CN108660442A - LaxTiyOzOxide includes the LaxTiyOzThe composite material and preparation method of oxide - Google Patents
LaxTiyOzOxide includes the LaxTiyOzThe composite material and preparation method of oxide Download PDFInfo
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- CN108660442A CN108660442A CN201810382638.4A CN201810382638A CN108660442A CN 108660442 A CN108660442 A CN 108660442A CN 201810382638 A CN201810382638 A CN 201810382638A CN 108660442 A CN108660442 A CN 108660442A
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- composite oxide
- tio
- lanthanum
- oxide coating
- coating
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 102
- 238000000576 coating method Methods 0.000 claims abstract description 102
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 229910003079 TiO5 Inorganic materials 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 229910017582 La2Ti2O7 Inorganic materials 0.000 claims abstract description 7
- 229910017587 La2Ti3O9 Inorganic materials 0.000 claims abstract description 7
- 229910017592 La4Ti9O24 Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims description 54
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 32
- 229910052719 titanium Inorganic materials 0.000 claims description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 150000002603 lanthanum Chemical class 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 15
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910009815 Ti3O5 Inorganic materials 0.000 claims description 3
- 229910009848 Ti4O7 Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000013459 approach Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- -1 is uniformly mixed Substances 0.000 claims description 2
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 2
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical group [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 239000011247 coating layer Substances 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 93
- 229910010271 silicon carbide Inorganic materials 0.000 description 40
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 39
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 20
- 229910052746 lanthanum Inorganic materials 0.000 description 19
- 238000010792 warming Methods 0.000 description 17
- 238000013019 agitation Methods 0.000 description 16
- 239000002356 single layer Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 235000011054 acetic acid Nutrition 0.000 description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 6
- 150000001243 acetic acids Chemical class 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- DRIUWMIAOYIBGN-UHFFFAOYSA-N lanthanum titanium Chemical compound [Ti][La] DRIUWMIAOYIBGN-UHFFFAOYSA-N 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000264877 Hippospongia communis Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011226 reinforced ceramic Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a kind of LaxTiyOzOxide, and include the LaxTiyOzThe composite oxide coating of oxide, LaxTiyOzOxide is amorphous state；Or it is LaTi3O49、La0.66TiO2.993、La2Ti6O5、La2Ti3O9、La5Ti5O17、La2TiO5、La4Ti9O24、La2Ti2O7And La4Ti3O12In one kind or arbitrary several mixtures.The invention also discloses the preparation method and application of above-mentioned composite oxide coating.The composite oxide coating preparation process of the present invention is simple, and coating raw material easily obtain, and coating covering is complete, even compact impurity is few, not easily to fall off, and coating layer thickness accurately controls, and can effectively promote the heat-resisting and corrosion resistance of treated object matrix.
Description
Technical field
The present invention relates to a kind of composite oxide coating and preparation method thereof, especially a kind of LaxTiyOzOxide includes
The LaxTiyOzThe composite material and preparation method of oxide.
Background technology
Fiber reinforced ceramic matrix composites with excellent performances such as corrosion-resistant, high temperature resistants in aerospace field due to obtaining
To extensive use, in the preparation process of composite material, the interface cohesion of fiber and matrix is influence composite property one
A key factor.In order to realize the optimized design at interface, coating appropriate is coated as fiber and matrix in fiber surface
Boundary layer is the most effective means.Interlayer materials itself will have higher inoxidizability；It can prevent ambient atmos and fibre
Dimension reacts；Under the premise of improving material against oxidative performance, the mechanical property of material is kept as much as possible.
Currently, mainly passing through chemical vapor deposition (CVD) method, magnetron sputtering method and sol-gel method etc. in fiber surface
Prepare pyrolysis carbon coating, BN and SiO2、Al2O3、TiO2Equal non-oxidized substances and oxide coating.Publication No. CN107540400A,
The patent application of CN 101497536 A and CN102251224 illustrates that preparing oxide by CVD method and magnetron sputtering method applies
The method of layer, the coating uniformity of preparation is good, and excellent to the protecting effect of fiber, but passes through CVD method and magnetron sputtering legal system
The cost of standby coating is higher, and equipment is expensive, and sample size is limited by settling chamber space, and target price used in magnetron sputtering is high
It is expensive, it is unfavorable for industrialization promotion, limits the application of the type coating.
