WO2019109718A1 - Oxygen barrier material in anti-oxidation coating structure for tungsten-rhenium thermocouple and application thereof - Google Patents
Oxygen barrier material in anti-oxidation coating structure for tungsten-rhenium thermocouple and application thereof Download PDFInfo
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- WO2019109718A1 WO2019109718A1 PCT/CN2018/108522 CN2018108522W WO2019109718A1 WO 2019109718 A1 WO2019109718 A1 WO 2019109718A1 CN 2018108522 W CN2018108522 W CN 2018108522W WO 2019109718 A1 WO2019109718 A1 WO 2019109718A1
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- oxygen barrier
- barrier material
- tungsten
- thermocouple
- layer
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- 239000000463 material Substances 0.000 title claims abstract description 176
- 239000001301 oxygen Substances 0.000 title claims abstract description 153
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 153
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 230000004888 barrier function Effects 0.000 title claims abstract description 133
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000000576 coating method Methods 0.000 title claims abstract description 78
- 239000011248 coating agent Substances 0.000 title claims abstract description 77
- 230000003064 anti-oxidating effect Effects 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims description 52
- 238000007254 oxidation reaction Methods 0.000 claims description 52
- 239000000758 substrate Substances 0.000 claims description 31
- 238000002679 ablation Methods 0.000 claims description 23
- CZBGCSZGIMINPA-UHFFFAOYSA-N [Rh].[W] Chemical compound [Rh].[W] CZBGCSZGIMINPA-UHFFFAOYSA-N 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 6
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 6
- 238000003980 solgel method Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003870 refractory metal Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- XTDAIYZKROTZLD-UHFFFAOYSA-N boranylidynetantalum Chemical compound [Ta]#B XTDAIYZKROTZLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 3
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 238000007751 thermal spraying Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 2
- 229910052721 tungsten Inorganic materials 0.000 claims 2
- 239000010937 tungsten Substances 0.000 claims 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 230000003628 erosive effect Effects 0.000 abstract 1
- 238000004861 thermometry Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 14
- 238000009529 body temperature measurement Methods 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 10
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 229910026551 ZrC Inorganic materials 0.000 description 5
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 2
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical compound [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 description 2
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910001006 Constantan Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910007948 ZrB2 Inorganic materials 0.000 description 1
- FNYLUKDQSKKYHG-UHFFFAOYSA-N [Ru].[W] Chemical compound [Ru].[W] FNYLUKDQSKKYHG-UHFFFAOYSA-N 0.000 description 1
- DBUTVDSHVUGWOZ-UHFFFAOYSA-N [Si].[Ni].[Cr].[Ni] Chemical compound [Si].[Ni].[Cr].[Ni] DBUTVDSHVUGWOZ-UHFFFAOYSA-N 0.000 description 1
- DZZDTRZOOBJSSG-UHFFFAOYSA-N [Ta].[W] Chemical compound [Ta].[W] DZZDTRZOOBJSSG-UHFFFAOYSA-N 0.000 description 1
- WIGAYVXYNSVZAV-UHFFFAOYSA-N ac1lavbc Chemical compound [W].[W] WIGAYVXYNSVZAV-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical group B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- -1 cerium oxychloride octahydrate Chemical compound 0.000 description 1
- WXANAQMHYPHTGY-UHFFFAOYSA-N cerium;ethyne Chemical compound [Ce].[C-]#[C] WXANAQMHYPHTGY-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- IREVRWRNACELSM-UHFFFAOYSA-J ruthenium(4+);tetrachloride Chemical compound Cl[Ru](Cl)(Cl)Cl IREVRWRNACELSM-UHFFFAOYSA-J 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect
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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
- C23C16/22—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 inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
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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
- C23C16/22—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 inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/38—Borides
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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
- C23C16/22—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 inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
Definitions
- thermocouples For the measurement of ultra-high temperature above 1600 °C, non-contact (infrared, optical, etc.) methods are often used for measurement, but the non-contact method not only has a slow response speed, but also the temperature measurement accuracy is far less than the direct contact type temperature measurement using a thermocouple.
- Platinum rhodium (Pt-Rh) thermocouples, nickel-chromium-nickel silicon thermocouples, iron-constantan thermocouples and tungsten-rhenium (W-Re) thermocouples are common types of high-temperature thermocouples, among which tungsten-rhodium thermocouples Compared with other thermocouples, it has obvious advantages:
- the temperature measurement range is large, and the upper limit of the working temperature can reach 2800 ° C;
- the tungsten-rhenium thermocouple starts to oxidize from about 300 ° C in an aerobic environment, and is only suitable for high-temperature measurement in environments such as reduction, inertness, and vacuum, and cannot be applied in a high-temperature oxidizing atmosphere. Therefore, how to improve the anti-oxidation ability of tungsten-rhenium thermocouples has been a topic of high concern in the field of high-temperature measurement at home and abroad.
- the temperature is measured by a tungsten-rhenium thermocouple in an aerobic environment.
- two methods are used: one is for one-time measurement, that is, each temperature measurement time is short, and the thermocouple is no longer used or reprocessed after oxidation failure. After use, another way is to take anti-oxidation treatment on the thermocouple.
- the commercial tungsten-tungsten thermocouple anti-oxidation technology is mainly an armored protection method, that is, quartz, corundum, refractory metal and high-temperature ceramics are used as protective tubes, and after being filled into a tungsten-rhenium thermocouple, the air-sealed seal is filled with an inert gas seal or Filled with an inert powder seal, creating a non-oxidizing atmosphere for the thermocouple in the protective tube to complete the temperature measurement mission before oxidation damage, but this non-removable solid anti-oxidation thermocouple has the following problems:
- thermocouple is limited by the temperature resistance of the protective tube, usually less than 1800 ° C;
- thermocouple After the protection of the casing and the filling material, the response speed of the thermocouple is greatly affected.
- thermocouple By coating the surface of the tungsten-rhenium thermocouple with an anti-oxidation coating, the upper limit of temperature measurement and the extended temperature measurement time of the thermocouple in high-temperature air and other high-temperature oxidizing atmospheres are improved without affecting the response speed, which solves the above problems.
- the ideal method In fact, research at home and abroad has been carried out since the 1960s, but there has been no continuous public reporting, and no relevant products have been put into practical use on a global scale.
- the invention provides a novel high-temperature anti-oxidation oxygen barrier material for the surface of a tungsten-rhenium thermocouple, so that it can realize long-time contact temperature measurement under an ultra-high temperature aerobic environment of 2000 ° C or higher.
- the present invention provides an oxygen barrier material in a tungsten-rhenium thermocouple high-temperature oxidation resistant coating structure and an application thereof, the object of which is to pass a high temperature oxidation resistant coating on a tungsten-rhenium thermocouple.
- the outermost part of the structure is provided with a multi-layered oxygen barrier material, and the oxygen barrier material in the multilayer structure has a composition gradient and a concentration gradient, that is, oxygen is adjusted by adjusting the ratio of each layer of material or material.
- the thermal expansion coefficient of each layer of the barrier material gradually increases away from the tungsten-rhenium thermocouple matrix, and the oxygen-resistant ablation ability of each layer of the oxygen barrier material gradually increases away from the tungsten-rhenium thermocouple matrix, thereby increasing
- the adhesion of the tungsten-rhenium thermocouple high-temperature anti-oxidation coating and the stress of the high-temperature anti-oxidation coating of the tungsten-rhenium thermocouple are solved, thereby solving the problem of long-time contact temperature measurement in an ultra-high temperature aerobic environment above 2000 °C.
- an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure is provided, which is a multilayer structure of not less than two layers, each of the oxygen barrier materials The coefficient of thermal expansion of the layer material gradually increases away from the tungsten-rhodium thermocouple matrix.
- the oxygen barrier material of the multilayer structure has a composition gradient or a concentration gradient, that is, each layer of the multilayer structure of the oxygen barrier material adopts different material species to form a composition gradient; or each layer has the same material type And at least a mixture of two materials, but the ratio of materials in each layer is different to form a concentration gradient.
- the absolute value of the difference between the thermal expansion coefficient of the outermost layer of the oxygen barrier material and the thermal expansion coefficient of the substrate is not more than 7 ⁇ 10 -6 K -1 .
- the oxygen ablative resistance of each layer of material in the oxygen barrier material gradually increases away from the tungsten rhodium thermocouple matrix.
- the oxygen barrier material is selected from a refractory metal oxide, a boride or a nitride which can function as an oxygen barrier or an oxygen ablation at 2000 ° C or higher.
- the oxygen barrier material is selected from one or more of the group consisting of silicon oxide, hafnium oxide, tantalum boride, tantalum nitride, zirconium oxide, zirconium boride, zirconium nitride, and hafnium oxide.
- the oxygen barrier material has a total thickness of from 50 to 200 microns.
- the number of layers of the oxygen barrier material is 5-20 layers.
- an oxygen barrier material of the tungsten-rhenium thermocouple oxidation-resistant coating structure as an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure, the oxygen The barrier material is located at the outermost portion of the tungsten-rhenium thermocouple oxidation-resistant coating structure.
- the oxygen barrier material is attached to the surface of the tungsten-rhodium thermocouple substrate.
- the oxygen barrier material is prepared on the surface of the tungsten-rhodium thermocouple substrate by a chemical vapor deposition method, a thermal spray method or a sol-gel method.
- the tungsten-rhenium thermocouple high-temperature oxidation-resistant coating structure proposed by the present invention comprises a multi-layered oxygen barrier material, and the oxygen barrier material in the multilayer structure has a composition gradient and a concentration gradient, that is, by adjusting each layer The material type or the ratio between the materials, so that the absolute value of the difference between the thermal expansion coefficient of the oxygen barrier material and the thermal expansion coefficient of the matrix of the oxygen barrier material formed near the tungsten-rectifier thermocouple substrate is not more than 7 ⁇ 10 -6 K -1 , Moreover, the thermal expansion coefficient of each layer of the oxygen barrier material gradually increases away from the tungsten-rhenium thermocouple matrix, so that the combination of the simple tungsten-rhenium matrix and the oxygen barrier layer having only one layer will have a large thermal expansion coefficient.
