaction in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a carbon fiber cylindrical blank by distilled water, drying the carbon fiber cylindrical blank for 10 hours at the temperature of 150 ℃, and then putting the carbon fiber cylindrical blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the carbon fiber cylindrical blank is not overlapped with the reaction gas outlet and is not blocked;
(3) vacuumizing to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating gas required by non-reaction and gas and impurities required by non-reaction which enter in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to 200Pa vacuum state, maintaining the 200Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is well sealed, controlling the vacuum degree in the vapor deposition equipment to 13500Pa by using a vacuum pump, and simultaneously heating the temperature in the reaction chamber to 1000 ℃;
(5) putting niobium pentachloride into a gasification chamber, heating to 500 ℃ to gasify the niobium pentachloride, introducing gasified niobium pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the niobium pentachloride gas to the carbon monoxide gas to the argon gas is 1: 1.5: 3, the flow rates are respectively 2 cubic meters per hour, 3 cubic meters per hour and 6 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 500 hours; preparing a carbon fiber/metal niobium composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared porous carbon/metal niobium composite material.
After appropriate heat treatment, the test was carried out. The bending strength performance of the prepared material is tested according to the bending test standard of GB/T232-. The prepared carbon fiber/metal niobium composite material is tested according to ISO/TR26946-2011 porosity test standard, and the test result shows that the porosity of the carbon fiber/metal niobium composite material is 5%. The embodiment result shows that the technical scheme of the invention overcomes the defects of the existing method and can be suitable for preparing the high-performance metal niobium composite material.
Example 22
The materials and reagents used were as follows: a 316L stainless steel cylindrical blank; high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity niobium pentachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities and non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning a 316L stainless steel cylindrical blank by distilled water, removing dirt, drying at 200 ℃ for 10 hours, and then putting into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blank is not overlapped and blocked;
(3) vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating gas required by non-reaction and gas and impurities required by non-reaction which enter in the process of placing a blank of the vapor deposition equipment into the blank through the steps;
(4) vacuumizing to 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, controlling the vacuum degree in the vapor deposition equipment to 15000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 800 ℃;
(5) putting niobium pentachloride into a gasification chamber, heating to 500 ℃ to gasify the niobium pentachloride, introducing gasified niobium pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the niobium pentachloride gas to the carbon monoxide gas to the argon gas is 1: 4: 4, the flow rates are respectively 2 cubic meters per hour, 8 cubic meters per hour and 8 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 1000 hours;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared metal niobium material;
(7) and removing the 316L stainless steel cylindrical blank of the material obtained by deposition through machining, and finally obtaining the pure metal niobium material with the thickness of 10 mm.
After appropriate heat treatment, the test was carried out. Bending the prepared material according to the bending test standard of GB/T232-2010 metal materialThe bending strength performance is tested, according to the GB/T22315-2008 metal material elastic modulus and Poisson's ratio test method standard, the elastic modulus performance of the prepared material is tested, the elastic modulus of the prepared metal niobium material is 235GPa, the bending strength is 883Mpa, compared with the existing method, the method overcomes hydrogen embrittlement, and the mechanical property of the material is obviously improved. The prepared niobium metal material is tested according to ISO TR26946-3The purity of the material is tested by adopting flame atomic absorption spectroscopy, and the test result shows that the purity of the metal niobium material is 99.999 percent. The embodiment result shows that the technical scheme of the invention overcomes the defects of the existing method and can be suitable for preparing high-purity and high-performance metal niobium materials.
Example 23
The materials and reagents used were as follows: a 316L stainless steel rivet; high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity niobium pentafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing chemical vapor deposition equipment to a 900Pa vacuum state, keeping the 900Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 12 minutes, closing an exhaust valve, and evacuating residual gases and impurities which are required by non-reaction and gases and impurities which are required by non-reaction in the vapor deposition equipment through the steps;
(2) cleaning 316L stainless steel rivet blanks by distilled water, removing dirt, drying at 120 ℃ for 7 hours, and then putting into a reaction chamber to ensure that the surfaces to be deposited of the blanks are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 900Pa vacuum state, keeping the 900Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 12 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber and the vacuum pipelines;
(4) vacuumizing to 900Pa vacuum state, maintaining the 900Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 12000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 850 ℃;
(5) putting niobium pentafluoride into a gasification chamber, heating to 300 ℃, gasifying the niobium pentafluoride, introducing the gasified niobium pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the niobium pentafluoride to the carbon monoxide to the argon gas is 1: 1.5: 2, the flow rates are respectively 2 cubic meters per hour, 3 cubic meters per hour and 4 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 10 hours; preparing a stainless steel/metal niobium coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared stainless steel/metal niobium coating material.
The product is tested after proper heat treatment, a metallographic microscope is used for detecting the thickness of the prepared stainless steel/metal niobium coating material niobium coating, the detection result shows that the thickness of the prepared stainless steel/metal niobium coating material niobium coating is 120 mu m, the adhesion of the prepared stainless steel/metal niobium coating material niobium coating is detected according to the ISO4624-2016 coating adhesion test standard, the adhesion of the metal niobium coating and a stainless steel matrix is 123MPa through testing, and compared with the existing method, the adhesion of the coating is remarkably improved.
FIG. 16 is a graph of the effect of different deposition temperatures on deposition rates for niobium pentafluoride on green bodies of example 23. At 750 ℃, the deposition rate was very slow, with little niobium deposition observed; the deposition rate increases with increasing reaction temperature. In the range of 800-850 ℃, the deposition rate is obviously improved, the speed in the range of 850-1200 ℃ is relatively slowly increased, and when the temperature exceeds a certain range, the influence of the temperature on the deposition rate becomes slow and is not obvious. The deposition rate can reach 12.8 mu m/h.
As shown in fig. 16, at 750 ℃, adhesion could not be tested because there was no deposited layer. When the temperature is more than 800 to 850 ℃, the deposition of niobium is observed, so the adhesion is remarkably improved. The adhesive force of the coating is reduced within the range of 850-1200 ℃, and when the temperature is higher than 1200 ℃, the adhesive force of the coating is obviously reduced to be less than 100 MPa. When the reaction temperature is 850 ℃, the maximum adhesion value can reach 126 MPa.
The observation of the surface morphology shows that the reaction temperature has no obvious change on the composition of the niobium deposition layer and has certain influence on the preferred growth; the grain size of the niobium deposit increases with increasing temperature. In comprehensive consideration, the reaction temperature is preferably in the range of 800-1180 ℃.
Chemical vapor deposition was carried out in accordance with the above-described steps (1) to (6) while changing only the reaction gas ratio under the process parameters using example 23, with the preferred gas volume ratio of niobium pentafluoride to carbon monoxide being 1:1 to 4 and the preferred gas volume ratio of tantalum pentafluoride to argon being 1:1 to 4. The preferred flow rate of niobium pentafluoride is 2 to 6m3H is used as the reference value. The preferred carbon monoxide flow rate is 2-24m3Adjusting within the range of/h. The preferred flow rate of argon is in the range of 2-24m3The effect of adjusting the gas ratio and flow rate on the chemical deposition rate and the adhesion of the deposited layer in the/h range is observed and described in detail in the implementation 19, which is not repeated here.
Example 24
The materials and reagents used were as follows: a porous carbon square blank (the carbon content is more than 99.999 percent, and the porosity is more than 96 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity niobium pentafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for evacuation, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a porous carbon square blank by distilled water, drying the blank for 5 hours at 200 ℃, and then putting the blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 15000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1200 ℃;
(5) putting niobium pentafluoride into a gasification chamber, heating to 300 ℃, gasifying the niobium pentafluoride, introducing the gasified niobium pentafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the niobium pentafluoride to the carbon monoxide to the argon gas is 1: 4: 4, the flow rates are respectively 2 cubic meters per hour, 8 cubic meters per hour and 8 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 100 hours; preparing a porous carbon/metal niobium composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared porous carbon/metal niobium composite material.