The equipment that sol-gel method prepares coating does not need CVD method and the such complex and expensive of magnetron sputtering method has technique
Advantage easy, equipment requirement is low, suitable large area prepares film coating, and chemical composition is easier to control.Publication number
For CN105133291A and CN100516348C patent application respectively illustrate by sol-gel method prepare silica with
The method of aluminum oxide coating layer, prepared coating is more uniform, but the high-temperature oxidation resistance of coating is poor and be difficult to cover completely
Lid, it is limited to the performance boost of fiber.
Currently, lanthana coating is mainly obtained by lanthana target electrochemical deposition or the coating of nano-powder direct impregnation
.The patent application of Publication No. CN106116555A illustrates to be mixed with by lanthanum oxide powder and other precursor sols
Ceramic honey comb with lanthana coating, but the coating uniformity prepared by this way is poor, nano-powder is easy to reunite,
Distribution differs and thickness is thicker.The patent application of Publication No. CN105441999A is disclosed through electrochemical deposition method in metal
The method that lanthana coating is prepared on carrier, but it is higher by the cost of the technique prepares coating, to preparing the shape of sample
Size has strict demand, and prepared by the coating for being simply possible to use in metallic-based support.
Invention content
The purpose of the present invention is to provide a kind of precursor materials to be easy to get, simple for process, and coating covering is complete, repeatability
Good, defect is less, complete fine and close, excellent to the protection effect of treated object matrix composite oxide coating.
Another object of the present invention is to provide a kind of preparation method of above-mentioned composite oxide coating and as interface
The application of layer material.
Technical solution：The present invention provides a kind of LaxTiyOzOxide, the LaxTiyOzOxide is the LaTi of crystalline state3O49、
La0.66TiO2.993、La2Ti6O5、La2Ti3O9、La5Ti5O17、La2TiO5、La4Ti9O24、La2Ti2O7And La4Ti3O12In one kind
Or arbitrary several mixture, or be non-crystal oxide LaxTiyOz, or be the LaTi of crystalline state3O49、La0.66TiO2.993、
La2Ti6O5、La2Ti3O9、La5Ti5O17、La2TiO5、La4Ti9O24、La2Ti2O7And La4Ti3O12In one kind or arbitrary several
Mixture and non-crystal oxide LaxTiyOzMixture.
Another aspect of the present invention provides a kind of composite oxide coating, and composite oxide coating includes lanthana, TimOnWith
Above-mentioned LaxTiyOzOxide, TimOnFor TiO, TiO of crystalline state2、TiO1.04、Ti4O7、Ti3O5And TiO2In one kind or arbitrary several
The mixture of kind, or be non-crystal oxide TimOn, or be TiO, TiO of crystalline state2、TiO1.04、Ti4O7、Ti3O5And TiO2
In one kind or arbitrary several mixture and non-crystal oxide TimOnMixture.
Another aspect of the present invention provides a kind of method preparing above-mentioned composite oxide coating, includes the following steps：
1) lanthanum salt solution in water by lanthanum salt uniform dissolution, is made；
2) organotitanium precursor body, alcohols and acid are uniformly mixed, titanium solution is made；
3) the lanthanum salt solution is added drop-wise in titanium solution, is uniformly mixed, composite oxide coating precursor sol is made；
4) carrier is placed in composite oxide coating precursor sol, is obtained after dipping, drying and heat treatment compound
Oxide coating.
In step 1), it is preferable that in lanthanum salt solution, the mass ratio of lanthanum salt and water is (2~30): (70~98)；Lanthanum salt is
One or more of lanthanum acetate, lanthanum nitrate, lanthanum carbonate, lanthanum chloride mixture.
In step 2), the mass ratio of organotitanium precursor body, alcohols and acid is (1~20): (40~80): (1~20)；It is organic
Titanium precursors are one or more of tetraisopropyl titanate, butyl titanate and titanoxane mixture, and alcohols is ethyl alcohol, isopropyl
One or more of alcohol and n-butanol mixture, acid are one or more of nitric acid, acetic acid, hydrochloric acid, sulfuric acid mixture.
In step 3), it is 0.1~5ml/min that lanthanum salt solution, which is added drop-wise to the rate of addition in titanium solution, to avoid because of water
It solves excessive velocities and generates precipitation；The lanthanum salt solution of addition mass fraction in composite oxide coating precursor sol is more than
0% is less than 100%, it is preferable that the molar ratio of La atoms and Ti atoms is between 4: 9 to 2: 1.