- the difference is dispersed in the gradual form between the layer and the layer by the composition gradient or the concentration gradient, so that the coefficient of thermal expansion gradually increases from the inside to the outside, effectively reducing the thermal stress of the high temperature oxidation resistant coating of the tungsten-rhenium thermocouple, and increasing The adhesion of the high temperature anti-oxidation coating of the tungsten-rhenium thermocouple is increased.
- the oxygen barrier material of the present invention has a multi-layer structure, and the material of each layer in the oxygen barrier material not only has an increasing coefficient of thermal expansion in a direction away from the tungsten-rhenium thermocouple substrate, but also ensures good stress dispersion, and the resistance of each layer of the material.
- the oxygen ablation ability is gradually increased away from the tungsten-rhenium thermocouple substrate, so that the oxygen-resistant ablation ability, that is, the oxidation resistance, is ensured while ensuring stress dispersion and high temperature resistance of the oxidation-resistant coating.
- the superiority of the oxygen barrier material in the tungsten-rhenium thermocouple oxidation resistant coating of the present invention is embodied.
- thermocouple anti-oxidation coating and the oxygen barrier material proposed by the invention are directly attached to the surface of the tungsten-rhodium thermocouple wire substrate, and the total thickness is within 200 micrometers, and the tungsten-rhenium thermocouple oxidation-resistant coating is above 2000 °C. It can work continuously for more than 30min without falling off, has long anti-oxidation time and fast temperature response.
- the oxygen barrier material of the multilayer structure in the tungsten-rhenium thermocouple anti-oxidation coating structure of the present invention material selection is essential, when different materials are used to realize a multilayer structure oxygen barrier material having a concentration gradient or a composition gradient, It not only satisfies the problem of increasing thermal expansion coefficient and achieving good stress dispersion.
- oxygen barrier materials of the same material are compared at the same thickness, and the oxygen-resistant ablation ability, that is, the antioxidant capacity is greatly enhanced, indicating the oxygen content of different components.
- the barrier material or the oxygen barrier material between the layers acts synergistically to enhance the oxidation resistance of the overall oxidation resistant coating, providing a strong guarantee for the coating to last for more than 30 minutes at 2000 °C.
- the present invention ingeniously designs a multilayer structure of an oxygen barrier material by selecting a specific oxygen barrier material, and sets a composition gradient or a concentration gradient between the layers, and combines the unique design concept with the careful selection of the material types. Specific preparation process and parameter selection, finally obtained a tungsten-tantalum thermocouple high-temperature anti-oxidation coating oxygen barrier material, which can resist oxidation for more than 30min above 2000 °C, oxidation resistance and thermocouple response speed are far Superior to prior art thermocouple oxidation resistant coatings.
- FIG. 1 is a schematic structural view of an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 1 of the present invention
- FIG. 2 is an external view of an oxygen barrier material covering a tungsten-rhenium thermocouple surface in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 1 of the present invention
- FIG. 3 is a SEM microstructure of an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 1 of the present invention after annealing at 1000 ° C;
- FIG. 4 is a surface morphology of a tungsten-rhenium thermocouple after ablation of an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 1 of the present invention
- Example 5 is a SEM photograph of an oxygen barrier material coating in a tungsten-rhenium thermocouple oxidation-resistant coating structure provided by Example 2 of the present invention after being ablated by an oxyacetylene flame at 2300 ° C for 10 minutes;
- Example 6 is a SEM photograph of an oxygen barrier material coating in a tungsten-rhenium thermocouple oxidation-resistant coating structure provided by Example 3 of the present invention after being ablated by an oxyacetylene flame at 2500 ° C for 35 minutes;
- FIG. 7 is a schematic structural view of an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 4 of the present invention.
- Embodiment 8 is an ablation of an oxygen barrier material coating in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 4 of the present invention after annealing at 1000 ° C, with an oxyacetylene flame of 2300 ° C or higher, and a thermoelectric potential thereof with ablation Time change chart.
- the invention provides an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure, which is located at the outermost part of the tungsten-rhenium thermocouple oxidation-resistant coating structure, which is a multilayer structure of not less than 2 layers.
- the coefficient of thermal expansion of each layer of material in the oxygen barrier material gradually increases away from the tungsten-rhodium thermocouple matrix.
- the oxygen barrier material is an oxidation resistant coating of the tungsten-rhenium thermocouple, which is directly attached to the surface of the tungsten-rhodium thermocouple substrate.
- the oxygen barrier material of the multilayer structure has a composition gradient or a concentration gradient, that is, each layer of the multilayer structure of the oxygen barrier material adopts different material species to form a composition gradient; or each layer has the same material type and at least two A mixture of materials, but the ratio of materials in each layer is different to form a concentration gradient.
- the absolute value of the difference between the thermal expansion coefficient of the outermost layer of the oxygen barrier material and the thermal expansion coefficient of the substrate is not more than 7 ⁇ 10 -6 K -1 .
- the oxygen ablative ability of each layer of material in the oxygen barrier material gradually increases away from the tungsten rhodium thermocouple matrix. The ability of the oxygen-resistant ablation ability can be tested for its resistance to oxygen ablation or oxidation by burning in an oxygen flame.
- the oxygen barrier material is a refractory metal oxide, a boride or a nitride which can function as an oxygen barrier or an oxygen ablation at 2000 ° C or higher.
- the oxygen barrier material is selected from one or more of the group consisting of silicon oxide, hafnium oxide, tantalum boride, tantalum nitride, zirconium oxide, zirconium boride, zirconium nitride, and hafnium oxide.
- the oxygen barrier material has a total thickness of 50 to 200 ⁇ m, preferably has a thickness ranging from 100 to 200 ⁇ m, and the number of layers of the oxygen barrier material may be set to 5 to 20 layers, preferably 10 to 20 layers.
- the thickness of the oxygen barrier material is very important, not too thick, otherwise the temperature response speed of the thermocouple is affected; of course, it should not be too thin, otherwise the oxidation resistant coating will fall off easily, and the oxidation resistance cannot be guaranteed, so how to respond to temperature and oxygen in temperature A balance between ablation capabilities is key.
- the oxygen barrier material of the multilayer structure in the tungsten-rhenium thermocouple anti-oxidation coating structure of the invention is crucial for material selection.
- a multi-layer oxygen barrier material having a concentration gradient or a composition gradient is realized by using different materials, the thermal expansion is not only satisfied.
- the coefficient is increased to achieve the problem of good stress dispersion.
- the oxygen barrier material of the same material is obtained at the same thickness, and the oxygen-resistant ablation ability, that is, the oxidation resistance is greatly enhanced, indicating that the oxygen barrier material or layer of different component types is different.
- the oxygen barrier material between the layers exerts a synergistic promoting effect, enhances the oxidation resistance of the overall antioxidant coating, and provides a strong guarantee for the coating to achieve continuous operation for more than 30 minutes at 2000 °C.
- the above-mentioned multilayer structure oxygen barrier material is used as an oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure, and can be directly disposed on the surface of the tungsten-rhenium thermocouple substrate as an anti-oxidation coating of the tungsten-rhenium thermocouple material.
- a transition layer may be provided between the substrate and the barrier material.
- the preparation method of the oxygen barrier material of the above-mentioned tungsten-rhenium thermocouple oxidation-resistant coating structure comprises the following steps:
- step (2) sequentially change the material type of each layer, or replace the material type, gradually adjust the concentration ratio of different materials in each layer, and deposit layer by layer in the same direction away from the tungsten-rhenium thermocouple substrate in the same way as step (1). So that the thermal expansion coefficient of each layer of the oxygen barrier material of the prepared multilayer structure is gradually increased away from the tungsten-rhenium thermocouple substrate, and the oxygen-resistant ablation ability of each layer of the oxygen barrier material is far away. The direction of the tungsten-rhodium thermocouple substrate is also gradually increased; the total thickness of the oxygen barrier material deposited layer by layer is 50-200 ⁇ m.
- the oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure of the present invention may deposit a multi-layered oxygen barrier material on the outer layer of the transition layer of the substrate or the substrate surface by plasma enhanced chemical vapor deposition, or by plasma spraying method.
- the outer layer of the transition layer on the surface of the substrate or the substrate is sprayed with a multi-layered oxygen barrier material, and the sol-gel method may also be used to condense the oxygen barrier material of the multilayer structure on the outer layer of the transition layer of the substrate or the substrate surface, preferably by a sol-gel method.
- An oxygen barrier material is prepared.
- an oxygen barrier material in a tungsten-rhenium thermocouple high-temperature oxidation-resistant coating structure the oxygen barrier material is directly disposed on a tungsten-rhenium thermocouple substrate, that is, a tungsten-rhenium thermocouple wire having a diameter of about 0.5 mm, that is, the oxygen barrier material is
- the oxidation-resistant coating has five layers, the first layer is ZrB2 material, the thermal expansion coefficient is 6.5 ⁇ 10 -6 K -1 , and the thickness is 10 ⁇ m.
- the second layer is ZrB2-5% SiC material, the thickness is 10 ⁇ m; the third layer is ZrB2-10% SiC, the thickness is 10 ⁇ m; the fourth layer is ZrB2-15% SiC, the thickness is 10 ⁇ m; the fifth layer is ZrB2- 20% SiC, having a thermal expansion coefficient of 9 ⁇ 10 -6 K -1 and a thickness of 10 ⁇ m.
- the multi-layered oxygen barrier material has a total thickness of 50 micrometers, and its thermal expansion coefficient and oxygen ablation resistance gradually increase toward the tungsten carbide thermocouple matrix.
- the preparation method of the oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure is:
- zirconium sol is prepared by using zirconium oxychloride octachloride (10-20 wt%), polyethylene glycol 4000 (10-20 wt%) and deionized water (60-80 wt%), and then adjusting the pH of the sol with ammonia water to 2 ⁇ 3, after a few days of stabilization, take a certain amount of zirconium dioxide powder (10-40% of the mass of the sol) in the beaker, stir evenly to make a suspension, and then use a pulling machine to immerse the tungsten-rhodium thermocouple into the pull-pull
- the first layer is obtained by drying-out; taking an equal amount of sol, adding zirconium dioxide powder and silicon carbide powder (total mass of 10 to 40% of the mass of the sol) to the sol at a mass ratio of 19:1, and repeating the immersion-
- the second layer is obtained by a pull-drying step; an equal amount of sol is taken, and the zirconium dioxide powder and the silicon carbide powder (
- FIG. 3 shows the SEM microstructure of the oxygen barrier layer after annealing at 1000 °C. It can be seen that the coating is dense and the porosity is small.