And carrying out performance test after proper heat treatment. The prepared porous carbon/metal niobium composite material is tested according to ISO TR 26946-.
The flame atomic absorption spectrum detection adopted in the embodiments 19 to 24 shows that the film structures are all metal niobium, the content is more than 99.999 percent, and the surface appearance of the coating observed by a scanning electron microscope has no cracking phenomenon. Preferably, the above embodiment controls the vacuum degree in the vapor deposition apparatus to 13000-15000Pa by the vacuum pump, and the change of the vacuum degree also has an influence on the deposition rate of the present invention. The deposition rate is increased along with the increase of the gas pressure of the reaction chamber; however, the degree of vacuum reaches a certain range, and the deposition rate changes slowly. The change of vacuum degree has no obvious change to the composition of the deposition layer, but has certain influence on the preferential growth. The test results of the above examples show that compared with the existing method, the product prepared by the invention overcomes the defects of the prior art, remarkably improves the mechanical properties of the material, and can be suitable for preparing high-performance metal niobium coatings or niobium composite materials in industrialized production.
Preparation of (penta) molybdenum, examples 25-30
In the prior art, the chemical vapor deposition of molybdenum usually uses hydrogen as a reducing gas, and the reaction equation is as follows:
2MoCl5+5H2——→2Mo+10HCl
combining literature and experimental practical conditions to obtain one of the kinetic models of chemical vapor deposition molybdenum: at a temperature above 1000 ℃ MoCl5Starting the conversion to MoCl under the action of hydrogen3，MoCl3The conversion is simple substance Mo, but the conversion rate is not high, and the specific process can be expressed as follows:
MoCl5+H2——→MoCl3+2HCl
2MoCl3+3H2——→2Mo+6HCl
this process can cause hydrogen embrittlement of the film, i.e., hydrogen induced cracking. The prior art generally adds a dehydrogenation step to stabilize the properties of the film layer, thereby reducing the risk of hydrogen induced cracking. The invention considers carbon monoxide as reducing gas, fundamentally solves the problem of hydrogen induced cracking, and simultaneously reduces the step of dehydrogenation treatment. The reaction equation involved in the invention is as follows:
2MoCl5+5CO→2Mo+5COCl2
2MoF5+5CO→2Mo+5COF2
examples 25-30 chemical vapor deposition of molybdenum metal was carried out using different blanks and the same procedure was followed, with examples 25-28 using molybdenum pentachloride as the reactant and examples 29 and 30 using molybdenum pentafluoride as the reactant.
Example 25
The materials and reagents used were as follows: a silicon carbide ceramic disc blank (99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity molybdenum pentachloride (99.99%). The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to a 800Pa vacuum state, keeping the 800Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon gas to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon gas, opening a gas valve to evacuate, continuing introducing the argon gas for 10 minutes, closing a gas exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating silicon carbide ceramic disc blanks by distilled water, drying for 6 hours at 150 ℃, and then putting the silicon carbide ceramic disc blanks into a reaction chamber to ensure that the surfaces to be deposited of the blanks are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to 800Pa vacuum state, keeping the 800Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to be in a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to 800Pa vacuum state, maintaining the 800Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 14000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1000 ℃;
(5) putting molybdenum pentachloride into a gasification chamber, heating to 350 ℃, gasifying the molybdenum pentachloride, introducing the gasified molybdenum pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the molybdenum pentachloride gas to the carbon monoxide gas to the argon gas is 1: 2: 2, the flow rates are respectively 4 cubic meters per hour, 8 cubic meters per hour and 8 cubic meters per hour, after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to carry out chemical vapor deposition reaction on a blank body, and the reaction time is 50 hours; preparing a silicon carbide/metal molybdenum coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the silicon carbide/metal molybdenum coating material which is prepared.
The product was tested after appropriate heat treatment. The thickness of the prepared molybdenum coating of the silicon carbide/metal molybdenum coating material is detected by using a metallographic microscope, and the detection result shows that the thickness of the coating is 480 mu m. The adhesion of the prepared silicon carbide/metal molybdenum coating material molybdenum coating is detected according to ISO4624-2016 coating adhesion test standard, the adhesion of the metal molybdenum coating and the silicon carbide substrate is 146MPa through test, compared with the existing method, the adhesion of the coating is remarkably improved, and the adhesion of the coating is generally less than 100MPa through other chemical vapor deposition molybdenum technical schemes. FIG. 21 shows a gold phase diagram of the surface of a molybdenum metal fault, wherein the magnification is 500 times, and no cracking phenomenon is observed.
Using the process conditions of example 25, chemical vapor deposition was performed according to the above steps (1) to (6) while changing only the chamber temperature, i.e., the deposition temperature, to obtain the deposition rate and the variation of the adhesion of the deposited layer at different deposition temperatures, as shown in table 11 and fig. 18, at 700 ℃, the deposition rate was very slow, and molybdenum deposition was hardly observed; the deposition rate increases with increasing reaction temperature. The deposition rate is obviously improved within the range of 850-1150 ℃, the speed is relatively slowly increased within the range of 1000-1200 ℃, and the deposition rate begins to be reduced when the temperature exceeds the range of 1200-1300 ℃. The deposition rate can reach 10.4 mu m/h.
As shown in FIG. 18, the general trend of the coating adhesion is increased with the temperature increase in the range of 770-1300 ℃, and the coating adhesion is increased and then decreased in a certain temperature range. At 700 ℃, the adhesion force cannot be tested because the deposition rate is very slow and molybdenum deposition is hardly observed; molybdenum deposition is observed within the range of 770-850 ℃, and the adhesive force is obviously changed; within the range of 850-1150 ℃, the adhesive force of the coating is in a descending trend, and the descending is slow and not obvious. When the temperature is higher than 1200 ℃, the adhesive force of the coating is obviously reduced to be lower than 100MPa, for example, the adhesive force of the prepared coating is 76MPa when the reaction temperature is 1300 ℃. When the reaction temperature is 850 ℃, the maximum adhesion value can reach 156 MPa.
The observation of the surface appearance shows that the reaction temperature has no obvious change on the composition of the molybdenum deposition layer, but has certain influence on the preferential growth; the grain size of the molybdenum deposition layer is increased along with the increase of the temperature, and the preferable range of the reaction temperature is 770-1200 ℃ in comprehensive consideration.
TABLE 11 Effect of reaction temperature on coating
Chemical vapor deposition was carried out according to the above-described steps (1) to (6) with only changing the reaction gas ratio under the process conditions using example 25, and the results of table 12 and fig. 19 were obtained. For convenience of explanation, the flow rate of molybdenum pentachloride was fixed to 4m3Other flow rates, with corresponding changes in deposition rate, may also be used. The results are shown in FIG. 19. From figure 19 it can be calculated that when the volume ratio of molybdenum pentachloride to carbon monoxide is 1:1,the thickness of the prepared coating is 123-141 mu m; when the volume ratio of the two is 1:2, the thickness of the prepared coating is 502-550 mu m; when the volume ratio of the two is 1:3, the thickness of the coating layer is 552 μm. Keeping the volume ratio of rhenium pentachloride to carbon monoxide unchanged, and adjusting the argon flow to 4m3/h、8m3/h、12m3/h、20m3The deposition rate and the adhesion of the deposited layer fluctuate within a certain range. However, the flow rate of the carrier gas is too large, which in turn reduces the deposition rate. In this embodiment, the adhesion to the deposition layer is greater than 100MPa at different flow rates of the reaction gases, and the influence of the change of the value is small.