Step 4) specifically includes following steps：A) by carrier impregnation 10 in composite oxide coating precursor sol~
20min makes precursor sol be uniformly distributed on treated object surface, then with the pull rate of 1~15mm/min by matrix from
It is taken out in composite oxide coating precursor sol, reduces the precursor accumulation generated during lifting since solution is assembled,
Drying, composite oxide coating precursor is obtained in carrier surface；
B) composite oxide coating precursor made from step a) is heat-treated 10min~3h at 500~1445 DEG C.
Preferably, treated in step b), and carrier heating rate is 1~20 DEG C/min, and soaking time is 1~3 hour；
Maximum heat treatment temperature is no more than 1445 DEG C of the temperature that coating material is stabilized, simultaneous not destroy treated object surface state
It is selected to care for the various specific conditions such as heat resistance and other proper properties of treated object；It is further preferred that heat treatment temperature
It is 500~1000 DEG C.
Preferably, in step 4), step a) is repeated as many times (step for repeatedly being impregnated, lifting and being dried), then
It is handled using step b) primary；Or repeatedly (i.e. the step of dipping, lifting, dry and heat treatment, is whole by entire step 4)
Body is repeated as many times), obtain MULTILAYER COMPOSITE oxide coating.Number of repetition can composite oxide coating according to specific needs the number of plies
It is configured.
Above-mentioned carrier can be metal alloy, ceramics, glass or plastics, and form is unrestricted, can be fiber, powder
Or bulk, the process conditions such as treatment temperature can be determined according to the heated or heat resisting temperature of various carriers.
The present invention also provides application of the above-mentioned composite oxide coating in boundary layer.
Advantageous effect：The composite oxide coating preparation process of the present invention is simple, and coating raw material easily obtain, coating covering
Completely, even compact, impurity are few, not easily to fall off, and thickness accurately controls, and can effectively promote the heat-resisting and resistance to of treated object matrix
Corrosive nature.
Description of the drawings
Fig. 1 is scanning electron microscope diagram (the addition lanthana mole of fiber surface single layer titanium lanthanium complex oxide coating
48%) score is；
Fig. 2 is the scanning electron microscope diagram of fiber surface Double-layer titanium lanthanium complex oxide coating；
Fig. 3 is the scanning electron microscope diagram of fiber surface titanium lanthanium complex oxide coating high-temp processing；
Fig. 4 is X-ray diffraction (XRD) figure of fiber surface different type composite oxide coating under treatment of different temperature
Spectrum；
Fig. 5 is the XRD results of the coating material of 800 DEG C of processing and various standard LaxTiyOzDetailed comparison；
Fig. 6 is the XRD results of the coating material of 800 DEG C of processing and various standard TimOnDetailed comparison；
Fig. 7 is La2O3-TiO2Phasor；
Fig. 8 (A) is the scanning electron microscope of the mono-layer oxidized lanthanum of fiber surface (pure zirconia lanthanum) coating；Fig. 8 (B) is fiber
The energy spectrum diagram of monolayer surface lanthana (pure zirconia lanthanum) coating；
Fig. 9 (A) is the scanning electron microscope of fiber surface single layer pure titinium dioxide coating (addition of non-oxidation lanthanum)；Fig. 9
(B) it is the energy spectrum diagram of fiber surface single layer pure titinium dioxide coating (addition of non-oxidation lanthanum)；
Before Figure 10 is the silicon carbide fibre ultrasonic vibration of fiber surface bilayer pure titinium dioxide coating (addition of non-oxidation lanthanum)
Pictorial diagram；
After Figure 11 is the silicon carbide fibre ultrasonic vibration of fiber surface bilayer pure titinium dioxide coating (addition of non-oxidation lanthanum)
Pictorial diagram.
Specific implementation mode
With reference to specific example, the present invention is described in detail.Embodiment has been used to be converted by polycarbosilane precusor
Basis material of special high insulating silicon carbide (Si-C-O) fiber of method as treated object.Fibre strength, surface topography observation,
Ingredient and phase composition have used Tensile strength of single fiber instrument, scanning electron microscope (SEM), X-ray energy spectrum (EDS) and X to penetrate respectively
Line diffractometer (XRD) carries out phenetic analysis.