- Figure 4 shows the surface morphology of the tungsten-rhenium thermocouple after ablation for 10 min. It can be seen that the molten material produced on the surface of the coating will be filled with cracks and the grains will become larger, indicating that the coating has a good protective effect in a short time. Not significantly oxidized.
- the oxygen barrier material in a tungsten-rhenium thermocouple high-temperature oxidation-resistant coating structure, the oxygen barrier material is directly disposed on a tungsten-rhenium thermocouple substrate, that is, a tungsten-rhenium thermocouple wire having a diameter of about 0.5 mm, that is, the oxygen barrier material is
- the anti-oxidation coating has a total of six layers, the first layer is SiC material, the thermal expansion coefficient is 4.5 ⁇ 10 -6 K -1 , the thickness is 20 ⁇ m; the second layer is SiC -20% HfC material, thickness 20 ⁇ m; third layer is SiC-40%HfC, thickness is 20 ⁇ m; fourth layer is SiC-60%HfC, thickness is 20 ⁇ m; fifth layer is SiC-80%HfC, thickness is 20 ⁇ m; the sixth layer is HfC, the coefficient of thermal expansion is 6.7 ⁇ 10 -6 K -1 , and the thickness is 20
- the preparation method of the oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure is:
- the coating composition adjusts the proportion of each gas source in the reaction gas phase, and a thin layer of multi-layer x% SiC-y%HfC with a compositional composition gradient can be obtained by low pressure chemical vapor deposition at a low pressure of about 850 mTorr and a high temperature of about 900 °C.
- the deposition rate is about 3 ⁇ m/h.
- FIG. 5 is a SEM photograph of the coating after ablation of the oxyacetylene flame at 2300 ° C for 10 minutes. It can be seen from Fig. 5 that the surface of the coating is cracked by a long time high temperature flame scouring, but no obvious through crack is observed.
- an oxygen barrier material in a tungsten-rhenium thermocouple high-temperature oxidation-resistant coating structure the oxygen barrier material is directly disposed on a tungsten-rhenium thermocouple substrate, that is, a tungsten-rhenium thermocouple wire having a diameter of about 0.5 mm, that is, the oxygen barrier material is
- the preparation method of the oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure is:
- cerium sol is prepared by using cerium oxychloride octahydrate (10-20% by weight), polyethylene glycol 4000 (10-20% by weight) and deionized water (60-80% by weight), and then adjusting the pH of the sol with ammonia water to 2 ⁇ 3, after a few days of stabilization, take a certain amount of cerium oxide powder (10-40% of the mass of the sol) in the beaker, stir evenly to make a suspension, and then use a pulling machine to immerse the tungsten-rhodium thermocouple into the pull-pull
- the first layer is obtained by drying-out; the same amount of sol is used, and the cerium oxide powder and the zirconia-6% molar cerium oxide powder (the total mass is 10-40% of the mass of the sol) are added to the sol at a mass ratio of 9:1.
- the third layer was prepared by repeating the immersion-drawing-drying step at a mass ratio of 8:2; and eleven layers of a tungsten-rhenium thermocouple oxidation-resistant coating having a composition gradient were obtained.
- FIG. 6 is a SEM photograph of the coating after ablation of the oxyacetylene flame at 2500 ° C for 35 minutes. It can be seen from Fig. 6 that the surface of the coating is peeled off and cracked layer by layer due to long-time high-temperature flame scouring, but the morphology of the WRe thermocouple substrate remains basically intact.
- An oxygen barrier material in a tungsten-rhenium thermocouple high-temperature oxidation-resistant coating structure the oxygen barrier material and a tungsten-rhenium thermocouple substrate, that is, a tungsten-rhenium thermocouple wire having a diameter of about 0.5 mm, further having a thickness of about 10 ⁇ m
- the TaC transition layer as shown in Figure 7, has seven layers of oxygen barrier material, the first layer is close to the tungsten-rhenium thermocouple substrate, and the first layer is HfC-10% ZrC material with a thermal expansion coefficient of 6 ⁇ 10 -6 K.
- the multi-layered oxygen barrier material has a total thickness of 140 micrometers, and its thermal expansion coefficient and oxygen ablation resistance gradually increase away from the tungsten-rhenium thermocouple matrix.
- the preparation method of the oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure is:
- the cerium carbide, zirconium carbide and zirconia powder are refined by ball milling, and their mass ratios are adjusted according to the above-mentioned components, and then the spraying distance is controlled by a plasma spraying machine to be 150 mm, the spraying power is 30 kW, and the powder feeding rate is 3 kg/h.
- a coated powder of a%HfC-b%ZrC-c%ZrO2 having a different composition ratio was sprayed on the outer layer of the transition layer, and seven layers of a tungsten-rhenium thermocouple oxygen barrier material having a composition gradient were sequentially prepared.
- thermoelectric potential with the ablation time. It can be seen that there is still a thermoelectromotive force at 850 s, indicating that tungsten ruthenium is present.
- the thermocouple is not damaged and still works normally, and the anti-oxidation coating has a significant protective effect.
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Abstract
The present invention belongs to the technical field of thermometry and provides an oxygen barrier material in a high temperature anti-oxidation coating structure for a tungsten-rhenium thermocouple and an application thereof. The oxygen barrier material has a multilayer structure with a total thickness of 50-200 μm. The oxygen barrier material in the multilayer structure has a composition gradient and concentration gradient. By adjusting the type of the material in each layer or the ratios between the materials, the coefficients of thermal expansion of the materials of respective layers of the oxygen barrier material gradually increase in a direction away from a tungsten-rhenium thermocouple base body, and the oxygen erosion resistances of the materials in respective layers of the oxygen barrier material also gradually increase in a direction away from the tungsten-rhenium thermocouple base body. Thus, the adhesive force of the high temperature anti-oxidation coating for a tungsten-rhenium thermocouple is increased, while the stress thereon is reduced.
Description
本发明属于温度测量技术领域，更具体地，涉及一种钨铼热电偶高温抗氧化涂层结构中的氧阻挡材料及其应用。The invention belongs to the technical field of temperature measurement, and more particularly to an oxygen barrier material in a tungsten-rhenium thermocouple high-temperature oxidation resistant coating structure and an application thereof.
对于1600℃以上超高温度的测量，目前多采用非接触(红外、光学等)方法测量，但非接触方法不仅响应速度慢，而且测温精度远不如采用热电偶进行直接接触式测温。铂铑(Pt-Rh)热电偶、镍铬-镍硅热电偶、铁-康铜热电偶和钨铼(W-Re)热电偶是比较常见的几种高温热电偶，其中钨铼热电偶与其它热电偶相比，具有明显的优势：For the measurement of ultra-high temperature above 1600 °C, non-contact (infrared, optical, etc.) methods are often used for measurement, but the non-contact method not only has a slow response speed, but also the temperature measurement accuracy is far less than the direct contact type temperature measurement using a thermocouple. Platinum rhodium (Pt-Rh) thermocouples, nickel-chromium-nickel silicon thermocouples, iron-constantan thermocouples and tungsten-rhenium (W-Re) thermocouples are common types of high-temperature thermocouples, among which tungsten-rhodium thermocouples Compared with other thermocouples, it has obvious advantages:
(1)熔点高(>3000℃)，强度大，抗热震性好，化学性质稳定；(1) High melting point (>3000 ° C), high strength, good thermal shock resistance and stable chemical properties;
(2)热电动势大(约为铂铑热电偶的2～3倍)，灵敏度高；(2) The thermal electromotive force is large (about 2 to 3 times that of the platinum-iridium thermocouple), and the sensitivity is high;
(3)测温范围大，工作温度上限可达2800℃；(3) The temperature measurement range is large, and the upper limit of the working temperature can reach 2800 ° C;
(4)价格便宜(约为铂铑热电偶的十分之一)。(4) The price is cheap (about one tenth of the platinum-iridium thermocouple).
然而，钨铼热电偶在有氧环境下从300℃左右即开始氧化，只适用于还原、惰性、真空等环境的高温测量，不能在高温氧化性气氛中应用。因此，如何提高钨铼热电偶抗氧化能力，一直是国内外高温测量领域高度关注的课题。However, the tungsten-rhenium thermocouple starts to oxidize from about 300 ° C in an aerobic environment, and is only suitable for high-temperature measurement in environments such as reduction, inertness, and vacuum, and cannot be applied in a high-temperature oxidizing atmosphere. Therefore, how to improve the anti-oxidation ability of tungsten-rhenium thermocouples has been a topic of high concern in the field of high-temperature measurement at home and abroad.
目前在有氧环境下使用钨铼热电偶测温，一般采取两种方式：一种是一次性测量使用，即每次测温时间很短，热电偶氧化失效后即不再使用或重新处理加工后使用，另一种方式是对热电偶采取抗氧化处理。目前商业化的钨铼热电偶防氧化技术主要为铠装保护法，即采用石英、刚玉、难熔金属以及高温陶瓷等作为保护管，装入钨铼热电偶后抽空密封、充惰性气体密封或充填惰性粉体密封，在保护管内为热电偶人为创造出非氧化性气 氛，使其在氧化蚀损前完成测温使命，但这种不可拆卸的实体型抗氧化热电偶，存在以下问题：At present, the temperature is measured by a tungsten-rhenium thermocouple in an aerobic environment. Generally, two methods are used: one is for one-time measurement, that is, each temperature measurement time is short, and the thermocouple is no longer used or reprocessed after oxidation failure. After use, another way is to take anti-oxidation treatment on the thermocouple. At present, the commercial tungsten-tungsten thermocouple anti-oxidation technology is mainly an armored protection method, that is, quartz, corundum, refractory metal and high-temperature ceramics are used as protective tubes, and after being filled into a tungsten-rhenium thermocouple, the air-sealed seal is filled with an inert gas seal or Filled with an inert powder seal, creating a non-oxidizing atmosphere for the thermocouple in the protective tube to complete the temperature measurement mission before oxidation damage, but this non-removable solid anti-oxidation thermocouple has the following problems:
(1)热电偶使用温度受保护管耐温能力的限制，通常低于1800℃；(1) The temperature of the thermocouple is limited by the temperature resistance of the protective tube, usually less than 1800 ° C;
(2)热电偶铠装保护后体积和重量增大，在体积要求比较严格的系统中使用受到限制；(2) The volume and weight increase after thermocouple armor protection, and the use in systems with strict volume requirements is limited;
(3)采用套管和填充物质保护后，热电偶的响应速度受到很大影响。(3) After the protection of the casing and the filling material, the response speed of the thermocouple is greatly affected.