TABLE 12 Effect of the reaction gas ratio on the coating
Example 26
The materials and reagents used were as follows: a quartz glass cylindrical body (silica content greater than 99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity molybdenum pentachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a vacuum state of 100Pa, keeping the vacuum state of 100Pa for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 5 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning a quartz glass cylindrical blank by distilled water, removing dirt, drying at 105 ℃ for 5 hours, and then putting into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the surfaces are not overlapped and blocked;
(3) vacuumizing to a 100Pa vacuum state, keeping the 100Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 5 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to a 100Pa vacuum state, keeping the 100Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 6000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 770 ℃;
(5) putting molybdenum pentachloride into a gasification chamber, heating to 500 ℃ to gasify the molybdenum pentachloride, introducing gasified molybdenum pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the molybdenum pentachloride gas to the carbon monoxide gas to the argon gas is 1: 2: 2, the flow rates are respectively 4 cubic meters per hour, 8 cubic meters per hour and 8 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 1 hour; preparing a glass/metal molybdenum coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared glass/metal molybdenum composite material.
After appropriate heat treatment, the test was carried out. The thickness of the prepared molybdenum coating of the glass/metal molybdenum coating material is detected by using a metallographic microscope, the detection result shows that the thickness of the coating is 10 mu m, the adhesion of the prepared molybdenum coating of the glass/metal molybdenum coating material is detected according to the adhesion test standard of ISO4624-2016 coating, and the adhesion of the metal molybdenum coating and a glass substrate is 126MPa through the test.
Example 27
The materials and reagents used were as follows: a carbon fiber cylindrical blank (the carbon content is more than 99.99 percent, and the porosity is 85 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity molybdenum pentachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a carbon fiber cylindrical blank by distilled water, drying the carbon fiber cylindrical blank for 10 hours at the temperature of 150 ℃, and then putting the carbon fiber cylindrical blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the carbon fiber cylindrical blank is not overlapped with the reaction gas outlet and is not blocked;
(3) vacuumizing to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to 200Pa vacuum state, maintaining the 200Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is well sealed, controlling the vacuum degree in the vapor deposition equipment to 13500Pa by using a vacuum pump, and simultaneously heating the temperature in the reaction chamber to 1000 ℃;
(5) putting molybdenum pentachloride into a gasification chamber, heating to 550 ℃, gasifying the molybdenum pentachloride, introducing the gasified molybdenum pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the molybdenum pentachloride gas to the carbon monoxide gas to the argon gas is 1: 1.5: 3, the flow rates are respectively 2 cubic meters per hour, 3 cubic meters per hour and 6 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 500 hours; preparing a carbon fiber/metal molybdenum composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared porous carbon/metal molybdenum composite material.
After appropriate heat treatment, the test was carried out. The bending strength performance of the prepared material is tested according to the bending test standard of GB/T232-. The prepared carbon fiber/metal molybdenum composite material is tested according to the ISOTR 26946-2011 porosity test standard, and the test result shows that the porosity of the carbon fiber/metal molybdenum composite material is 5%. The embodiment result shows that the technical scheme of the invention overcomes the defects of the existing method and can be suitable for preparing the high-performance metal molybdenum composite material.
Example 28
The materials and reagents used were as follows: a 316L stainless steel cylindrical blank; high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity molybdenum pentachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning a 316L stainless steel cylindrical blank by distilled water, removing dirt, drying at 200 ℃ for 10 hours, and then putting into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blank is not overlapped and blocked;
(3) vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, controlling the vacuum degree in the vapor deposition equipment to 9000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 770 ℃;
(5) putting molybdenum pentachloride into a gasification chamber, heating to 550 ℃, gasifying the molybdenum pentachloride, introducing the gasified molybdenum pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the molybdenum pentachloride gas to the carbon monoxide gas to the argon gas is 1: 2: 3, the flow rates are respectively 3 cubic meters per hour, 6 cubic meters per hour and 9 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 1000 hours;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared metal molybdenum material;
(7) and removing the 316L stainless steel cylindrical blank of the deposited material by machining to finally prepare the pure metal molybdenum material with the thickness of 10 mm.
After appropriate heat treatment, the test was carried out. The bending strength performance of the prepared material is tested according to the bending test standard of GB/T232-. According to ISO TR26946-And (3) performing tests, wherein the test result shows that the porosity of the metal molybdenum material is 0, and the metal molybdenum material is 10.23g/cm calculated according to the method of mass/volume-density3The material purity is tested by adopting flame atomic absorption spectroscopy, and the test result shows that the purity of the metal molybdenum material is 99.999 percent. The embodiment result shows that the technical scheme of the invention overcomes the defects of the existing method and can be suitable for preparing high-purity and high-performance metal molybdenum materials.
Example 29
The materials and reagents used were as follows: a 316L stainless steel rivet; high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity molybdenum pentafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing chemical vapor deposition equipment to a 900Pa vacuum state, keeping the 900Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for evacuation, continuing introducing the argon for 12 minutes, closing an exhaust valve, and evacuating residual gases and impurities required by non-reaction in the vapor deposition equipment through the steps;
(2) cleaning 316L stainless steel rivet blanks by distilled water, removing dirt, drying at 120 ℃ for 7 hours, and then putting into a reaction chamber to ensure that the surfaces to be deposited of the blanks are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 900Pa vacuum state, keeping the 900Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 12 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to 900Pa vacuum state, maintaining the 900Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 6000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 850 ℃;
(5) putting molybdenum pentafluoride into a gasification chamber, heating to 550 ℃, gasifying the molybdenum pentafluoride, introducing the gasified molybdenum pentachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the molybdenum pentafluoride to the carbon monoxide to the argon gas is 1: 1.5: 2, the flow rates are respectively 4 cubic meters per hour, 6 cubic meters per hour and 8 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 10 hours; preparing a stainless steel/metal molybdenum coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared stainless steel/metal molybdenum coating material.
The product was tested after appropriate heat treatment. The thickness of the molybdenum coating of the prepared stainless steel/metal molybdenum coating material is detected by using a metallographic microscope, the detection result shows that the thickness of the molybdenum coating of the prepared stainless steel/metal molybdenum coating material is 120 mu m, the adhesion of the molybdenum coating of the prepared stainless steel/metal molybdenum coating material is detected according to the ISO4624-2016 coating adhesion test standard, the adhesion of the metal molybdenum coating and a stainless steel substrate is 142MPa through the test, and compared with the existing method, the adhesion of the coating is remarkably improved.
Using the process parameters of example 29, only the chamber temperature, i.e., the deposition temperature, was varied according to the above steps (1) - (6) to obtain variations in deposition rate and adhesion of the deposited layer at different deposition temperatures, as shown in fig. 20. At 700 ℃, the deposition rate was very slow, with almost no molybdenum deposition observed; the deposition rate increases with increasing reaction temperature. In the range of 770-850 ℃, the deposition rate is obviously improved, the speed in the range of 850-1200 ℃ is relatively slowly increased, and when the temperature exceeds a certain range, the influence of the temperature on the deposition rate is retarded and not obvious. The deposition rate can reach 13.9 mu m/h.
The effect of different deposition temperatures on the adhesion of the deposited layers is also shown in fig. 20. At 700 c, adhesion could not be tested because there was no deposited layer. When the temperature is more than 770 ℃ to 850 ℃, molybdenum deposition is observed, and the adhesion is remarkably improved. The adhesive force of the coating is reduced within the range of 850-1200 ℃, and when the temperature is higher than 1200 ℃, the adhesive force of the coating is obviously reduced to be less than 100 MPa. When the reaction temperature is 850 ℃, the maximum adhesion value can reach 142 MPa.