Embodiment 1
Prepare lanthanum solution：0.37g lanthanum acetate powder is slowly added in 8g deionized waters, magnetic agitation at room temperature after adding
30min makes lanthanum acetate be completely dissolved, and solution becomes clear.
Prepare titanium solution：8g glacial acetic acids and 0.4g butyl titanates are successively slowly added in 8g ethyl alcohol, under room temperature
Magnetic agitation 30min makes solution be sufficiently mixed uniformly.
Above-mentioned lanthanum solution is slowly added dropwise with the speed of 0.1ml/min into titanium solution under the conditions of magnetic agitation, until
Lanthanum solution is added dropwise, and butyl titanate is made to be fully hydrolyzed, and continues to stir 10min at room temperature, and the titanium lanthanum for obtaining stable transparent is multiple
Close oxide sol.
Silicon carbide fibre is soaked in above-mentioned titanium lanthanium complex oxide colloidal sol after ultrasonic vibration 20min with 5mm/min's
Pull rate is taken out.The silicon carbide fibre placement of taking-up is dried in an oven, baking oven is warming up to the heating rate of 5 DEG C/min
1h is kept the temperature after 70 DEG C, is taken out after Temperature fall, and obtaining surface has the silicon carbide fibre of titanium lanthanium complex oxide presoma.It should
Fiber is placed into Muffle furnace, is warming up to 500 DEG C with the heating rate of 3 DEG C/min and is kept the temperature 1 hour, is taken out after furnace cooling,
It can be prepared by the silicon carbide fibre with single layer titanium lanthanium complex oxide coating.Fig. 1, which is the present embodiment, has single layer titanium lanthanum compound
The silicon carbide fibre scanning electron microscope (SEM) photograph of oxide coating.The surfacing, smooth, fine and close of coating prepared by the embodiment, thus
Explainable adhesion property of the coating on silicon carbide fibre surface is preferable, not easily to fall off.
Embodiment 2
Prepare lanthanum solution：0.37g lanthanum acetate powder is slowly added in 8g deionized waters, magnetic agitation at room temperature after adding
30min makes lanthanum acetate be completely dissolved, and solution becomes clear.
Prepare titanium solution：8g glacial acetic acids and 0.4g butyl titanates and priority are slowly added in 8g ethyl alcohol, room temperature condition
Lower magnetic agitation 30min, makes solution be sufficiently mixed uniformly.
Lanthanum solution is slowly added dropwise with the speed of 3ml/min into titanium solution under the conditions of magnetic agitation, until lanthanum solution
It is added dropwise, butyl titanate is made to be fully hydrolyzed, continue to stir 10min at room temperature, obtain the titanium lanthanum combined oxidation of stable transparent
Object colloidal sol.
Silicon carbide fibre is impregnated in above-mentioned titanium lanthanium complex oxide colloidal sol after ultrasonic vibration 20min with 5mm/min's
Pull rate is taken out.The silicon carbide fibre placement of taking-up is dried in an oven, baking oven is warming up to the heating rate of 5 DEG C/min
1h is kept the temperature after 70 DEG C, is taken out after Temperature fall, and obtaining surface has the silicon carbide fibre of titanium lanthanium complex oxide presoma.It should
Fiber is placed into Muffle furnace, is warming up to 500 DEG C with the heating rate of 3 DEG C/min and is sintered 1 hour, is taken out after furnace cooling,
It can be prepared by the silicon carbide fibre with single layer titanium lanthanium complex oxide coating.Repeated impregnations, drying and sintering step 2 times, i.e.,
The silicon carbide fibre with two layers of titanium lanthanium complex oxide coating can be made.Fig. 2, which is the present embodiment, has Double-layer titanium lanthanum composite oxygen
The silicon carbide fibre scanning electron microscope (SEM) photograph of compound coating.The surfacing, smooth, fine and close of coating prepared by the embodiment, thus may be used
Illustrate that coating is preferable in the adhesion property on silicon carbide fibre surface, it is not easily to fall off.
Embodiment 3
Prepare lanthanum solution：0.37g lanthanum acetate powder is slowly added in 8g deionized waters, magnetic agitation at room temperature after adding
30min makes lanthanum acetate be completely dissolved, and solution becomes clear.
Prepare titanium solution：By 8g glacial acetic acids and 0.4g parts of butyl titanates and successively it is slowly added in 8g ethyl alcohol, room temperature item
Magnetic agitation 30min under part makes solution be sufficiently mixed uniformly.