通过在钨铼热电偶表面涂覆抗氧化涂层，在不影响响应速度的前提下，提高热电偶在高温空气及其它高温氧化气氛中的测温上限、延长测温工作时间，是解决以上问题的比较理想的方法。实际上，国内外这方面的研究从上世纪六十年代起就已开展，但始终未见持续性的公开报道，而且全球范围内至今没有相关产品投入实际使用。By coating the surface of the tungsten-rhenium thermocouple with an anti-oxidation coating, the upper limit of temperature measurement and the extended temperature measurement time of the thermocouple in high-temperature air and other high-temperature oxidizing atmospheres are improved without affecting the response speed, which solves the above problems. The ideal method. In fact, research at home and abroad has been carried out since the 1960s, but there has been no continuous public reporting, and no relevant products have been put into practical use on a global scale.
本发明提出了一种新型的用于钨铼热电偶表面的高温抗氧化氧阻挡材料，使之能实现2000℃以上超高温有氧环境下的长时间接触式测温。The invention provides a novel high-temperature anti-oxidation oxygen barrier material for the surface of a tungsten-rhenium thermocouple, so that it can realize long-time contact temperature measurement under an ultra-high temperature aerobic environment of 2000 ° C or higher.
发明内容Summary of the invention
针对现有技术的以上缺陷或改进需求，本发明提供了一种钨铼热电偶高温抗氧化涂层结构中的氧阻挡材料及其应用，其目的在于通过在钨铼热电偶高温抗氧化涂层结构中的最外部设置一种多层结构的氧阻挡材料，该多层结构中的氧阻挡材料存在成分梯度和浓度梯度，即通过调整每一层材料种类或材料之间的配比，使得氧阻挡材料中各层材料热膨胀系数向远离钨铼热电偶基体的方向逐渐增大，氧阻挡材料中各层材料的耐氧烧蚀能力向远离钨铼热电偶基体的方向也逐渐增大，从而增加钨铼热电偶高温抗氧化涂层的附着力，同时减小钨铼热电偶高温抗氧化涂层的应力，由此解决2000℃以上超高温有氧环境中的长时间接触式测温的问题。In view of the above defects or improvement requirements of the prior art, the present invention provides an oxygen barrier material in a tungsten-rhenium thermocouple high-temperature oxidation resistant coating structure and an application thereof, the object of which is to pass a high temperature oxidation resistant coating on a tungsten-rhenium thermocouple. The outermost part of the structure is provided with a multi-layered oxygen barrier material, and the oxygen barrier material in the multilayer structure has a composition gradient and a concentration gradient, that is, oxygen is adjusted by adjusting the ratio of each layer of material or material. The thermal expansion coefficient of each layer of the barrier material gradually increases away from the tungsten-rhenium thermocouple matrix, and the oxygen-resistant ablation ability of each layer of the oxygen barrier material gradually increases away from the tungsten-rhenium thermocouple matrix, thereby increasing The adhesion of the tungsten-rhenium thermocouple high-temperature anti-oxidation coating and the stress of the high-temperature anti-oxidation coating of the tungsten-rhenium thermocouple are solved, thereby solving the problem of long-time contact temperature measurement in an ultra-high temperature aerobic environment above 2000 °C.
为实现上述目的，按照本发明的一个方面，提供了一种钨铼热电偶抗氧化涂层结构中的氧阻挡材料，其为不低于2层的多层结构，所述氧阻挡材料中各层材料的热膨胀系数向远离所述钨铼热电偶基体的方向逐渐增 大。In order to achieve the above object, according to an aspect of the invention, an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure is provided, which is a multilayer structure of not less than two layers, each of the oxygen barrier materials The coefficient of thermal expansion of the layer material gradually increases away from the tungsten-rhodium thermocouple matrix.
优选地，所述多层结构的氧阻挡材料存在成分梯度或浓度梯度，即所述氧阻挡材料的多层结构中每一层采用不同的材料种类以形成成分梯度；或者每一层材料种类相同且至少为两种材料的混合物，但是各层中材料的配比不同以形成浓度梯度。Preferably, the oxygen barrier material of the multilayer structure has a composition gradient or a concentration gradient, that is, each layer of the multilayer structure of the oxygen barrier material adopts different material species to form a composition gradient; or each layer has the same material type And at least a mixture of two materials, but the ratio of materials in each layer is different to form a concentration gradient.
优选地，所述氧阻挡材料最外层的热膨胀系数与所述基体热膨胀系数之差的绝对值不大于7×10
-6K
-1。
Preferably, the absolute value of the difference between the thermal expansion coefficient of the outermost layer of the oxygen barrier material and the thermal expansion coefficient of the substrate is not more than 7 × 10 -6 K -1 .
优选地，所述氧阻挡材料中各层材料的耐氧烧蚀能力向远离所述钨铼热电偶基体的方向逐渐增大。Preferably, the oxygen ablative resistance of each layer of material in the oxygen barrier material gradually increases away from the tungsten rhodium thermocouple matrix.
优选地，所述氧阻挡材料选用在2000℃以上能起到氧阻挡或耐氧烧蚀作用的难熔金属氧化物、硼化物或氮化物。Preferably, the oxygen barrier material is selected from a refractory metal oxide, a boride or a nitride which can function as an oxygen barrier or an oxygen ablation at 2000 ° C or higher.
优选地，所述氧阻挡材料选自氧化硅、氧化铪、硼化铪、氮化铪、氧化锆、硼化锆、氮化锆和氧化钇中的一种或多种。Preferably, the oxygen barrier material is selected from one or more of the group consisting of silicon oxide, hafnium oxide, tantalum boride, tantalum nitride, zirconium oxide, zirconium boride, zirconium nitride, and hafnium oxide.
优选地，所述氧阻挡材料总厚度为50～200微米。Preferably, the oxygen barrier material has a total thickness of from 50 to 200 microns.
优选地，所述氧阻挡材料的层数为5～20层。Preferably, the number of layers of the oxygen barrier material is 5-20 layers.
按照本发明的另一个方面，提供了一种所述的钨铼热电偶抗氧化涂层结构的氧阻挡材料的应用，用作钨铼热电偶抗氧化涂层结构中的氧阻挡材料，该氧阻挡材料位于所述钨铼热电偶抗氧化涂层结构的最外部。According to another aspect of the present invention, there is provided an application of an oxygen barrier material of the tungsten-rhenium thermocouple oxidation-resistant coating structure as an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure, the oxygen The barrier material is located at the outermost portion of the tungsten-rhenium thermocouple oxidation-resistant coating structure.
优选地，所述氧阻挡材料附着于所述钨铼热电偶基体表面。Preferably, the oxygen barrier material is attached to the surface of the tungsten-rhodium thermocouple substrate.
优选地，通过化学气相沉积法、热喷涂法或溶胶凝胶法在所述钨铼热电偶基体表面制备得到所述氧阻挡材料。Preferably, the oxygen barrier material is prepared on the surface of the tungsten-rhodium thermocouple substrate by a chemical vapor deposition method, a thermal spray method or a sol-gel method.
总体而言，通过本发明所构思的以上技术方案与现有技术相比，能够取得下列有益效果：In general, the above technical solutions conceived by the present invention can achieve the following beneficial effects compared with the prior art:
(1)本发明提出的钨铼热电偶高温抗氧化涂层结构中包含有多层结构的氧阻挡材料，该多层结构中的氧阻挡材料存在成分梯度和浓度梯度，即通过调整每一层材料种类或材料之间的配比，使得形成的氧阻挡材料在靠 近钨铼热电偶基体的氧阻挡层材料热膨胀系数与基体热膨胀系数之差的绝对值不大于7×10
-6K
-1，且氧阻挡材料中各层材料热膨胀系数向远离钨铼热电偶基体的方向逐渐增大，这样，相比简单的钨铼基体与只有一层的氧阻挡层的组合，它将原本热膨胀系数大的差异通过成分梯度或浓度梯度以渐变的形式分散到了层与层之间，使得热膨胀系数由内而外缓缓增大，有效减小了钨铼热电偶高温抗氧化涂层的热应力，同时增大了钨铼热电偶高温抗氧化涂层的附着力。
(1) The tungsten-rhenium thermocouple high-temperature oxidation-resistant coating structure proposed by the present invention comprises a multi-layered oxygen barrier material, and the oxygen barrier material in the multilayer structure has a composition gradient and a concentration gradient, that is, by adjusting each layer The material type or the ratio between the materials, so that the absolute value of the difference between the thermal expansion coefficient of the oxygen barrier material and the thermal expansion coefficient of the matrix of the oxygen barrier material formed near the tungsten-rectifier thermocouple substrate is not more than 7×10 -6 K -1 , Moreover, the thermal expansion coefficient of each layer of the oxygen barrier material gradually increases away from the tungsten-rhenium thermocouple matrix, so that the combination of the simple tungsten-rhenium matrix and the oxygen barrier layer having only one layer will have a large thermal expansion coefficient. The difference is dispersed in the gradual form between the layer and the layer by the composition gradient or the concentration gradient, so that the coefficient of thermal expansion gradually increases from the inside to the outside, effectively reducing the thermal stress of the high temperature oxidation resistant coating of the tungsten-rhenium thermocouple, and increasing The adhesion of the high temperature anti-oxidation coating of the tungsten-rhenium thermocouple is increased.
