CN108660442B - LaxTiyOzOxide comprising the LaxTiyOzComposite material of oxide and preparation method thereof - Google Patents
LaxTiyOzOxide comprising the LaxTiyOzComposite material of oxide and preparation method thereof Download PDFInfo
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- CN108660442B CN108660442B CN201810382638.4A CN201810382638A CN108660442B CN 108660442 B CN108660442 B CN 108660442B CN 201810382638 A CN201810382638 A CN 201810382638A CN 108660442 B CN108660442 B CN 108660442B
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- lanthanum
- composite oxide
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000463 material Substances 0.000 title description 12
- 238000000576 coating method Methods 0.000 claims abstract description 99
- 239000011248 coating agent Substances 0.000 claims abstract description 89
- 239000002131 composite material Substances 0.000 claims abstract description 63
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229910003079 TiO5 Inorganic materials 0.000 claims abstract description 7
- 229910017582 La2Ti2O7 Inorganic materials 0.000 claims abstract description 6
- 229910017587 La2Ti3O9 Inorganic materials 0.000 claims abstract description 6
- 229910017592 La4Ti9O24 Inorganic materials 0.000 claims abstract description 6
- 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 63
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 62
- 239000010936 titanium Substances 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 43
- 239000002243 precursor Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 150000002603 lanthanum Chemical class 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 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
- 150000001298 alcohols Chemical class 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 compound [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
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 97
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 44
- 229910010271 silicon carbide Inorganic materials 0.000 description 44
- DRIUWMIAOYIBGN-UHFFFAOYSA-N lanthanum titanium Chemical compound [Ti][La] DRIUWMIAOYIBGN-UHFFFAOYSA-N 0.000 description 21
- 239000004408 titanium dioxide Substances 0.000 description 20
- 238000001816 cooling Methods 0.000 description 15
- 239000002356 single layer Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 229910052746 lanthanum Inorganic materials 0.000 description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 230000010355 oscillation Effects 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 238000003618 dip coating Methods 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
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- 239000000919 ceramic Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 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
- 239000007788 liquid Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
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- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000011226 reinforced ceramic Substances 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
Abstract
The invention discloses LaxTiyOzOxide, and an oxide composition comprising the samexTiyOzComposite oxide coating of oxide, LaxTiyOzThe oxide is in an amorphous state; or is LaTi3O49、La0.66TiO2.993、La2Ti6O5、La2Ti3O9、La5Ti5O17、La2TiO5、La4Ti9O24、La2Ti2O7And La4Ti3O12One or any mixture of several of them. The invention also discloses a preparation method and application of the composite oxide coating. The composite oxide coating disclosed by the invention is simple in preparation process, raw materials of the coating are easy to obtain, the coating is completely covered, uniform and compact, few in impurities and not easy to fall off, the thickness of the coating can be accurately controlled, and the heat resistance and corrosion resistance of a treated substrate can be effectively improved.
Description
Technical Field
The invention relates to a composite oxide coating and a preparation method thereof, in particular to LaxTiyOzOxide comprising the LaxTiyOzOxide composite material and its preparation method.
Background
The fiber reinforced ceramic matrix composite has excellent performances of corrosion resistance, high temperature resistance and the like, and is widely applied to the field of aerospace, and in the preparation process of the composite, the interface combination of fibers and a matrix is a key factor influencing the performance of the composite. In order to achieve an optimal design of the interface, it is most effective to apply an appropriate coating on the surface of the fiber as an interface layer between the fiber and the matrix. The interface layer material has high oxidation resistance; the reaction between the outside air and the fiber can be prevented; on the premise of improving the oxidation resistance of the material, the mechanical property of the material is kept as much as possible.
At present, in the fiberThe surface is mainly prepared into pyrolytic carbon coating, BN and SiO by a Chemical Vapor Deposition (CVD) method, a magnetron sputtering method, a sol-gel method and the like2、Al2O3、TiO2And the like non-oxide and oxide coatings. Patent applications with publication numbers CN107540400A, CN 101497536 a and CN102251224 describe methods for preparing oxide coatings by CVD and magnetron sputtering methods, the prepared coatings have good uniformity and excellent protection effect on fibers, but the cost of preparing coatings by CVD and magnetron sputtering methods is high, the equipment is expensive, the size of a sample is limited by the space of a deposition chamber, and the target material used for magnetron sputtering is expensive, which is not beneficial to industrial popularization and limits the application of the coatings.