The observation of the surface appearance shows that the reaction temperature has no obvious change on the composition of the molybdenum deposition layer, but has certain influence on the preferential growth; the grain size of the molybdenum deposition layer increases with the increase of the temperature. In comprehensive consideration, the preferable range of the reaction temperature is 770-1200 ℃.
Chemical vapor deposition was carried out according to the above-described steps (1) to (6) while changing only the reaction gas ratio under the process parameters using example 29, such that the preferred gas volume ratio of molybdenum pentafluoride to carbon monoxide was 1:1 to 2 and the preferred gas volume ratio of molybdenum pentafluoride to argon was 1:1 to 3. The preferred flow rate of molybdenum pentafluoride is 2-6m3H is used as the reference value. The preferred carbon monoxide flow is in the range of 2 to 12m3Adjusting within the range of/h. The preferred flow rate of argon is in the range of 2-18m3The effect of the gas ratio and flow rate on the chemical deposition rate and adhesion of the deposited layer was observed, and the effect of the reaction gas flow rate and ratio was described in detail in example 25 and will not be repeated here.
Example 30
The materials and reagents used were as follows: a porous carbon square blank (the carbon content is more than 99.999 percent, and the porosity is more than 96 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity molybdenum pentafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for evacuation, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a porous carbon square blank by distilled water, drying the blank for 5 hours at 200 ℃, and then putting the blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 9000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1150 ℃;
(5) putting molybdenum pentafluoride into a gasification chamber, heating to 350 ℃ to gasify the molybdenum pentafluoride, introducing gasified molybdenum pentafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the molybdenum pentafluoride gas to the carbon monoxide gas to the argon gas is 1: 2: 3, the flow rates are respectively 2 cubic meters per hour, 4 cubic meters per hour and 6 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 100 hours; preparing a porous carbon/metal molybdenum composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared porous carbon/metal molybdenum composite material.
And carrying out performance test after proper heat treatment. The prepared porous carbon/metal molybdenum composite material is tested according to ISO TR 26946-.
The flame atomic absorption spectrum test adopted in the examples 25-30 shows that the film structures are all metallic molybdenum, the content is more than 99.999 percent, and the surface appearance of the coating observed by a scanning electron microscope has no cracking phenomenon. Preferably, the above embodiment controls the vacuum degree in the vapor deposition equipment to 6000-9000Pa by the vacuum pump, and the change of the vacuum degree also has influence on the deposition rate of the invention. The deposition rate is increased along with the increase of the gas pressure of the reaction chamber; however, the degree of vacuum reaches a certain range, and the deposition rate changes slowly. The change of vacuum degree has no obvious change to the composition of the deposition layer, but has certain influence on the preferential growth. The test results of the above embodiments show that, compared with the existing method, the product prepared by the invention overcomes the defects of the prior art, obviously improves the mechanical properties of the material, and can be suitable for preparing high-performance metal molybdenum coatings or molybdenum composite materials in industrialized production.
Preparation of (Hexa) hafnium, example 31-example 36
In the prior art, the chemical vapor deposition of hafnium generally uses hydrogen as reducing gas, and the reaction equation is as follows:
HfCl4+2H2——→Hf+4HCl
this process can cause hydrogen embrittlement of the film, i.e., hydrogen induced cracking. The prior art generally adds a dehydrogenation step to stabilize the properties of the film layer, thereby reducing the risk of hydrogen induced cracking. The invention considers carbon monoxide as reducing gas, fundamentally solves the problem of hydrogen induced cracking, and simultaneously reduces the step of dehydrogenation treatment. The reaction equation involved in the invention is as follows:
HfCl4+2CO→Hf+2COCl2
HfF4+2CO→Hf+2COF2
examples 31-36 chemical vapor deposition of hafnium metal was carried out using different blanks, the same procedure, wherein examples 31-34 used hafnium tetrachloride as the reactant and examples 35 and 36 used hafnium tetrafluoride as the reactant.
Example 31
The materials and reagents used were as follows: a silicon carbide ceramic disc blank (99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity hafnium tetrachloride (99.99%). The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to a 800Pa vacuum state, keeping the 800Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon gas to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon gas, opening a gas valve to evacuate, continuing introducing the argon gas for 10 minutes, closing a gas exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating silicon carbide ceramic disc blanks by distilled water, drying for 6 hours at 150 ℃, and then putting the silicon carbide ceramic disc blanks into a reaction chamber to ensure that the surfaces to be deposited of the blanks are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to 800Pa vacuum state, keeping the 800Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to be in a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 15 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to 800Pa vacuum state, maintaining the 800Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 14000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1000 ℃;
(5) putting hafnium tetrachloride into a gasification chamber, heating to 350 ℃, gasifying the hafnium tetrachloride, introducing the gasified hafnium tetrachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of the hafnium tetrachloride to the carbon monoxide to the argon gas is 1: 2: 2, the flow rates are respectively 4 cubic meters per hour, 8 cubic meters per hour and 8 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 50 hours; preparing a silicon carbide/metal hafnium coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the silicon carbide/metal hafnium coating material which is prepared.
The product was tested after appropriate heat treatment. The thickness of the prepared silicon carbide/metal hafnium coating material hafnium coating is detected by using a metallographic microscope, and the detection result shows that the thickness of the coating is 523 mu m. According to the adhesion test standard of ISO4624-2016 coating, the adhesion of the prepared hafnium coating of the silicon carbide/metal hafnium coating material is detected, and the adhesion of the metal hafnium coating and the silicon carbide substrate is 137MPa through the test, so that compared with the existing method, the adhesion of the coating is remarkably improved, and the adhesion of the coating is generally less than 100MPa through other chemical vapor deposition hafnium technical schemes. FIG. 25 shows a gold phase diagram of the surface of a hafnium metal layer, which is magnified 2000 times and no cracking phenomenon is observed.
Using the process conditions of example 31, chemical vapor deposition was performed according to the above steps (1) to (6) while changing only the chamber temperature, i.e., the deposition temperature, to obtain the deposition rates and the variations in the adhesion of the deposited layers at different deposition temperatures, as shown in table 13 and fig. 22. At 750 ℃, the deposition rate was very slow, with almost no hafnium deposition observed; the deposition rate increases with increasing reaction temperature. In the range of 800 to 850 ℃, the deposition rate shows an increasing trend; in the range of 850-1000 ℃, the deposition rate is obviously improved, the speed in the range of 1000-1300 ℃ is relatively slowly increased, and when the temperature exceeds a certain range, the influence of the temperature on the deposition rate becomes slow and is not obvious. The deposition rate can reach 12.02 mu m per hour.
As shown in fig. 22, the general trend of the coating adhesion is increased with the temperature increase in the range of 750 to 1300 ℃, and the coating adhesion is increased and then decreased in a certain temperature range. At 750 ℃, the adhesion cannot be tested because the deposition rate is very slow and almost no hafnium deposition is observed; within the range of 800 to 1000 ℃, hafnium deposition is observed, and the adhesive force is obviously changed; within the range of 1000-1300 ℃, the adhesive force of the coating layer shows a descending trend, and the descending is slow and not obvious. When the temperature is higher than 1300 ℃, the adhesive force of the coating is obviously reduced to be less than 100 MPa. The adhesive force value can reach 137MPa when the reaction temperature is 1000 ℃.
The observation of the surface morphology shows that the reaction temperature has no obvious change on the composition of the hafnium deposition layer, but has certain influence on the preferred growth; the grain size of the hafnium deposition layer increases with the temperature. In comprehensive consideration, the preferable range of the reaction temperature is 800-1300 ℃.