(2)本发明氧阻挡材料为多层结构，其氧阻挡材料中各层材料不仅热膨胀系数向远离钨铼热电偶基体的方向呈递增状态，保证良好的应力分散，而且其各层材料的耐氧烧蚀能力向远离钨铼热电偶基体的方向也逐渐增大，这样在确保应力分散、抗氧化涂层高温下稳定不脱落的同时，耐氧烧蚀能力即抗氧化能力也得到保证，进一步体现本发明的钨铼热电偶抗氧化涂层中氧阻挡材料的优越性。(2) The oxygen barrier material of the present invention has a multi-layer structure, and the material of each layer in the oxygen barrier material not only has an increasing coefficient of thermal expansion in a direction away from the tungsten-rhenium thermocouple substrate, but also ensures good stress dispersion, and the resistance of each layer of the material. The oxygen ablation ability is gradually increased away from the tungsten-rhenium thermocouple substrate, so that the oxygen-resistant ablation ability, that is, the oxidation resistance, is ensured while ensuring stress dispersion and high temperature resistance of the oxidation-resistant coating. The superiority of the oxygen barrier material in the tungsten-rhenium thermocouple oxidation resistant coating of the present invention is embodied.
(3)本发明提出的钨铼热电偶抗氧化涂层及氧阻挡材料直接附着于钨铼热电偶丝基体表面，总厚度为200微米以内，该钨铼热电偶抗氧化涂层在2000℃以上能够持续工作30min以上不脱落，抗氧化时间长且温度响应速度快。(3) The tungsten-rhenium thermocouple anti-oxidation coating and the oxygen barrier material proposed by the invention are directly attached to the surface of the tungsten-rhodium thermocouple wire substrate, and the total thickness is within 200 micrometers, and the tungsten-rhenium thermocouple oxidation-resistant coating is above 2000 °C. It can work continuously for more than 30min without falling off, has long anti-oxidation time and fast temperature response.
(4)本发明钨铼热电偶抗氧化涂层结构中的多层结构的氧阻挡材料，材料选择至关重要，当采用不同材料实现具有浓度梯度或成分梯度的多层结构氧阻挡材料时，不仅满足了热膨胀系数递增，实现应力良好分散的问题，同时实验证实了在同等厚度下相比较同一种材料的氧阻挡材料，耐氧烧蚀能力即抗氧化能力大大增强，说明不同成分种类的氧阻挡材料或层与层之间的氧阻挡材料发挥了协同促进作用，增强了总体抗氧化涂层的抗氧化能力，为该涂层实现2000℃以上持续工作30分钟以上提供了有力保证。(4) The oxygen barrier material of the multilayer structure in the tungsten-rhenium thermocouple anti-oxidation coating structure of the present invention, material selection is essential, when different materials are used to realize a multilayer structure oxygen barrier material having a concentration gradient or a composition gradient, It not only satisfies the problem of increasing thermal expansion coefficient and achieving good stress dispersion. At the same time, it is confirmed by experiments that oxygen barrier materials of the same material are compared at the same thickness, and the oxygen-resistant ablation ability, that is, the antioxidant capacity is greatly enhanced, indicating the oxygen content of different components. The barrier material or the oxygen barrier material between the layers acts synergistically to enhance the oxidation resistance of the overall oxidation resistant coating, providing a strong guarantee for the coating to last for more than 30 minutes at 2000 °C.
(5)本发明通过选择特定的氧阻挡材料，巧妙设计氧阻挡材料的多层结构，并设置层与层之间的成分梯度或浓度梯度，通过独特的设计构思与 材料种类的精心选择，结合特定的制备工艺和参数选择，最终获得了一种钨铼热电偶高温抗氧化涂层的氧阻挡材料，其能够在2000℃以上持续抗氧化30min以上，抗氧化性能以及热电偶响应速度均远远优于现有技术的热电偶抗氧化涂层。(5) The present invention ingeniously designs a multilayer structure of an oxygen barrier material by selecting a specific oxygen barrier material, and sets a composition gradient or a concentration gradient between the layers, and combines the unique design concept with the careful selection of the material types. Specific preparation process and parameter selection, finally obtained a tungsten-tantalum thermocouple high-temperature anti-oxidation coating oxygen barrier material, which can resist oxidation for more than 30min above 2000 °C, oxidation resistance and thermocouple response speed are far Superior to prior art thermocouple oxidation resistant coatings.
图1是本发明实施例1提供的钨铼热电偶抗氧化涂层结构中的氧阻挡材料的结构示意图；1 is a schematic structural view of an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 1 of the present invention;
图2是本发明实施例1提供的钨铼热电偶抗氧化涂层结构中的氧阻挡材料覆盖在钨铼热电偶表面的外观图；2 is an external view of an oxygen barrier material covering a tungsten-rhenium thermocouple surface in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 1 of the present invention;
图3是本发明实施例1提供的钨铼热电偶抗氧化涂层结构中的氧阻挡材料经1000℃退火后的SEM微观结构；3 is a SEM microstructure of an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 1 of the present invention after annealing at 1000 ° C;
图4是本发明实施例1提供的钨铼热电偶抗氧化涂层结构中的氧阻挡材料烧蚀10min后钨铼热电偶表面形貌；4 is a surface morphology of a tungsten-rhenium thermocouple after ablation of an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 1 of the present invention;
图5本发明实施例2提供的钨铼热电偶抗氧化涂层结构中的氧阻挡材料涂层经2300℃氧乙炔焰烧蚀10分钟后的SEM照片；5 is a SEM photograph of an oxygen barrier material coating in a tungsten-rhenium thermocouple oxidation-resistant coating structure provided by Example 2 of the present invention after being ablated by an oxyacetylene flame at 2300 ° C for 10 minutes;
图6为本发明实施例3提供的钨铼热电偶抗氧化涂层结构中的氧阻挡材料涂层经2500℃氧乙炔焰烧蚀35分钟后的SEM照片；6 is a SEM photograph of an oxygen barrier material coating in a tungsten-rhenium thermocouple oxidation-resistant coating structure provided by Example 3 of the present invention after being ablated by an oxyacetylene flame at 2500 ° C for 35 minutes;
图7为本发明实施例4提供的钨铼热电偶抗氧化涂层结构中的氧阻挡材料的结构示意图；7 is a schematic structural view of an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 4 of the present invention;
图8为本发明实施例4提供的钨铼热电偶抗氧化涂层结构中的氧阻挡材料涂层经1000℃退火处理后，用2300℃以上氧乙炔焰进行烧蚀，其热电势随烧蚀时间的变化图。8 is an ablation of an oxygen barrier material coating in a tungsten-rhenium thermocouple oxidation-resistant coating structure according to Embodiment 4 of the present invention after annealing at 1000 ° C, with an oxyacetylene flame of 2300 ° C or higher, and a thermoelectric potential thereof with ablation Time change chart.
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的 本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Further, the technical features involved in the various embodiments of the present invention described below may be combined with each other as long as they do not constitute a conflict with each other.
本发明提供了一种钨铼热电偶抗氧化涂层结构中的氧阻挡材料，该氧阻挡材料位于钨铼热电偶抗氧化涂层结构的最外部，其为不低于2层的多层结构，所述氧阻挡材料中各层材料的热膨胀系数向远离所述钨铼热电偶基体的方向逐渐增大。作为其中的一种方案，该氧阻挡材料即为所述钨铼热电偶的抗氧化涂层，其直接附着于钨铼热电偶基体表面。多层结构的氧阻挡材料存在成分梯度或浓度梯度，即所述氧阻挡材料的多层结构中每一层采用不同的材料种类以形成成分梯度；或者每一层材料种类相同且至少为两种材料的混合物，但是各层中材料的配比不同以形成浓度梯度。氧阻挡材料最外层的热膨胀系数与所述基体热膨胀系数之差的绝对值不大于7×10
-6K
-1。氧阻挡材料中各层材料的耐氧烧蚀能力向远离所述钨铼热电偶基体的方向逐渐增大。耐氧烧蚀能力大小可以通过在氧焰中燃烧测试其耐氧烧蚀即抗氧化能力。氧阻挡材料选用在2000℃以上能起到氧阻挡或耐氧烧蚀作用的难熔金属氧化物、硼化物或氮化物。氧阻挡材料选自氧化硅、氧化铪、硼化铪、氮化铪、氧化锆、硼化锆、氮化锆和氧化钇中的一种或多种。氧阻挡材料总厚度为50～200微米，优选的厚度范围为100～200微米，氧阻挡材料的层数可以设置为5～20层，优选为10～20层。氧阻挡材料的厚度很重要，不能太厚否则热电偶温度响应速度受影响；当然也不能太薄，否则抗氧化涂层容易脱落，抗氧化性能不能得到保证，所以如何在温度响应速度与耐氧烧蚀能力之间取得平衡是关键。
The invention provides an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure, which is located at the outermost part of the tungsten-rhenium thermocouple oxidation-resistant coating structure, which is a multilayer structure of not less than 2 layers. The coefficient of thermal expansion of each layer of material in the oxygen barrier material gradually increases away from the tungsten-rhodium thermocouple matrix. As one of the solutions, the oxygen barrier material is an oxidation resistant coating of the tungsten-rhenium thermocouple, which is directly attached to the surface of the tungsten-rhodium thermocouple substrate. The oxygen barrier material of the multilayer structure has a composition gradient or a concentration gradient, that is, each layer of the multilayer structure of the oxygen barrier material adopts different material species to form a composition gradient; or each layer has the same material type and at least two A mixture of materials, but the ratio of materials in each layer is different to form a concentration gradient. The absolute value of the difference between the thermal expansion coefficient of the outermost layer of the oxygen barrier material and the thermal expansion coefficient of the substrate is not more than 7 × 10 -6 K -1 . The oxygen ablative ability of each layer of material in the oxygen barrier material gradually increases away from the tungsten rhodium thermocouple matrix. The ability of the oxygen-resistant ablation ability can be tested for its resistance to oxygen ablation or oxidation by burning in an oxygen flame. The oxygen barrier material is a refractory metal oxide, a boride or a nitride which can function as an oxygen barrier or an oxygen ablation at 2000 ° C or higher. The oxygen barrier material is selected from one or more of the group consisting of silicon oxide, hafnium oxide, tantalum boride, tantalum nitride, zirconium oxide, zirconium boride, zirconium nitride, and hafnium oxide. The oxygen barrier material has a total thickness of 50 to 200 μm, preferably has a thickness ranging from 100 to 200 μm, and the number of layers of the oxygen barrier material may be set to 5 to 20 layers, preferably 10 to 20 layers. The thickness of the oxygen barrier material is very important, not too thick, otherwise the temperature response speed of the thermocouple is affected; of course, it should not be too thin, otherwise the oxidation resistant coating will fall off easily, and the oxidation resistance cannot be guaranteed, so how to respond to temperature and oxygen in temperature A balance between ablation capabilities is key.