The sol-gel method for preparing the coating does not need complex and expensive equipment such as a CVD method and a magnetron sputtering method, has the advantages of simple and convenient process and low equipment requirement, is suitable for preparing a film coating in a large area, and has easily controlled chemical composition. Patent applications with publication numbers CN105133291A and CN100516348C respectively describe methods for preparing silica and alumina coatings by a sol-gel method, and the prepared coatings are relatively uniform, but the coatings have poor high-temperature oxidation resistance and are difficult to completely cover, and the improvement on the performance of fibers is limited.
At present, the lanthanum oxide coating is mainly obtained by electrochemical deposition of a lanthanum oxide target or direct dip coating of nano powder. Patent application publication No. CN106116555A describes that a honeycomb ceramic having a lanthanum oxide coating is prepared by mixing lanthanum oxide powder with other precursor sol, but the coating prepared by this method has poor uniformity, and the nano-powder is easy to agglomerate, has nonuniform distribution and is thick. Patent application publication No. CN105441999A discloses a method for preparing lanthanum oxide coating on a metal carrier by electrochemical deposition, but the cost of preparing the coating by this process is high, the shape and size of the prepared sample are strictly required, and the method can only be used for preparing the coating of the metal-based carrier.
Disclosure of Invention
The invention aims to provide a composite oxide coating which has the advantages of easily obtained precursor raw materials, simple process, complete coating coverage, good repeatability, fewer defects, completeness and compactness and excellent protection effect on a treated substrate.
The invention also aims to provide a preparation method of the composite oxide coating and application of the composite oxide coating as an interface layer material.
The technical scheme is as follows: the invention provides LaxTiyOzOxide of the LaxTiyOzLaTi with crystalline oxide3O49、La0.66TiO2.993、La2Ti6O5、La2Ti3O9、La5Ti5O17、La2TiO5、La4Ti9O24、 La2Ti2O7And La4Ti3O12One or a mixture of any more of them, or amorphous oxide LaxTiyOzOr crystalline LaTi3O49、La0.66TiO2.993、La2Ti6O5、La2Ti3O9、La5Ti5O17、 La2TiO5、La4Ti9O24、La2Ti2O7And La4Ti3O12One or a mixture of any of them and amorphous oxide LaxTiyOzA mixture of (a).
In another aspect, the invention provides a composite oxide coating comprising lanthanum oxide and TimOnAnd La as described abovexTiyOzOxide of TimOnCrystalline TiO, TiO2、TiO1.04、Ti4O7、Ti3O5And TiO2One or a mixture of any of the above, or amorphous oxide TimOnOr crystalline TiO, TiO2、TiO1.04、Ti4O7、Ti3O5And TiO2One or any ofMixtures of several with amorphous oxides of TimOnA mixture of (a).
In another aspect, the present invention provides a method for preparing the above composite oxide coating, comprising the steps of:
1) dissolving lanthanum salt in water uniformly to prepare a lanthanum salt solution;
2) uniformly mixing an organic titanium precursor, alcohols and acid to prepare a titanium solution;
3) dropwise adding the lanthanum salt solution into the titanium solution, and uniformly mixing to prepare composite oxide coating precursor sol;
4) and placing the carrier in the precursor sol of the composite oxide coating, and performing dipping, drying and heat treatment to obtain the composite oxide coating.
In the step 1), preferably, the mass ratio of the lanthanum salt to the water in the lanthanum salt solution is (2-30) to (70-98); the lanthanum salt is one or a mixture of more of lanthanum acetate, lanthanum nitrate, lanthanum carbonate and lanthanum chloride.
In the step 2), the mass ratio of the organic titanium precursor to the alcohol to the acid is (1-20) to (40-80) to (1-20); the organic titanium precursor is one or a mixture of more of tetraisopropyl titanate, tetrabutyl titanate and titanium alkyl oxide, the alcohol is one or a mixture of more of ethanol, isopropanol and n-butanol, and the acid is one or a mixture of more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid.
In the step 3), the dripping speed of the lanthanum salt solution into the titanium solution is 0.1-5 ml/min, so as to avoid the generation of precipitation caused by overhigh hydrolysis speed; the added lanthanum salt solution has a mass fraction of more than 0% and less than 100% in the precursor sol of the composite oxide coating, and preferably, the molar ratio of La atoms to Ti atoms is between 4: 9 and 2: 1.