TABLE 13 Effect of reaction temperature on coating
Using the process conditions of example 31, chemical vapor deposition was carried out in accordance with the above-mentioned steps (1) to (6) while changing only the reaction gas ratio, and for convenience of explanation, the flow rate of hafnium tetrachloride was fixed at 4m3Other flow rates, with corresponding changes in deposition rate, may also be used. The results are shown in Table 14 and FIG. 23.
From FIG. 23, it can be calculated that when the volume ratio of hafnium tetrachloride to carbon monoxide is 1:1, the thickness of the coating layer is 98-525 μm, and the average value of the calculated deposition rate is 2.6 μm/h; when the volume ratio of the two is 1:2, the thickness of the prepared coating is 567-590 mu m, and the average value of the calculated deposition rate is 10.4 mu m/h; when the volume ratio of the two is 1:3, the coating thickness is 601 μm, and the average value of the calculated deposition rate is 10.6 μm/h. Keeping the volume ratio of rhenium pentachloride to carbon monoxide unchanged, and adjusting the argon flow to 4m3/h、8m3/h、12m3/h、20m3The deposition rate and the adhesion of the deposited layer fluctuate within a certain range. However, the flow rate of the carrier gas is too large, which in turn reduces the deposition rate. In this embodiment, the adhesion to the deposition layer is greater than 100MPa at different flow rates of the reaction gases, and the numerical value changesThe influence of (c) is small.
TABLE 14 Effect of the reaction gas ratio on the coating
Example 32
The materials and reagents used were as follows: a quartz glass cylindrical body (silica content greater than 99.99%); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity hafnium tetrachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a vacuum state of 100Pa, keeping the vacuum state of 100Pa for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 5 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning a quartz glass cylindrical blank by distilled water, removing dirt, drying at 105 ℃ for 5 hours, and then putting into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the surfaces are not overlapped and blocked;
(3) vacuumizing to a 100Pa vacuum state, keeping the 100Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 5 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to a vacuum state of 100Pa, maintaining the vacuum state of 100Pa for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 11000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 850 ℃;
(5) putting hafnium tetrachloride into a gasification chamber, heating to 500 ℃ to gasify the hafnium tetrachloride, introducing the gasified hafnium tetrachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of the hafnium tetrachloride, the carbon monoxide and the argon gas is 1: 2: 2, the flow rates are respectively 4 cubic meters per hour, 8 cubic meters per hour and 8 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 1 hour; preparing a glass/metal hafnium coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared glass/metal hafnium composite material.
After appropriate heat treatment, the test was carried out. The thickness of the prepared hafnium coating of the glass/metal hafnium coating material is detected by using a metallographic microscope, the detection result shows that the thickness of the coating is 10 mu m, the adhesion of the prepared hafnium coating of the glass/metal hafnium coating material is detected according to the adhesion test standard of ISO4624-2016 coating, and the adhesion of the metal hafnium coating and a glass substrate is 129MPa through the test.
Example 33
The materials and reagents used were as follows: a carbon fiber cylindrical blank (the carbon content is more than 99.99 percent, and the porosity is 85 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity hafnium tetrachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a carbon fiber cylindrical blank by distilled water, drying the carbon fiber cylindrical blank for 10 hours at the temperature of 150 ℃, and then putting the carbon fiber cylindrical blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the carbon fiber cylindrical blank is not overlapped with the reaction gas outlet and is not blocked;
(3) vacuumizing to a vacuum state of 200Pa, keeping the vacuum state of 200Pa for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to 200Pa vacuum state, maintaining the 200Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is well sealed, controlling the vacuum degree in the vapor deposition equipment to 13500Pa by using a vacuum pump, and simultaneously heating the temperature in the reaction chamber to 1000 ℃;
(5) putting hafnium tetrachloride into a gasification chamber, heating to 550 ℃, gasifying the hafnium tetrachloride, introducing the gasified hafnium tetrachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of the hafnium tetrachloride to the carbon monoxide to the argon gas is 1: 2: 1, the flow rates are respectively 2 cubic meters per hour, 4 cubic meters per hour and 2 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on a blank body for 500 hours; preparing a carbon fiber/metal hafnium composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared porous carbon/metal hafnium composite material.
After appropriate heat treatment, the test was carried out. The bending strength performance of the prepared material is tested according to the bending test standard of GB/T232-. The prepared carbon fiber/metal hafnium composite material is tested according to the ISOTR 26946-2011 porosity test standard, and the test result shows that the porosity of the carbon fiber/metal hafnium composite material is 4%. The embodiment result shows that the technical scheme of the invention overcomes the defects of the existing method and can be suitable for preparing the high-performance metal hafnium composite material.
Example 34
The materials and reagents used were as follows: a 316L stainless steel cylindrical blank; high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity hafnium tetrachloride (99.99%). The chemical vapor deposition equipment is an alumina reaction chamber. The implementation steps are as follows:
(1) vacuumizing the equipment to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve to evacuate, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning a 316L stainless steel cylindrical blank by distilled water, removing dirt, drying at 200 ℃ for 10 hours, and then putting into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blank is not overlapped and blocked;
(3) vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to a 1000Pa vacuum state, keeping the 1000Pa vacuum state for 15 minutes, controlling the vacuum degree in the vapor deposition equipment to 15500Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 850 ℃;
(5) putting hafnium tetrachloride into a gasification chamber, heating to 550 ℃, gasifying the hafnium tetrachloride, introducing the gasified hafnium tetrachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of the hafnium tetrachloride to the carbon monoxide to the argon gas is 1: 2: 2, the flow rates are respectively 3 cubic meters per hour, 6 cubic meters per hour and 6 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 1000 hours;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared metal hafnium material;
(7) and removing the 316L stainless steel cylindrical blank of the deposited material by machining to finally prepare the pure metal hafnium material with the thickness of 10 mm.
After appropriate heat treatment, the test was carried out. The bending strength performance of the prepared material is tested according to the bending test standard of GB/T232-. The prepared hafnium metal material is tested according to ISO TR26946-3The purity of the material is tested by adopting flame atomic absorption spectroscopy, and the test result shows that the purity of the metal hafnium material is 99.999 percent. The embodiment result shows that the technical scheme of the invention overcomes the defects of the existing method and can be suitable for preparing the metal hafnium material with high purity and high performance.
Example 35
The materials and reagents used were as follows: a 316L stainless steel rivet; high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity hafnium tetrafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing chemical vapor deposition equipment to a 900Pa vacuum state, keeping the 900Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for evacuation, continuing introducing the argon for 12 minutes, closing an exhaust valve, and evacuating residual gases and impurities required by non-reaction in the vapor deposition equipment through the steps;
(2) cleaning 316L stainless steel rivet blanks by distilled water, removing dirt, drying at 120 ℃ for 7 hours, and then putting into a reaction chamber to ensure that the surfaces to be deposited of the blanks are opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 900Pa vacuum state, keeping the 900Pa vacuum state for 12 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 12 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to 900Pa vacuum state, maintaining the 900Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 11000Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 850 ℃;
(5) putting hafnium tetrafluoride into a gasification chamber, heating to 550 ℃, gasifying the hafnium tetrafluoride, introducing the gasified hafnium tetrachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the three gases of the hafnium tetrafluoride, the carbon monoxide and the argon gas is 1: 1:2, the flow rates are respectively 4 cubic meters per hour, 4 cubic meters per hour and 8 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on the blank body for 10 hours; preparing a stainless steel/metal hafnium coating material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared stainless steel/metal hafnium coating material.