本发明钨铼热电偶抗氧化涂层结构中多层结构的氧阻挡材料，材料选择至关重要，当采用不同材料实现具有浓度梯度或成分梯度的多层结构氧阻挡材料时，不仅满足了热膨胀系数递增，实现应力良好分散的问题，同时也取得了在同等厚度下相比较同一种材料的氧阻挡材料，耐氧烧蚀能力即抗氧化能力大大增强，说明不同成分种类的氧阻挡材料或层与层之间的 氧阻挡材料发挥了协同促进作用，增强了总体抗氧化涂层的抗氧化能力，为该涂层实现2000℃以上持续工作30分钟以上提供了有力保证。The oxygen barrier material of the multilayer structure in the tungsten-rhenium thermocouple anti-oxidation coating structure of the invention is crucial for material selection. When a multi-layer oxygen barrier material having a concentration gradient or a composition gradient is realized by using different materials, the thermal expansion is not only satisfied. The coefficient is increased to achieve the problem of good stress dispersion. At the same time, the oxygen barrier material of the same material is obtained at the same thickness, and the oxygen-resistant ablation ability, that is, the oxidation resistance is greatly enhanced, indicating that the oxygen barrier material or layer of different component types is different. The oxygen barrier material between the layers exerts a synergistic promoting effect, enhances the oxidation resistance of the overall antioxidant coating, and provides a strong guarantee for the coating to achieve continuous operation for more than 30 minutes at 2000 °C.
上述多层结构的氧阻挡材料用作钨铼热电偶抗氧化涂层结构中的氧阻挡材料，可直接设置于于钨铼热电偶基体表面作为该钨铼热电偶材料的抗氧化涂层，也可以在基体与该样阻挡材料之间设置过渡层。The above-mentioned multilayer structure oxygen barrier material is used as an oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure, and can be directly disposed on the surface of the tungsten-rhenium thermocouple substrate as an anti-oxidation coating of the tungsten-rhenium thermocouple material. A transition layer may be provided between the substrate and the barrier material.
上述钨铼热电偶抗氧化涂层结构的氧阻挡材料的制备方法，包括如下步骤：The preparation method of the oxygen barrier material of the above-mentioned tungsten-rhenium thermocouple oxidation-resistant coating structure comprises the following steps:
(1)选择热膨胀系数与钨铼热电偶基体热膨胀系数之差的绝对值不大于6×10
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-1的材料或材料的混合物作为氧阻挡材料，通过化学气相沉积法、热喷涂法或溶胶凝胶法在钨铼热电偶基体表面进行第一层氧阻挡材料的制备；
(1) selecting a material or a mixture of materials having an absolute value of a difference between a thermal expansion coefficient and a thermal expansion coefficient of a tungsten-rhenium thermocouple substrate of not more than 6 × 10 -6 K -1 as an oxygen barrier material by chemical vapor deposition, thermal spraying or Sol-gel method for preparing a first layer of oxygen barrier material on a surface of a tungsten-rhenium thermocouple substrate;
(2)依次更换每一层材料种类，或材料种类不更换，逐渐调配每一层中不同材料的浓度配比，按照步骤(1)相同的方法向远离钨铼热电偶基体的方向逐层沉积，使得制备得到的多层结构的氧阻挡材料中各层材料热膨胀系数向远离所述钨铼热电偶基体的方向逐渐增大，所述氧阻挡材料中各层材料的耐氧烧蚀能力向远离所述钨铼热电偶基体的方向也逐渐增大；逐层沉积至氧阻挡材料总厚度为50～200μm。(2) sequentially change the material type of each layer, or replace the material type, gradually adjust the concentration ratio of different materials in each layer, and deposit layer by layer in the same direction away from the tungsten-rhenium thermocouple substrate in the same way as step (1). So that the thermal expansion coefficient of each layer of the oxygen barrier material of the prepared multilayer structure is gradually increased away from the tungsten-rhenium thermocouple substrate, and the oxygen-resistant ablation ability of each layer of the oxygen barrier material is far away. The direction of the tungsten-rhodium thermocouple substrate is also gradually increased; the total thickness of the oxygen barrier material deposited layer by layer is 50-200 μm.
本发明钨铼热电偶抗氧化涂层结构中的氧阻挡材料可通过等离子体增强化学气相沉积法在基体或基体表面的过渡层外层沉积多层结构的氧阻挡材料，或用等离子喷涂法在基体或基体表面的过渡层外层喷涂多层结构的氧阻挡材料，也可采用溶胶凝胶法在基体或基体表面的过渡层外层凝结多层结构的氧阻挡材料，优选采用溶胶凝胶法制备氧阻挡材料。The oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure of the present invention may deposit a multi-layered oxygen barrier material on the outer layer of the transition layer of the substrate or the substrate surface by plasma enhanced chemical vapor deposition, or by plasma spraying method. The outer layer of the transition layer on the surface of the substrate or the substrate is sprayed with a multi-layered oxygen barrier material, and the sol-gel method may also be used to condense the oxygen barrier material of the multilayer structure on the outer layer of the transition layer of the substrate or the substrate surface, preferably by a sol-gel method. An oxygen barrier material is prepared.
以下为实施例：The following are examples:
实施例1Example 1
一种钨铼热电偶高温抗氧化涂层结构中的氧阻挡材料，该氧阻挡材料直接设置于钨铼热电偶基体即直径约为0.5mm的钨铼热电偶丝表面，即该 氧阻挡材料即为该钨铼热电偶的抗氧化涂层，如图1所示，该抗氧化涂层一共有五层，第一层为ZrB2材料，热膨胀系数为6.5×10
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-1，厚度为10μm；第二层为ZrB2-5％SiC材料，厚度为10μm；第三层为ZrB2-10％SiC，厚度为10μm；第四层为ZrB2-15％SiC，厚度为10μm；第五层为ZrB2-20％SiC，热膨胀系数为9×10
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-1，厚度为10μm。该多层结构的氧阻挡材料总厚度为50微米，其热膨胀系数以及耐氧烧蚀能力向远离钨铼热电偶基体的方向均逐渐增大。
An oxygen barrier material in a tungsten-rhenium thermocouple high-temperature oxidation-resistant coating structure, the oxygen barrier material is directly disposed on a tungsten-rhenium thermocouple substrate, that is, a tungsten-rhenium thermocouple wire having a diameter of about 0.5 mm, that is, the oxygen barrier material is For the anti-oxidation coating of the tungsten-rhenium thermocouple, as shown in FIG. 1, the oxidation-resistant coating has five layers, the first layer is ZrB2 material, the thermal expansion coefficient is 6.5×10 -6 K -1 , and the thickness is 10 μm. The second layer is ZrB2-5% SiC material, the thickness is 10μm; the third layer is ZrB2-10% SiC, the thickness is 10μm; the fourth layer is ZrB2-15% SiC, the thickness is 10μm; the fifth layer is ZrB2- 20% SiC, having a thermal expansion coefficient of 9 × 10 -6 K -1 and a thickness of 10 μm. The multi-layered oxygen barrier material has a total thickness of 50 micrometers, and its thermal expansion coefficient and oxygen ablation resistance gradually increase toward the tungsten carbide thermocouple matrix.
该钨铼热电偶抗氧化涂层结构中氧阻挡材料的制备方法为：The preparation method of the oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure is:
先用八水合氧氯化锆(10～20wt％)、聚乙二醇4000(10～20wt％)和去离子水(60～80wt％)制备锆溶胶，然后用氨水调节溶胶PH值为2～3，陈化数日稳定后取一定量于烧杯中掺入二氧化锆粉(溶胶质量的10～40％)，均匀搅拌制成悬浮液，再采用提拉机将钨铼热电偶浸入-拉出-干燥制得第一层；取等量溶胶，将二氧化锆粉和碳化硅粉(总质量占溶胶质量的10～40％)按质量比19：1加入到溶胶中去，重复浸入-拉出-干燥步骤制得第二层；另取等量溶胶，将二氧化锆粉和碳化硅粉(总质量占溶胶质量的10～40％)按质量比18：2加入到溶胶中去，重复浸入-拉出-干燥步骤制得第三层；另取等量溶胶，将二氧化锆粉和碳化硅粉(总质量占溶胶质量的10～40％)按质量比17：3加入到溶胶中去，重复浸入-拉出-干燥步骤制得第四层；另取等量溶胶，将二氧化锆粉和碳化硅粉(总质量占溶胶质量的10～40％)按质量比16：4加入到溶胶中去，重复浸入-拉出-干燥步骤制得第五层；制得五层具有成分梯度的钨铼热电偶抗氧化涂层。图2是氧阻挡材料覆盖在钨铼热电偶表面的外观图。First, zirconium sol is prepared by using zirconium oxychloride octachloride (10-20 wt%), polyethylene glycol 4000 (10-20 wt%) and deionized water (60-80 wt%), and then adjusting the pH of the sol with ammonia water to 2~ 3, after a few days of stabilization, take a certain amount of zirconium dioxide powder (10-40% of the mass of the sol) in the beaker, stir evenly to make a suspension, and then use a pulling machine to immerse the tungsten-rhodium thermocouple into the pull-pull The first layer is obtained by drying-out; taking an equal amount of sol, adding zirconium dioxide powder and silicon carbide powder (total mass of 10 to 40% of the mass of the sol) to the sol at a mass ratio of 19:1, and repeating the immersion- The second layer is obtained by a pull-drying step; an equal amount of sol is taken, and the zirconium dioxide powder and the silicon carbide powder (the total mass is 10-40% of the mass of the sol) are added to the sol at a mass ratio of 18:2. Repeating the immersion-drawing-drying step to obtain the third layer; taking an equal amount of sol, adding zirconium dioxide powder and silicon carbide powder (total mass of 10-40% of the mass of the sol) to the sol at a mass ratio of 17:3 In the middle, repeat the immersion-drawing-drying step to obtain the fourth layer; another equal amount of sol, the zirconia powder and the silicon carbide powder (the total mass accounts for 10 of the sol quality) ～40%) was added to the sol at a mass ratio of 16:4, and the fifth layer was prepared by repeating the immersion-drawing-drying step; five layers of a tungsten-rhenium thermocouple oxidation-resistant coating having a composition gradient were obtained. 2 is an external view of an oxygen barrier material covering a surface of a tungsten-rhodium thermocouple.