The step 4) specifically comprises the following steps: a) dipping the carrier in the precursor sol of the composite oxide coating for 10-20 min to ensure that the precursor sol is uniformly distributed on the surface of the treated object, then taking the carrier out of the precursor sol of the composite oxide coating at a lifting speed of 1-15 mm/min, reducing the accumulation of the precursor generated by solution aggregation in the lifting process, drying and obtaining the precursor of the composite oxide coating on the surface of the carrier;
b) carrying out heat treatment on the composite oxide coating precursor prepared in the step a) at 500-1445 ℃ for 10 min-3 h.
Preferably, the temperature rising speed of the carrier treated in the step b) is 1-20 ℃/min, and the heat preservation time is 1-3 hours; the highest heat treatment temperature is not more than 1445 ℃ which is the stable existing temperature of the coating material, so that the surface state of the treated object is not damaged, and the temperature resistance and other inherent properties of the treated object are considered; further preferably, the heat treatment temperature is 500 to 1000 ℃.
Preferably, in step 4), step a) is repeated a plurality of times (i.e. a plurality of steps of dipping, pulling and drying are performed), and then treated once using step b); or repeating the whole step 4) for multiple times (namely, repeating the steps of dipping, pulling, drying and heat treatment for multiple times in a whole), and obtaining the multilayer composite oxide coating. The number of repetitions can be set according to the number of layers of the composite oxide coating as required.
The carrier can be metal alloy, ceramic, glass or plastic, the shape of the carrier is not limited, the carrier can be fiber, powder or block, and the processing conditions such as processing temperature can be determined according to the heating or heat-resisting temperature of various carriers.
The invention also provides the application of the composite oxide coating in the interface layer.
Has the advantages that: the composite oxide coating has the advantages of simple preparation process, easily obtained coating raw materials, complete, uniform and compact coating coverage, less impurities, difficulty in falling off, accurate thickness control and capability of effectively improving the heat resistance and corrosion resistance of a treated substrate.
Drawings
FIG. 1 is a scanning electron microscope image of a single-layer titanium lanthanum composite oxide coating on the surface of a fiber (the mole fraction of added lanthanum oxide is 48%);
FIG. 2 is a scanning electron microscope image of a double-layer titanium lanthanum composite oxide coating on the surface of a fiber;
FIG. 3 is a scanning electron microscope image of a high temperature treatment of a titanium lanthanum composite oxide coating on the surface of a fiber;
FIG. 4 is an X-ray diffraction (XRD) pattern of different types of composite oxide coatings on the surface of a fiber under different temperature treatments;
FIG. 5 is a graph of XRD results of 800 ℃ treated coating materials versus various standard LaxTiyOzDetailed comparison of (1);
FIG. 6 is a graph of XRD results of 800 ℃ treated coating materials with various standard TimOnDetailed comparison of (1);
FIG. 7 is La2O3-TiO2A phase diagram;
FIG. 8(A) is a scanning electron microscope of a single layer lanthanum oxide (pure lanthanum oxide) coating on the surface of a fiber; FIG. 8(B) is a spectrum of a single layer lanthanum oxide (pure lanthanum oxide) coating on the surface of a fiber;
FIG. 9(A) is a scanning electron microscope of a single layer of pure titanium dioxide coating (no lanthanum oxide addition) on the surface of a fiber; FIG. 9(B) is an energy spectrum of a single layer of pure titanium dioxide coating (no lanthanum oxide addition) on the surface of the fiber;
FIG. 10 is a diagram of a silicon carbide fiber with a double-layer pure titanium dioxide coating (without lanthanum oxide addition) on the fiber surface before ultrasonic oscillation;
fig. 11 is a graph of a silicon carbide fiber with a double-layer pure titanium dioxide coating (without lanthanum oxide addition) on the surface of the fiber after ultrasonic oscillation.
Detailed Description
The present invention will be described in detail with reference to specific examples. In the examples, highly insulating silicon carbide (Si-C-O) fibers produced by polycarbosilane precursor conversion were used as a substrate for a workpiece. Fiber strength, surface topography observations, composition and phase composition were characterized and analyzed using a fiber filament strength instrument, Scanning Electron Microscope (SEM), X-ray energy spectroscopy (EDS) and X-ray diffractometer (XRD), respectively.