The product was tested after appropriate heat treatment. The thickness of the prepared stainless steel/metal hafnium coating material hafnium coating is detected by using a metallographic microscope, the detection result shows that the thickness of the prepared stainless steel/metal hafnium coating material hafnium coating is 120 mu m, the adhesion of the prepared stainless steel/metal hafnium coating material hafnium coating is detected according to the ISO4624-2016 coating adhesion test standard, the adhesion of the metal hafnium coating and a stainless steel matrix is 123MPa through testing, and compared with the existing method, the adhesion of the coating is remarkably improved.
With the process parameters of example 35, only the chamber temperature, i.e., the deposition temperature, was changed according to the above steps (1) to (6), resulting in the variation of the deposition rate and the adhesion of the deposited layer at different deposition temperatures, as shown in fig. 24. At 750 ℃, the deposition rate was very slow, with almost no hafnium deposition observed; the deposition rate increases with increasing reaction temperature. In the range of 800-850 ℃, the deposition rate is obviously improved, the speed rise in the range of 850-1200 ℃ is relatively slow, and when the temperature exceeds a certain range, the influence of the temperature on the deposition rate becomes slow and is not obvious. The deposition rate can reach 13.9 mu m/h.
The effect of different deposition temperatures on the adhesion of the deposited layers is also shown in fig. 24. At 750 c, adhesion cannot be tested because there is no deposited layer. Deposition of hafnium was observed at 800 ℃ to 1000 ℃, so adhesion was significantly improved. The adhesive force of the coating is reduced within the range of 1000-1200 ℃, and when the temperature is higher than 1200 ℃, the adhesive force of the coating is obviously reduced to be less than 100 MPa. When the reaction temperature is 1000 ℃, the maximum adhesion value can reach 130 MPa.
The observation of the surface morphology shows that the reaction temperature has no obvious change on the composition of the hafnium deposition layer, but has certain influence on the preferred growth; the grain size of the hafnium deposition layer increases with increasing temperature. In comprehensive consideration, the preferable range of the reaction temperature is 800-1200 ℃.
Using the process parameters of example 35, the reaction gas ratio was varied only, and the above-described steps (1) to (6) were carried outAnd (3) performing chemical vapor deposition, wherein the preferred gas volume ratio of the hafnium tetrafluoride to the carbon monoxide is 1:1-2, and the preferred gas volume ratio of the hafnium tetrafluoride to the argon is 1: 1-5. The preferred flow rate of hafnium tetrafluoride is 2 to 6m3H is used as the reference value. The preferred carbon monoxide flow is in the range of 2 to 12m3Adjusting within the range of/h. The preferred flow rate of argon is 2-12m3Adjusting within a/h range, observing the influence of the gas proportion and the flow on the chemical deposition rate and the adhesive force of the deposition layer, wherein the deposition rate and the adhesive force of the deposition layer fluctuate within a certain range. A detailed description is given in embodiment 31 and will not be repeated here.
Example 36
The materials and reagents used were as follows: a porous carbon square blank (the carbon content is more than 99.999 percent, and the porosity is more than 96 percent); high purity carbon monoxide (99.999%); high purity argon (99.999%); high purity hafnium tetrafluoride (99.99%). The implementation steps are as follows:
(1) vacuumizing the chemical vapor deposition equipment to a 500Pa vacuum state, keeping the 500Pa vacuum state for 15 minutes, checking that the vapor deposition equipment is well sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with the argon, opening an air valve for evacuation, continuing introducing the argon for 10 minutes, closing an exhaust valve, and evacuating residual non-reaction required gas and impurities in the vapor deposition equipment through the steps;
(2) cleaning and decontaminating a porous carbon square blank by distilled water, drying the blank for 5 hours at 200 ℃, and then putting the blank into a reaction chamber to ensure that the surface to be deposited of the blank is opposite to the direction of a reaction gas outlet, and the blanks are not overlapped and blocked;
(3) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, checking that the vapor deposition equipment is completely sealed, then introducing argon to a normal pressure state, filling the reaction chamber and all vacuum pipelines with argon, opening an air valve to evacuate, continuing introducing argon for 10 minutes, closing an exhaust valve, and evacuating non-reaction required gas and impurities entering in the process of placing a blank of the vapor deposition equipment into the reaction chamber;
(4) vacuumizing to a 500Pa vacuum state, keeping the 500Pa vacuum state for 10 minutes, controlling the vacuum degree in the vapor deposition equipment to 15500Pa by a vacuum pump after checking that the vapor deposition equipment is completely sealed, and simultaneously heating the temperature in the reaction chamber to 1250 ℃;
(5) putting hafnium tetrafluoride into a gasification chamber, heating to 400 ℃ to gasify the hafnium tetrafluoride, introducing gasified hafnium tetrafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the three gases of the hafnium tetrafluoride, the carbon monoxide and the argon gas is 1: 1:2, the flow rates are respectively 2 cubic meters per hour, 2 cubic meters per hour and 4 cubic meters per hour, and after the materials are fully mixed in a gas mixing tank, the materials are introduced into a reaction chamber to perform chemical vapor deposition reaction on a blank body for 100 hours; preparing a porous carbon/metal hafnium composite material;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared porous carbon/metal hafnium composite material.
And carrying out performance test after proper heat treatment. The prepared porous carbon/metal hafnium composite material is tested according to ISO TR 26946-.
In the embodiments 31 to 36, the metal hafnium is detected by flame atomic absorption spectroscopy, the content of the metal hafnium is more than 99.999 percent, and the surface appearance of the coating is observed by a scanning electron microscope without cracking. Preferably, the above embodiment controls the vacuum degree in the vapor deposition equipment to 11000-15500Pa through the vacuum pump, and the change of the vacuum degree also has influence on the deposition rate of the invention. The deposition rate is increased along with the increase of the gas pressure of the reaction chamber; however, the degree of vacuum reaches a certain range, and the deposition rate changes slowly. The change of vacuum degree has no obvious change to the composition of the deposition layer, but has certain influence on the preferential growth. The test results of the above embodiments show that, compared with the existing method, the product prepared by the invention overcomes the defects of the prior art, remarkably improves the mechanical properties of the material, and can be suitable for preparing high-performance metal hafnium coating or hafnium composite material in industrial production.
The above embodiments and drawings are not intended to limit the form and style of the product of the present invention, and any suitable changes or modifications, such as changes in reaction temperature, gasification temperature, gas flow rate, etc., made by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (41)
1. A method for preparing refractory metal material is characterized in that: taking refractory metal halide as a reaction source, gasifying the refractory metal halide, carrying out reduction reaction on the gasified refractory metal halide and carbon monoxide in chemical vapor deposition equipment, and depositing on the surface of a blank to prepare the required refractory metal material.
2. A method of producing a refractory metal material as claimed in claim 1, further comprising the step of, prior to vaporizing the refractory metal halide:
(1) removing non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing a blank to be deposited into a reaction chamber of equipment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of the reaction chamber.
3. A method of producing a refractory metal material as claimed in claim 1, wherein: the refractory metal is any elementary metal of tantalum, tungsten, rhenium, niobium, molybdenum and hafnium or an alloy formed by combining the elementary metals with one another.
4. A method of producing a refractory metal material as claimed in claim 1, wherein: the refractory metal halide is one or more of tantalum pentachloride, tantalum pentafluoride, tungsten hexachloride, tungsten hexafluoride, rhenium pentachloride, rhenium pentafluoride, niobium pentachloride, molybdenum pentafluoride, molybdenum pentachloride, hafnium tetrafluoride and hafnium tetrachloride.
5. A method of producing a refractory metal material as claimed in claim 1, wherein: the metal material comprises alloy, coating and composite material.