Lanthanum solution is slowly added dropwise with the speed of 5ml/min into titanium solution under the conditions of magnetic agitation, until lanthanum solution
It is added dropwise, butyl titanate is made to be fully hydrolyzed, continue to stir 10min at room temperature, obtain the titanium lanthanum combined oxidation of stable transparent
Object colloidal sol.
Silicon carbide fibre is soaked in above-mentioned titanium lanthanium complex oxide colloidal sol after ultrasonic vibration 20min with 5mm/min's
Pull rate is taken out.The silicon carbide fibre placement of taking-up is dried in an oven, baking oven is warming up to the heating rate of 5 DEG C/min
1h is kept the temperature after 70 DEG C, is taken out after Temperature fall, and obtaining surface has the silicon carbide fibre of titanium lanthanium complex oxide presoma.It should
Fiber is placed into Muffle furnace, is warming up to 700 DEG C with the heating rate of 3 DEG C/min and is kept the temperature 1 hour, is taken out after furnace cooling,
It can be prepared by the silicon carbide fibre with single layer titanium lanthanium complex oxide coating.Fig. 3 is to be applied with single layer titanium lanthanium complex oxide
The silicon carbide fibre scanning electron microscope (SEM) photograph of layer.The surfacing of coating prepared by the embodiment, smooth, fine and close, thus explainable painting
Adhesion property of the layer on silicon carbide fibre surface is preferable, not easily to fall off.
Embodiment 4
According to the proportioning of embodiment 1, the titanium lanthanium complex oxide colloidal sol of stable transparent is obtained.With the heating speed of 3 DEG C/min
Degree heating, this titanium lanthanium complex oxide colloidal sol is dried and is separately heated to 500 DEG C, 600 DEG C, 700 DEG C and 800 DEG C, obtains four
The powder of kind different disposal temperature.By the X-ray diffraction interpretation of result discovery to these powder, 500 DEG C and 600 DEG C of powder
X-ray diffraction peak value is notable not as good as 700 DEG C shown in Fig. 4 and 800 DEG C of powder.After 700 DEG C of comparison diagram 4 and 800 DEG C processing
X-ray diffraction peak it is found that 800 DEG C treated that peak value significantly increases.Coating composition is mainly by lanthana and LaxTiyOzWith
TimOnComposition.
In order to accurately determine LaxTiyOzComposition, will pass through 800 degree of treated powder x-ray diffraction results with it is various
Standard LaxTiyOzDiffraction maximum and the relationship at the angles 2-theta are compared in detail, and the results are shown in Figure 5.According to similar approach, mark
Determine TimOnComponent, the results are shown in Figure 6.The result of Fig. 4 and Fig. 5 demonstrates the coating material La of the present inventionxTiyOzIt is compound
The presence of oxide, LaxTiyOzOxide can be LaTi3O49、La0.66TiO2.993、La2Ti6O5、La2Ti3O9、La5Ti5O17With
La2TiO5.Titanium oxide Ti in Fig. 4 and Fig. 6mOnCan also be a variety of oxidation titanium components.
Deduced according to above-mentioned X-ray diffraction result, coating material has occurred significantly from 500 DEG C of amorphous state to 800 DEG C
Crystalline growth, amorphous La at 500 DEG C of lower temperaturexTiyOzAnd TimOnIn each composition atomic ratio can deviate crystal
The stoichiometric ratio of form.
When treatment temperature continues to increase, these composite oxides can be deduced by the equilbrium phase diagram of titanium dioxide and lanthana.
Fig. 7 is entitled " Phase stability and equilibria in the La2O3-TiO2The bibliography of system "
(Journal of the European Ceramic Society 2000 volume 20, page 1179 to page 1185) is provided
Titanium dioxide and lanthana phasor.If titanium dioxide and lanthana are in strict accordance with the ratio in figure, high temperatures are deposited
Will be mutually La2O3、TiO2、La2TiO5、La4Ti9O24、La2Ti2O7And La4Ti3O12In one kind or arbitrary several mixing
Object.In conjunction with Fig. 4's -7 as a result, the present invention coating composite material according to different disposal temperature include lanthana, titanium oxide and
LaxTiyOzOxide, wherein LaxTiyOzOxide is LaTi3O49、La0.66TiO2.993、La2Ti6O5、La2Ti3O9、
La5Ti5O17、La2TiO5、La4Ti9O24、La2Ti2O7And La4Ti3O12In one kind or arbitrary several mixtures, the lanthanum salt of addition
Solution mass fraction in the composite oxide coating precursor sol is more than 0% and is less than 100%, is analyzed according to Fig. 7, corresponding
Between the molar ratio of La atoms and Ti atoms is 4: 9 to 2: 1, under the conditions of theoretic phasor, it can be prepared in the proportional region
Pure LaxTiyOzOxide, non-oxidation lanthanum and titanium oxide are remaining.