经1000℃退火处理后，用2000℃左右氧乙炔焰进行烧蚀，图3是氧阻挡层材料经1000℃退火后的SEM微观结构，可以看到涂层较为致密，孔隙率较少。图4是烧蚀10min后钨铼热电偶表面形貌，可以看出涂层表面产生的熔融态物质将裂纹填充，晶粒明显变大，说明短时间内涂层具有较好 的保护作用，基底未被明显氧化。After annealing at 1000 °C, it is ablated with an oxyacetylene flame at about 2000 °C. Figure 3 shows the SEM microstructure of the oxygen barrier layer after annealing at 1000 °C. It can be seen that the coating is dense and the porosity is small. Figure 4 shows the surface morphology of the tungsten-rhenium thermocouple after ablation for 10 min. It can be seen that the molten material produced on the surface of the coating will be filled with cracks and the grains will become larger, indicating that the coating has a good protective effect in a short time. Not significantly oxidized.
实施例2Example 2
一种钨铼热电偶高温抗氧化涂层结构中的氧阻挡材料，该氧阻挡材料直接设置于钨铼热电偶基体即直径约为0.5mm的钨铼热电偶丝表面，即该氧阻挡材料即为该钨铼热电偶的抗氧化涂层，该抗氧化涂层一共有六层，第一层为SiC材料，热膨胀系数为4.5×10
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-1，厚度为20μm；第二层为SiC-20％HfC材料，厚度为20μm；第三层为SiC-40％HfC，厚度为20μm；第四层为SiC-60％HfC，厚度为20μm；第五层为SiC-80％HfC，厚度为20μm；第六层为HfC，热膨胀系数为6.7×10
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-1，厚度为20μm。该多层结构的氧阻挡材料总厚度为120微米，其热膨胀系数以及耐氧烧蚀能力向远离钨铼热电偶基体的方向均逐渐增大。
An oxygen barrier material in a tungsten-rhenium thermocouple high-temperature oxidation-resistant coating structure, the oxygen barrier material is directly disposed on a tungsten-rhenium thermocouple substrate, that is, a tungsten-rhenium thermocouple wire having a diameter of about 0.5 mm, that is, the oxygen barrier material is For the anti-oxidation coating of the tungsten-rhenium thermocouple, the anti-oxidation coating has a total of six layers, the first layer is SiC material, the thermal expansion coefficient is 4.5×10 -6 K -1 , the thickness is 20 μm; the second layer is SiC -20% HfC material, thickness 20μm; third layer is SiC-40%HfC, thickness is 20μm; fourth layer is SiC-60%HfC, thickness is 20μm; fifth layer is SiC-80%HfC, thickness is 20 μm; the sixth layer is HfC, the coefficient of thermal expansion is 6.7×10 -6 K -1 , and the thickness is 20 μm. The oxygen barrier material of the multilayer structure has a total thickness of 120 micrometers, and its thermal expansion coefficient and oxygen ablation resistance gradually increase toward the tungsten carbide thermocouple matrix.
该钨铼热电偶抗氧化涂层结构中氧阻挡材料的制备方法为：The preparation method of the oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure is:
以氢气(流速约为750sccm)、甲基三氯硅烷(流速约为200sccm)和四氯化铪(流速约为100sccm)作为反应气相，以氩气为载体(流速约为350sccm)，按各层涂层成分调节反应气相中各气源的占比，在850mTorr左右低压、900℃左右高温下通过低压化学气相沉积的方法可以制得成分占比渐变的多层x％SiC-y％HfC薄层，沉积速度约为3μm/h。Hydrogen (flow rate about 750sccm), methyltrichlorosilane (flow rate about 200sccm) and ruthenium tetrachloride (flow rate about 100sccm) as the reaction gas phase, argon gas as the carrier (flow rate is about 350sccm), according to each layer The coating composition adjusts the proportion of each gas source in the reaction gas phase, and a thin layer of multi-layer x% SiC-y%HfC with a compositional composition gradient can be obtained by low pressure chemical vapor deposition at a low pressure of about 850 mTorr and a high temperature of about 900 °C. The deposition rate is about 3 μm/h.
制得的多层涂层经1000℃退火处理后，用2300℃以上氧乙炔焰进行烧蚀，图5为涂层经2300℃氧乙炔焰烧蚀10分钟后的SEM照片。由图5可见，涂层表面经长时间高温火焰冲刷而出现开裂，但未见明显贯通裂纹。The obtained multilayer coating was annealed at 1000 ° C and then ablated with an oxyacetylene flame of 2300 ° C or higher. FIG. 5 is a SEM photograph of the coating after ablation of the oxyacetylene flame at 2300 ° C for 10 minutes. It can be seen from Fig. 5 that the surface of the coating is cracked by a long time high temperature flame scouring, but no obvious through crack is observed.
实施例3Example 3
一种钨铼热电偶高温抗氧化涂层结构中的氧阻挡材料，该氧阻挡材料直接设置于钨铼热电偶基体即直径约为0.5mm的钨铼热电偶丝表面，即该氧阻挡材料即为该钨铼热电偶的抗氧化涂层，该抗氧化涂层一共有十一层，第一层为HfO2材料，热膨胀系数为4.3×10
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-1，厚度为20μm；第二层为HfO2-10％YSZ(钇稳定氧化锆，摩尔比Y：Zr＝6：100)材料，厚度为20μm； 第三层为HfO2-20％YSZ，厚度为20μm；第四层为HfO2-30％YSZ，厚度为20μm；第五层为HfO2-40％YSZ，厚度为20μm；第六层为HfO2-50％YSZ，厚度为20μm；第七层为HfO2-60％YSZ，厚度为20μm；第八层为HfO2-70％YSZ，厚度为20μm；第九层为HfO2-80％YSZ，厚度为20μm；第十层为HfO2-90％YSZ，厚度为20μm；第十一层为YSZ，热膨胀系数为11.5×10
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-1，厚度为20μm。该多层结构的氧阻挡材料总厚度为210微米，其热膨胀系数以及耐氧烧蚀能力向远离钨铼热电偶基体的方向均逐渐增大。
An oxygen barrier material in a tungsten-rhenium thermocouple high-temperature oxidation-resistant coating structure, the oxygen barrier material is directly disposed on a tungsten-rhenium thermocouple substrate, that is, a tungsten-rhenium thermocouple wire having a diameter of about 0.5 mm, that is, the oxygen barrier material is For the anti-oxidation coating of the tungsten-rhenium thermocouple, the anti-oxidation coating has a total of eleven layers, the first layer is HfO2 material, the thermal expansion coefficient is 4.3×10 -6 K -1 , and the thickness is 20 μm; the second layer is HfO2-10%YSZ (yttrium-stabilized zirconia, molar ratio Y:Zr=6:100) material, thickness 20μm; third layer is HfO2-20%YSZ, thickness is 20μm; fourth layer is HfO2-30%YSZ , thickness is 20μm; fifth layer is HfO2-40%YSZ, thickness is 20μm; sixth layer is HfO2-50%YSZ, thickness is 20μm; seventh layer is HfO2-60%YSZ, thickness is 20μm; eighth layer It is HfO2-70%YSZ, the thickness is 20μm; the ninth layer is HfO2-80%YSZ, the thickness is 20μm; the tenth layer is HfO2-90%YSZ, the thickness is 20μm; the eleventh layer is YSZ, the thermal expansion coefficient is 11.5 ×10 -6 K -1 , thickness 20 μm. The multi-layered oxygen barrier material has a total thickness of 210 micrometers, and its thermal expansion coefficient and oxygen ablation resistance gradually increase away from the tungsten-rhenium thermocouple matrix.
该钨铼热电偶抗氧化涂层结构中氧阻挡材料的制备方法为：The preparation method of the oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure is:
先用八水合氧氯化铪(10～20wt％)、聚乙二醇4000(10～20wt％)和去离子水(60～80wt％)制备铪溶胶，然后用氨水调节溶胶PH值为2～3，陈化数日稳定后取一定量于烧杯中掺入二氧化铪粉(溶胶质量的10～40％)，均匀搅拌制成悬浮液，再采用提拉机将钨铼热电偶浸入-拉出-干燥制得第一层；取等量溶胶，将二氧化铪粉和氧化锆-6％摩尔氧化钇粉(总质量占溶胶质量的10～40％)按质量比9：1加入到溶胶中去，重复浸入-拉出-干燥步骤制得第二层；另取等量溶胶，将二氧化铪粉和氧化锆-6％摩尔氧化钇粉(总质量占溶胶质量的10～40％)按质量比8：2加入到溶胶中去，重复浸入-拉出-干燥步骤制得第三层；依次类推，制得十一层具有成分梯度的钨铼热电偶抗氧化涂层。First, cerium sol is prepared by using cerium oxychloride octahydrate (10-20% by weight), polyethylene glycol 4000 (10-20% by weight) and deionized water (60-80% by weight), and then adjusting the pH of the sol with ammonia water to 2~ 3, after a few days of stabilization, take a certain amount of cerium oxide powder (10-40% of the mass of the sol) in the beaker, stir evenly to make a suspension, and then use a pulling machine to immerse the tungsten-rhodium thermocouple into the pull-pull The first layer is obtained by drying-out; the same amount of sol is used, and the cerium oxide powder and the zirconia-6% molar cerium oxide powder (the total mass is 10-40% of the mass of the sol) are added to the sol at a mass ratio of 9:1. In the middle, repeat the immersion-extraction-drying step to obtain the second layer; another equal amount of sol, cerium oxide powder and zirconia-6% molar cerium oxide powder (total mass of 10-40% of the mass of the sol) The third layer was prepared by repeating the immersion-drawing-drying step at a mass ratio of 8:2; and eleven layers of a tungsten-rhenium thermocouple oxidation-resistant coating having a composition gradient were obtained.