6. A method of producing a refractory metal material as claimed in claim 2, wherein: in the step (4), the vacuum degree is 6000-22000 Pa; the reaction temperature is 770-1300 ℃.
7. A method of producing a refractory metal material as claimed in claim 2, wherein: the reaction chamber is an alumina reaction chamber.
8. A method of producing a refractory metal material as claimed in claim 1 or claim 2, wherein: the refractory metal halide is introduced into the reaction chamber after being vaporized by a carrier gas, which is argon.
9. The method of claim 6, wherein: the refractory metal halide is tantalum pentachloride or tantalum pentafluoride, and the reaction temperature is 820-1300 ℃.
10. The method of claim 6, wherein: the refractory metal halide is tungsten hexachloride or tungsten hexafluoride, and the reaction temperature is 850-1250 ℃.
11. The method of claim 6, wherein: the refractory metal halide is rhenium pentachloride or rhenium pentafluoride, and the reaction temperature is 820-1300 ℃.
12. The method of claim 6, wherein: the refractory metal halide is niobium pentafluoride or niobium pentachloride, and the reaction temperature is 800-1200 ℃.
13. The method of claim 6, wherein: the refractory metal halide is molybdenum pentafluoride or molybdenum pentachloride, and the reaction temperature is 770-1200 ℃.
14. The method of claim 6, wherein: the refractory metal halide is hafnium tetrafluoride or hafnium tetrachloride, and the reaction temperature is 800-1300 ℃.
15. The method of claim 6, wherein: the refractory metal halide is tantalum pentachloride or tantalum pentafluoride, and the vacuum degree of the equipment is 12000-15000 Pa.
16. The method of claim 6, wherein: the refractory metal halide is tungsten hexachloride or tungsten hexafluoride, and the vacuum degree of the equipment is controlled to be 18000-22000 Pa.
17. The method of claim 6, wherein: the refractory metal halide is rhenium pentachloride or rhenium pentafluoride, and the vacuum degree of the equipment is controlled to be 15000-20000 Pa.
18. The method of claim 6, wherein: the refractory metal halide is niobium pentachloride or niobium pentafluoride, and the vacuum degree of the equipment is controlled to be 12000-15000 Pa.
19. The method of claim 6, wherein: the refractory metal halide is molybdenum pentachloride or molybdenum pentafluoride, and the vacuum degree of the equipment is controlled to be 6000-14000 Pa.
20. The method of claim 6, wherein: the refractory metal halide is hafnium tetrafluoride or hafnium tetrachloride, and the vacuum degree of the equipment is controlled to be 11000-15500 Pa.
21. A method of producing a refractory metal material as claimed in claim 1 or claim 2, wherein: the chemical vapor deposition equipment comprises a gasification chamber, wherein the gasification of the refractory metal halide is carried out in the gasification chamber, and the temperature of the gasification chamber is set to be 260-700 ℃.
22. A method of producing a refractory metal material as claimed in claim 21, wherein: when the refractory metal halide is tantalum pentachloride or tantalum pentafluoride, the temperature of the gasification chamber is set to be 300-600 ℃.
23. A method of producing a refractory metal material as claimed in claim 21, wherein: when the refractory metal halide is tungsten hexachloride or tungsten hexafluoride, the temperature of the gasification chamber is set to be 400-700 ℃.
24. A method of producing a refractory metal material as claimed in claim 21, wherein: when the refractory metal halide is rhenium pentachloride or rhenium pentafluoride, the temperature of the gasification chamber is set to be 260-520 ℃.
25. A method of producing a refractory metal material as claimed in claim 21, wherein: when the refractory metal halide is niobium pentachloride or niobium pentafluoride, the temperature of the gasification chamber is set to be 300-500 ℃.
26. A method of producing a refractory metal material as claimed in claim 21, wherein: when the refractory metal halide is molybdenum pentachloride or molybdenum pentafluoride, the temperature of the gasification chamber is set to be 350-550 ℃.
27. A method of producing a refractory metal material as claimed in claim 21, wherein: when the refractory metal halide is hafnium tetrafluoride or hafnium tetrachloride, the temperature of the gasification chamber is set to be 350-550 ℃.
28. A method of producing a refractory metal material as claimed in claim 1, wherein: the volume ratio of the refractory metal halide to the carbon monoxide gas is 1:1 to 4.
29. A method of producing a refractory metal material as claimed in claim 28, wherein: the refractory metal halide is one of tantalum pentachloride, tantalum pentafluoride, tungsten hexachloride, tungsten hexafluoride, niobium pentachloride, niobium pentafluoride, molybdenum pentachloride, molybdenum pentafluoride, hafnium tetrafluoride and hafnium tetrachloride, and the volume ratio of gas to carbon monoxide is 1: 2.
30. A method of producing a refractory metal material as claimed in claim 28, wherein: the volume ratio of the rhenium pentachloride or rhenium pentafluoride gas to the carbon monoxide is 1: 4.
31. A method of producing a refractory metal material as claimed in claim 8, wherein: the volume ratio of the refractory metal halide to the carrier gas is 1:1 to 5.
32. A method of producing a refractory metal material as claimed in claim 28 or claim 31, wherein: the gas flow of the refractory metal halide is 1-9 cubic meters per hour, the gas flow of the carrier gas is 1-30 cubic meters per hour, and the gas flow of the carbon monoxide is 1-24 cubic meters per hour.
33. The method of claim 2, wherein the steps (1) and (3) for removing non-reactive gases and impurities in the vapor deposition apparatus are carried out by: firstly, vacuumizing the vapor deposition equipment to a vacuum state of 0-1000Pa, keeping the vacuum state of 0-1000Pa for 5-20 minutes, checking that the vapor deposition equipment is well sealed, then introducing carrier gas to a normal pressure state, filling the reaction chamber and all vacuum pipelines of the vapor deposition equipment with the carrier gas, opening an air valve to empty, continuing introducing the carrier gas for 5-20 minutes, and closing an exhaust valve.
34. A method of producing a refractory metal material as claimed in claim 2, wherein: in the step (2), the blank body to be deposited is pretreated before being placed into a reaction chamber of equipment, and the pretreatment comprises the following steps: cleaning and decontaminating the blank to be deposited by distilled water, and drying for 3-15 hours at 105-200 ℃ until the blank is completely dried.
35. A method of producing a refractory metal material as claimed in claim 2, wherein: the tightness of the equipment in the step (4) is checked by adopting the following steps: the vapor deposition equipment is vacuumized to 0-1000Pa vacuum state and kept at the 0-1000Pa vacuum state for 5-20 minutes to check that the vapor deposition equipment is well sealed.