Comparative example 1
Lanthanum acetate 0.6g and deionized water 20g are taken, magnetic agitation 10min after the two is mixed is added after solution clarification
10g absolute ethyl alcohols continue magnetic agitation 10min, and lotion is made.By fiber impregnation in lotion, after sonic oscillation 20min
It is taken out with the pull rate of 5mm/min.The fiber placement of taking-up is dried in an oven, baking oven is with the heating rate of 5 DEG C/min
20min is kept the temperature after being warming up to 60 DEG C, continues thereafter with and is warming up to 80 DEG C of heat preservation 20min, taken out after Temperature fall, obtaining surface has
The fiber of lanthanum acetate.There is the fiber of lanthanum acetate to be placed into Muffle furnace the surface, is heated up with the heating rate of 10 DEG C/min
To 500 DEG C and 1 hour is kept the temperature, is taken out after furnace cooling, you can the silicon carbide fibre with mono-layer oxidized lanthanum coating is made.Fig. 8
(A) it is that there is the SEM of the silicon carbide fibre of mono-layer oxidized lanthanum coating to scheme made from this comparative example, Fig. 8 (B) is made for this comparative example
The silicon carbide fibre with mono-layer oxidized lanthanum coating EDS figure.The surfacing of coating prepared by this comparative example, smooth, cause
Close, thus explainable adhesion property of the coating on silicon carbide fibre surface is preferable, not easily to fall off.However, lanthana coating lacks
Point is, lanthana in air can the moisture absorption, and be dissolved in acid, influence its extensive use.
Comparative example 2
Lanthanum acetate 1.2g and deionized water 20g are taken, lotion is made in magnetic agitation 10min after the two is mixed.It will carbonization
Silica fibre is immersed in lotion, is taken out with the pull rate of 10mm/min after sonic oscillation 20min.The fiber of taking-up is placed
It dries in an oven, baking oven keeps the temperature 10min after being warming up to 60 DEG C with the heating rate of 5 DEG C/min, continues thereafter with and is warming up to 80 DEG C
20min is kept the temperature, is taken out after Temperature fall, obtaining surface has the fiber of lanthanum acetate.There is the fiber of lanthanum acetate to put the surface
It sets in Muffle furnace, 500 DEG C of heat preservation 1h is warming up to the heating rate of 10 DEG C/min, is taken out after furnace cooling, obtains fiber A.
In addition, the silicon carbide fibre of uncoated processing is placed into Muffle furnace, 500 DEG C are warming up to the heating rate of 10 DEG C/min
1h is kept the temperature, is taken out after furnace cooling, obtains fiber B.
Fiber A and fiber B are carried out to the test of monofilament tensile strength respectively, fiber B intensity is 1.96GPa, and fiber A's is strong
It is about 100% to spend retention rate.Wherein, strength retention ratio is the ratio of fiber A and fiber B intensity.