制得的多层涂层经1000℃退火处理后，用2500℃以上氧乙炔焰进行烧蚀，图6为涂层经2500℃氧乙炔焰烧蚀35分钟后的SEM照片。由图6可见，涂层表面经长时间高温火焰冲刷而逐层剥离、开裂，但WRe热电偶基体形态基本保持完好。The obtained multilayer coating was annealed at 1000 ° C and then ablated with an oxyacetylene flame of 2500 ° C or higher. FIG. 6 is a SEM photograph of the coating after ablation of the oxyacetylene flame at 2500 ° C for 35 minutes. It can be seen from Fig. 6 that the surface of the coating is peeled off and cracked layer by layer due to long-time high-temperature flame scouring, but the morphology of the WRe thermocouple substrate remains basically intact.
实施例4Example 4
一种钨铼热电偶高温抗氧化涂层结构中的氧阻挡材料，该氧阻挡材料与钨铼热电偶基体即直径约为0.5mm的钨铼热电偶丝表面之间还加有一层10μm左右厚度的TaC过渡层，如图7所示，氧阻挡材料一共有七层，靠近 钨铼热电偶基体为第一层，第一层为HfC-10％ZrC材料，热膨胀系数为6×10
-6K
-1，厚度为20μm；第二层为HfC-30％ZrC材料，厚度为20μm；第三层为HfC-50％ZrC，厚度为20μm；第四层为ZrC，热膨胀系数为7.3×10
-6K
-1，厚度为20μm；第五层为ZrC-10％ZrO
2，厚度为20μm；第六层为ZrC-30％ZrO
2，厚度为20μm；第七层为ZrC-50％ZrO
2，厚度为20μm。该多层结构的氧阻挡材料总厚度为140微米，其热膨胀系数以及耐氧烧蚀能力向远离钨铼热电偶基体的方向均逐渐增大。
An oxygen barrier material in a tungsten-rhenium thermocouple high-temperature oxidation-resistant coating structure, the oxygen barrier material and a tungsten-rhenium thermocouple substrate, that is, a tungsten-rhenium thermocouple wire having a diameter of about 0.5 mm, further having a thickness of about 10 μm The TaC transition layer, as shown in Figure 7, has seven layers of oxygen barrier material, the first layer is close to the tungsten-rhenium thermocouple substrate, and the first layer is HfC-10% ZrC material with a thermal expansion coefficient of 6×10 -6 K. -1 , thickness 20 μm; second layer is HfC-30% ZrC material, thickness 20 μm; third layer is HfC-50% ZrC, thickness is 20 μm; fourth layer is ZrC, thermal expansion coefficient is 7.3×10 -6 K -1 , thickness 20 μm; the fifth layer is ZrC-10% ZrO 2 , the thickness is 20 μm; the sixth layer is ZrC-30% ZrO 2 , the thickness is 20 μm; the seventh layer is ZrC-50% ZrO 2 , thickness It is 20 μm. The multi-layered oxygen barrier material has a total thickness of 140 micrometers, and its thermal expansion coefficient and oxygen ablation resistance gradually increase away from the tungsten-rhenium thermocouple matrix.
该钨铼热电偶抗氧化涂层结构中氧阻挡材料的制备方法为：The preparation method of the oxygen barrier material in the tungsten-rhenium thermocouple oxidation-resistant coating structure is:
先通过球磨对碳化铪、碳化锆以及氧化锆粉末分别进行细化处理，按照上述成分含量调整它们的质量比，然后通过等离子喷涂机控制喷涂距离150mm，喷涂功率30kW，送粉速率3kg/h，分别将具有不同成分占比的a％HfC-b％ZrC-c％ZrO2的包覆粉末喷涂在过渡层外层，依次制得七层具有成分梯度的钨铼热电偶氧阻挡材料。Firstly, the cerium carbide, zirconium carbide and zirconia powder are refined by ball milling, and their mass ratios are adjusted according to the above-mentioned components, and then the spraying distance is controlled by a plasma spraying machine to be 150 mm, the spraying power is 30 kW, and the powder feeding rate is 3 kg/h. A coated powder of a%HfC-b%ZrC-c%ZrO2 having a different composition ratio was sprayed on the outer layer of the transition layer, and seven layers of a tungsten-rhenium thermocouple oxygen barrier material having a composition gradient were sequentially prepared.
制得的多层涂层经1000℃退火处理后，用2300℃以上氧乙炔焰进行烧蚀，图8是其热电势随烧蚀时间的变化，可见850s时仍有热电动势产生，说明钨铼热电偶未被破坏，仍能正常工作，抗氧化涂层的防护效果显著。The obtained multilayer coating was annealed at 1000 °C and then ablated with an oxyacetylene flame of 2300 ° C or higher. Figure 8 shows the change of the thermoelectric potential with the ablation time. It can be seen that there is still a thermoelectromotive force at 850 s, indicating that tungsten ruthenium is present. The thermocouple is not damaged and still works normally, and the anti-oxidation coating has a significant protective effect.
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。Those skilled in the art will appreciate that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and scope of the present invention, All should be included in the scope of protection of the present invention.
Claims (10)
- 一种钨铼热电偶抗氧化涂层结构中的氧阻挡材料，其特征在于，其为不低于2层的多层结构，所述氧阻挡材料中各层材料的热膨胀系数向远离所述钨铼热电偶基体的方向逐渐增大。An oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure, characterized in that it is a multilayer structure of not less than two layers, and a coefficient of thermal expansion of each layer of the oxygen barrier material is away from the tungsten The direction of the thermocouple base is gradually increased.
- 如权利要求1所述的氧阻挡材料，其特征在于，所述多层结构的氧阻挡材料存在成分梯度或浓度梯度，即所述氧阻挡材料的多层结构中每一层采用不同的材料种类以形成成分梯度；或者每一层材料种类相同且至少为两种材料的混合物，但是各层中材料的配比不同以形成浓度梯度。The oxygen barrier material according to claim 1, wherein the oxygen barrier material of the multilayer structure has a composition gradient or a concentration gradient, that is, each layer of the multilayer structure of the oxygen barrier material adopts a different material type To form a composition gradient; or each layer of material is of the same kind and at least a mixture of two materials, but the ratio of materials in each layer is different to form a concentration gradient.
- 如权利要求1所述的氧阻挡材料，其特征在于，所述氧阻挡材料最外层的热膨胀系数与所述基体热膨胀系数之差的绝对值不大于7×10 -6K -1。 The oxygen barrier material according to claim 1, wherein an absolute value of a difference between a thermal expansion coefficient of the outermost layer of the oxygen barrier material and a thermal expansion coefficient of the substrate is not more than 7 × 10 -6 K -1 .
- 如权利要求1所述的氧阻挡材料，其特征在于，所述氧阻挡材料中各层材料的耐氧烧蚀能力向远离所述钨铼热电偶基体的方向逐渐增大。The oxygen barrier material according to claim 1, wherein the oxygen ablative ability of each of the layers of the oxygen barrier material gradually increases away from the tungsten carbide thermocouple matrix.
- 如权利要求1所述的氧阻挡材料，其特征在于，所述氧阻挡材料选用在2000℃以上能起到氧阻挡或耐氧烧蚀作用的难熔金属氧化物、硼化物或氮化物。The oxygen barrier material according to claim 1, wherein said oxygen barrier material is selected from the group consisting of refractory metal oxides, borides or nitrides capable of exhibiting oxygen barrier or oxygen ablation at temperatures above 2000 °C.
- 如权利要求1所述的氧阻挡材料，其特征在于，所述氧阻挡材料选自氧化硅、氧化铪、硼化铪、氮化铪、氧化锆、硼化锆、氮化锆和氧化钇中的一种或多种。The oxygen barrier material according to claim 1, wherein said oxygen barrier material is selected from the group consisting of silicon oxide, hafnium oxide, tantalum boride, tantalum nitride, zirconium oxide, zirconium boride, zirconium nitride, and hafnium oxide. One or more.
- 如权利要求1所述的氧阻挡材料，其特征在于，所述氧阻挡材料总厚度为50～200微米。The oxygen barrier material according to claim 1 wherein said oxygen barrier material has a total thickness of from 50 to 200 microns.
- 如权利要求1所述的氧阻挡材料，其特征在于，所述氧阻挡材料的层数为5～20层。The oxygen barrier material according to claim 1, wherein the number of layers of the oxygen barrier material is 5 to 20 layers.
- 一种如权利要求1～8任意一项所述的氧阻挡材料的应用，其特征在于，用作钨铼热电偶抗氧化涂层结构中的氧阻挡材料，该氧阻挡材料位于所述钨铼热电偶抗氧化涂层结构的最外部。Use of an oxygen barrier material according to any one of claims 1 to 8 for use as an oxygen barrier material in a tungsten-rhenium thermocouple oxidation-resistant coating structure, the oxygen barrier material being located in the tungsten-rhenium The outermost part of the thermocouple anti-oxidation coating structure.
- 如权利要求9所述的应用，其特征在于，所述氧阻挡材料附着于所述钨铼热电偶基体表面；优选地，通过化学气相沉积法、热喷涂法或溶胶凝胶法在所述钨铼热电偶基体表面制备得到所述氧阻挡材料。The use according to claim 9, wherein said oxygen barrier material is attached to said tungsten-rhodium thermocouple substrate surface; preferably, said tungsten is formed by chemical vapor deposition, thermal spraying or sol-gel method The oxygen barrier material is prepared on the surface of the thermocouple substrate.
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