36. A method of producing a refractory metal material as claimed in claim 1 or claim 2, comprising the steps of:
(1) removing non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing a blank to be deposited into a reaction chamber of equipment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 820-1180 ℃;
(5) putting tantalum pentachloride or tantalum pentafluoride into a gasification chamber, heating to gasify the tantalum pentachloride or the tantalum pentafluoride, introducing gasified tantalum pentachloride or tantalum pentafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the tantalum pentachloride or tantalum pentafluoride gas, the carbon monoxide gas and the argon gas is 1: 2: 2, after fully mixing in a gas mixing tank, introducing the mixture into a reaction chamber to perform chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
37. A method of producing a refractory metal material as claimed in claim 1 or claim 2, comprising the steps of:
(1) removing non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing a blank to be deposited into a reaction chamber of equipment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 850-1200 ℃;
(5) putting tungsten hexachloride or tungsten hexafluoride into a gasification chamber, heating and gasifying the tungsten hexachloride or tungsten hexafluoride gas, introducing the gasified tungsten hexachloride or tungsten hexafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the proportion of the tungsten hexachloride or tungsten hexafluoride gas, the carbon monoxide gas and the argon gas is 1: 2: 3, after fully mixing in a gas mixing tank, introducing the mixture into a reaction chamber to perform chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
38. A method of producing a refractory metal material as claimed in claim 1 or claim 2, comprising the steps of:
(1) removing non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing a blank to be deposited into a reaction chamber of equipment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 820-1200 ℃;
(5) putting rhenium pentachloride or rhenium pentafluoride into a gasification chamber, heating to gasify the rhenium pentachloride or rhenium pentafluoride, introducing gasified rhenium pentachloride or rhenium pentafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the rhenium pentachloride or rhenium pentafluoride, the carbon monoxide and the argon gas is 1: 4: 2, after fully mixing in a gas mixing tank, introducing the mixture into a reaction chamber to perform chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
39. A method of producing a refractory metal material as claimed in claim 1 or claim 2, comprising the steps of:
(1) removing non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing a blank to be deposited into a reaction chamber of equipment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 850-1180 ℃;
(5) putting niobium pentachloride or niobium pentafluoride into a gasification chamber, heating to gasify the niobium pentachloride or niobium pentafluoride, introducing the gasified niobium pentachloride or niobium pentafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the niobium pentachloride or niobium pentafluoride, the carbon monoxide gas and the argon gas is 1: 2: 2, after fully mixing in a gas mixing tank, introducing the mixture into a reaction chamber to perform chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
40. A method of producing a refractory metal material as claimed in claim 1 or claim 2, comprising the steps of:
(1) removing non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing a blank to be deposited into a reaction chamber of equipment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 850-1150 ℃;
(5) putting molybdenum pentachloride or molybdenum pentafluoride into a gasification chamber, heating to gasify the molybdenum pentachloride or molybdenum pentafluoride, introducing the gasified molybdenum pentachloride or molybdenum pentafluoride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the molybdenum pentachloride or molybdenum pentafluoride, the carbon monoxide gas and the argon gas is 1: 2: 2, after fully mixing in a gas mixing tank, introducing the mixture into a reaction chamber to perform chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
41. A method of producing a refractory metal material as claimed in claim 1 or claim 2, comprising the steps of:
(1) removing non-reaction required gas and impurities in the chemical vapor deposition equipment;
(2) placing a blank to be deposited into a reaction chamber of equipment;
(3) removing non-reaction required gas and impurities entering the chemical vapor deposition equipment in the blank body placing process;
(4) checking the tightness of the chemical vapor deposition equipment, and setting the vacuum degree of the equipment and the reaction temperature of a reaction chamber; the reaction temperature is 850-1100 ℃;
(5) putting hafnium tetrafluoride or hafnium tetrachloride into a gasification chamber, heating to gasify the hafnium tetrafluoride or hafnium tetrachloride, introducing the gasified hafnium tetrafluoride or hafnium tetrachloride gas into a gas mixing tank, and simultaneously introducing argon gas and carbon monoxide gas into the gas mixing tank, wherein the ratio of the three gases of the hafnium tetrafluoride or hafnium tetrachloride, the carbon monoxide and the argon gas is 1: 2: 2, after fully mixing in a gas mixing tank, introducing the mixture into a reaction chamber to perform chemical vapor deposition reaction on the blank;
(6) cutting off the heating power supply, and naturally cooling the reaction chamber; and when the temperature in the reaction chamber is reduced to below 60 ℃, closing the vacuum pump, continuously introducing argon, stopping introducing the argon after the reaction chamber is filled to normal pressure, opening the exhaust valve, opening the reaction chamber, and taking out the prepared material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114411113A (en) * | 2022-01-26 | 2022-04-29 | 亚芯半导体材料(江苏)有限公司 | CVD system for preparing refractory high-entropy alloy target and control method thereof |
| CN114951675A (en) * | 2022-05-30 | 2022-08-30 | 中国科学院合肥物质科学研究院 | A kind of ultrafine tungsten-tantalum nanocrystalline alloy powder and preparation method thereof |
| CN115074693A (en) * | 2022-07-22 | 2022-09-20 | 海朴精密材料(苏州)有限责任公司 | Ultrahigh-purity molybdenum target blank and preparation method thereof |
| CN117305803A (en) * | 2023-09-25 | 2023-12-29 | 中船(邯郸)派瑞特种气体股份有限公司 | A method for preparing high-purity molybdenum-rhenium alloy |
| CN117448780A (en) * | 2023-10-27 | 2024-01-26 | 郑州大学 | A device and method for preparing tantalum powder by gas phase chemical reduction |
| WO2025072574A1 (en) * | 2023-09-26 | 2025-04-03 | Entegris, Inc. | Methods for controlling crystalline phase of molybdenum precursors and related compositions |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112439A (en) * | 1988-11-30 | 1992-05-12 | Mcnc | Method for selectively depositing material on substrates |
| US6139922A (en) * | 1999-05-18 | 2000-10-31 | Gelest, Inc. | Tantalum and tantalum-based films formed using fluorine-containing source precursors and methods of making the same |
| US20180294187A1 (en) * | 2017-04-10 | 2018-10-11 | Lam Research Corporation | Low resistivity films containing molybdenum |
| CN111151768A (en) * | 2019-04-10 | 2020-05-15 | 深圳乐钽医疗器材有限公司 | Preparation method of ultra-pure spherical tantalum powder for additive manufacturing |
-
2021
- 2021-06-11 CN CN202110652785.0A patent/CN113463063A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112439A (en) * | 1988-11-30 | 1992-05-12 | Mcnc | Method for selectively depositing material on substrates |
| US6139922A (en) * | 1999-05-18 | 2000-10-31 | Gelest, Inc. | Tantalum and tantalum-based films formed using fluorine-containing source precursors and methods of making the same |
| US20180294187A1 (en) * | 2017-04-10 | 2018-10-11 | Lam Research Corporation | Low resistivity films containing molybdenum |
| CN111151768A (en) * | 2019-04-10 | 2020-05-15 | 深圳乐钽医疗器材有限公司 | Preparation method of ultra-pure spherical tantalum powder for additive manufacturing |
Non-Patent Citations (1)
| Title |
|---|
| 张而耕主编: "<机械工程材料>", 上海科学技术出版社, pages: 183 - 185 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114411113A (en) * | 2022-01-26 | 2022-04-29 | 亚芯半导体材料(江苏)有限公司 | CVD system for preparing refractory high-entropy alloy target and control method thereof |
| CN114951675A (en) * | 2022-05-30 | 2022-08-30 | 中国科学院合肥物质科学研究院 | A kind of ultrafine tungsten-tantalum nanocrystalline alloy powder and preparation method thereof |
| CN114951675B (en) * | 2022-05-30 | 2024-01-30 | 中国科学院合肥物质科学研究院 | Superfine tungsten-tantalum nanocrystalline alloy powder and preparation method thereof |
| CN115074693A (en) * | 2022-07-22 | 2022-09-20 | 海朴精密材料(苏州)有限责任公司 | Ultrahigh-purity molybdenum target blank and preparation method thereof |
| CN117305803A (en) * | 2023-09-25 | 2023-12-29 | 中船(邯郸)派瑞特种气体股份有限公司 | A method for preparing high-purity molybdenum-rhenium alloy |
| WO2025072574A1 (en) * | 2023-09-26 | 2025-04-03 | Entegris, Inc. | Methods for controlling crystalline phase of molybdenum precursors and related compositions |
| CN117448780A (en) * | 2023-10-27 | 2024-01-26 | 郑州大学 | A device and method for preparing tantalum powder by gas phase chemical reduction |
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