Comparative example 3
12g ethyl alcohol, 1.05g glacial acetic acids and 1.2g butyl titanates are mixed, magnetic agitation 10min, makes under room temperature
Three kinds of substances are sufficiently mixed uniformly, obtain mixed solution；1.5g deionized waters are slowly added dropwise to mixed under the conditions of magnetic agitation
Close solution in, until deionized water drip it is complete, continue at room temperature stir 10min, so that butyl titanate is fully hydrolyzed, obtain light
The transparent TiO 2 sol of yellow.Silicon carbide fibre is impregnated in above-mentioned TiO 2 sol, after ultrasonic vibration 20min
It is taken out with the pull rate of 5mm/min.The silicon carbide fibre placement of taking-up is dried in an oven, baking oven is with the liter of 5 DEG C/min
Warm speed keeps the temperature 1h after being warming up to 70 DEG C, taken out after Temperature fall, and it is fine to obtain silicon carbide of the surface with TiO 2 precursor
Dimension.The fiber is placed into Muffle furnace, 500 DEG C are warming up to the heating rate of 3 DEG C/min and keeps the temperature 1 hour, furnace cooling
After take out, you can be made with single layer coating of titanium dioxide silicon carbide fibre, be denoted as fiber C.By untreated carbonization
Silica fibre is placed into Muffle furnace, is warming up to 500 DEG C with the heating rate of 3 DEG C/min and is kept the temperature 1 hour, is taken after furnace cooling
Go out, obtains fiber D.The test of monofilament tensile strength is carried out to fiber C and fiber D, fiber D intensity is 1.96GPa, fiber C's
Strength retention ratio is 98%.Wherein, strength retention ratio is the ratio of fiber C and fiber D intensity.Fig. 9 (A) is this comparative fibers
Scanning electron microscope (SEM) figure of C；Fig. 9 (B) is power spectrum (EDS) collection of illustrative plates of this comparative fibers C.Prepared by the embodiment
It is the surfacing of coating, smooth, fine and close.
Comparative example 4
12g ethyl alcohol, 1.05g glacial acetic acids and 0.8g butyl titanates are mixed, magnetic agitation 10min, makes under room temperature
Three kinds of substances are sufficiently mixed uniformly, obtain mixed solution；1.5g deionized waters are slowly added dropwise to mixed under the conditions of magnetic agitation
Close solution in, until deionized water drip it is complete, continue at room temperature stir 10min, so that butyl titanate is fully hydrolyzed, obtain light
The transparent TiO 2 sol of yellow.Silicon carbide fibre cloth is impregnated in above-mentioned TiO 2 sol, ultrasonic vibration 20min
It is taken out afterwards with the pull rate of 5mm/min.The silicon carbide fibre cloth placement of taking-up is dried in an oven, baking oven is with 5 DEG C/min
Heating rate be warming up to 70 DEG C after keep the temperature 1h, taken out after Temperature fall, obtain surface have TiO 2 precursor carbonization
Silica fibre cloth.There is the silicon carbide fibre cloth of TiO 2 precursor to be placed into Muffle furnace the surface, with the liter of 3 DEG C/min
Warm speed is warming up to 500 DEG C and keeps the temperature 1 hour, is taken out after furnace cooling, you can the carbon with single layer coating of titanium dioxide is made
SiClx fiber cloth.Repeated impregnations, drying and sintering step 2 times, you can it is fine that the silicon carbide with two-layer titanium dioxide coating is made
Wei Bu.To there is the silicon carbide fibre cloth of two-layer titanium dioxide coating to carry out ultrasonic vibration 2 minutes.Figure 10 is made from the present embodiment
Picture before silicon carbide fibre cloth ultrasonic vibration with two-layer titanium dioxide coating, Figure 11 are to have made from the present embodiment
Picture of the silicon carbide fibre cloth ultrasonic vibration of two-layer titanium dioxide coating after 2 minutes, comparison diagram 10 and Figure 11 can be seen that
The binding force of two-layer titanium dioxide coating and fiber is not strong, and fiber cloth periphery has part to scatter.
From above example and comparative example it is found that individually lanthana or titania coating have the shortcomings that intrinsic, such as implementation
Shown in result under the treatment conditions of example, although treatment conditions do not reach the formation of theoretical ideal a variety of composite oxides
Condition, lanthana and titanium oxide appearance are certain remaining, but a variety of composite oxides LaxTiyOz, lanthana and titanium oxide can
Make up independent lanthana or the intrinsic defect of titania coating.
Although only giving the example that composite oxide coating is coated in silicon carbide fibre in specific implementation mode, however,
Those skilled in the art are it is recognised that the composite oxide coating of the present invention can be used for common needing to coat interlayer materials
Surface, such as fiber and metal.
The above is only a preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of LaxTiyOzOxide, which is characterized in that the LaxTiyOzOxide is the LaTi of crystalline state3O49、
La0.66TiO2.993、La2Ti6O5、La2Ti3O9、La5Ti5O17、La2TiO5、La4Ti9O24、La2Ti2O7And La4Ti3O12And amorphous
One kind in state oxide or arbitrary several mixtures.
2. a kind of composite oxide coating, which is characterized in that the composite oxide coating includes lanthana, TimOnAnd LaxTiyOz
Oxide, the LaxTiyOzOxide is the LaTi of crystalline state3O49、La0.66TiO2.993、La2Ti6O5、La2Ti3O9、La5Ti5O17、
La2TiO5、La4Ti9O24、La2Ti2O7And La4Ti3O12And one kind in non-crystal oxide or arbitrary several mixtures, institute
State TimOnFor TiO, TiO of crystalline state2、TiO1.04、Ti4O7、Ti3O5And TiO2And one kind or arbitrary several in non-crystal oxide
Kind mixture.
3. a kind of method preparing composite oxide coating, which is characterized in that this approach includes the following steps：
1) lanthanum salt solution in water by lanthanum salt uniform dissolution, is made；
2) organotitanium precursor body is uniformly mixed with alcohols and acid, titanium solution is made；
3) the lanthanum salt solution is added drop-wise in the titanium solution, is uniformly mixed, composite oxide coating precursor sol is made；
4) carrier is placed in the composite oxide coating precursor sol, after dipping, drying and heat treatment described in acquisition
Composite oxide coating.
4. according to the method described in claim 3, it is characterized in that, in step 1), in the lanthanum salt solution, the lanthanum salt and water
Mass percent be (2~30): (70~98)；The lanthanum salt is one kind in lanthanum acetate, lanthanum nitrate, lanthanum carbonate, lanthanum chloride
Or several mixtures.
5. according to the method described in claim 3, it is characterized in that, in step 2), the organotitanium precursor body, alcohols and acid
Mass percent is (1~20): (40~80): (1~20)；The organotitanium precursor body is tetraisopropyl titanate, four fourth of metatitanic acid
One or more of ester and titanoxane mixture, the alcohols are that one or more of ethyl alcohol, isopropanol and n-butanol are mixed
Object is closed, the acid is one or more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid mixture.
6. according to the method described in claim 3, it is characterized in that, in step 3), by the lanthanum salt solution be added drop-wise to it is described in
Rate of addition be 0.1~5ml/min；The lanthanum salt solution of addition quality point in the composite oxide coating precursor sol
Number is more than 0% and is less than 100%.
7. according to the method described in claim 3, it is characterized in that, in step 3), the composite oxide coating presoma is molten
In glue, the molar ratio of La atoms and Ti atoms is 4: 9 to 2: 1.
8. according to the method described in claim 3, it is characterized in that, step 4) specifically includes following steps：
A) by carrier impregnation in composite oxide coating precursor sol 10~20min, then with the lifting of 1~15mm/min
Speed takes out described matrix from composite oxide coating precursor sol, and drying obtains composite oxides in carrier surface
Coating precursor；
B) composite oxide coating precursor made from step a) is heat-treated 1~3h at 500~1000 DEG C.
9. according to the method described in claim 8, it is characterized in that, this method includes：Step a) is repeated as many times, is then carried out
Step b)；Or be repeated as many times step 4), obtain MULTILAYER COMPOSITE oxide coating.
10. application of the composite oxide coating described in claim 2 in boundary layer.
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| CN113200566A (en) * | 2021-04-15 | 2021-08-03 | 有研资源环境技术研究院(北京)有限公司 | Pre-melted high-refractive-index optical coating material and preparation method and application thereof |
| CN113903483A (en) * | 2021-09-13 | 2022-01-07 | 哈尔滨工业大学 | Multilayer flexible composite material for protecting X/gamma rays and preparation method thereof |
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| CN1394680A (en) * | 2002-02-01 | 2003-02-05 | 重庆大学 | Nano-grade lanthanum titanium compound oxide, its preparation method and application |
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| US6077344A (en) * | 1997-09-02 | 2000-06-20 | Lockheed Martin Energy Research Corporation | Sol-gel deposition of buffer layers on biaxially textured metal substances |
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| CN113200566A (en) * | 2021-04-15 | 2021-08-03 | 有研资源环境技术研究院(北京)有限公司 | Pre-melted high-refractive-index optical coating material and preparation method and application thereof |
| CN113200566B (en) * | 2021-04-15 | 2022-06-17 | 有研资源环境技术研究院(北京)有限公司 | Pre-melted high-refractive-index optical coating material and preparation method and application thereof |
| CN113903483A (en) * | 2021-09-13 | 2022-01-07 | 哈尔滨工业大学 | Multilayer flexible composite material for protecting X/gamma rays and preparation method thereof |
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