Example 1
Preparing a lanthanum solution: slowly adding 0.37g of lanthanum acetate powder into 8g of deionized water, and magnetically stirring at room temperature for 30min after the addition is finished, so that lanthanum acetate is completely dissolved, and the solution becomes clear and transparent.
Preparing a titanium solution: 8g of glacial acetic acid and 0.4g of tetrabutyl titanate are slowly added into 8g of ethanol in sequence, and the mixture is magnetically stirred for 30min at room temperature, so that the solution is fully and uniformly mixed.
Slowly dripping the lanthanum solution into the titanium solution at the speed of 0.1ml/min under the condition of magnetic stirring until the lanthanum solution is completely dripped, fully hydrolyzing tetrabutyl titanate, and continuously stirring for 10min at room temperature to obtain the stable and transparent titanium-lanthanum composite oxide sol.
And soaking the silicon carbide fiber in the titanium lanthanum composite oxide sol, ultrasonically vibrating for 20min, and taking out at a pulling speed of 5 mm/min. And (3) placing the taken silicon carbide fiber in an oven for drying, heating the oven to 70 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 1h, naturally cooling, and taking out to obtain the silicon carbide fiber with the titanium lanthanum composite oxide precursor on the surface. And (3) placing the fiber into a muffle furnace, heating to 500 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 hour, cooling along with the furnace, and taking out to obtain the silicon carbide fiber with the single-layer titanium lanthanum composite oxide coating. FIG. 1 is a scanning electron microscope image of a silicon carbide fiber with a single-layer titanium lanthanum composite oxide coating according to the embodiment. The coating prepared by the embodiment has a flat, smooth and compact surface, so that the coating has good adhesion performance on the surface of the silicon carbide fiber and is not easy to fall off.
Example 2
Preparing a lanthanum solution: slowly adding 0.37g of lanthanum acetate powder into 8g of deionized water, and magnetically stirring at room temperature for 30min after the addition is finished, so that lanthanum acetate is completely dissolved, and the solution becomes clear and transparent.
Preparing a titanium solution: adding glacial acetic acid 8g and tetrabutyl titanate 0.4g successively and slowly into ethanol 8g, and magnetically stirring at room temperature for 30min to mix the solution completely and uniformly.
Slowly dripping the lanthanum solution into the titanium solution at the speed of 3ml/min under the condition of magnetic stirring until the dripping of the lanthanum solution is finished, fully hydrolyzing tetrabutyl titanate, and continuously stirring for 10min at room temperature to obtain stable and transparent titanium-lanthanum composite oxide sol.
And (3) soaking the silicon carbide fiber in the titanium lanthanum composite oxide sol, performing ultrasonic oscillation for 20min, and taking out at a pulling speed of 5 mm/min. And (3) placing the taken silicon carbide fiber in an oven for drying, heating the oven to 70 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 1h, naturally cooling, and taking out to obtain the silicon carbide fiber with the titanium lanthanum composite oxide precursor on the surface. And placing the fiber into a muffle furnace, heating to 500 ℃ at the heating rate of 3 ℃/min, sintering for 1 hour, cooling along with the furnace, and taking out to obtain the silicon carbide fiber with the single-layer titanium lanthanum composite oxide coating. And repeating the steps of dipping, drying and sintering for 2 times to obtain the silicon carbide fiber with two titanium lanthanum composite oxide coatings. FIG. 2 is a scanning electron microscope image of the silicon carbide fiber with a double-layer titanium lanthanum composite oxide coating according to the embodiment. The coating prepared by the embodiment has a flat, smooth and compact surface, so that the coating has good adhesion performance on the surface of the silicon carbide fiber and is not easy to fall off.
Example 3
Preparing a lanthanum solution: slowly adding 0.37g of lanthanum acetate powder into 8g of deionized water, and magnetically stirring at room temperature for 30min after the addition is finished, so that lanthanum acetate is completely dissolved, and the solution becomes clear and transparent.
Preparing a titanium solution: 8g of glacial acetic acid and 0.4g of tetrabutyl titanate are successively and slowly added into 8g of ethanol, and the mixture is magnetically stirred for 30min at room temperature, so that the solution is fully and uniformly mixed.
Slowly dripping the lanthanum solution into the titanium solution at the speed of 5ml/min under the condition of magnetic stirring until the dripping of the lanthanum solution is finished, fully hydrolyzing tetrabutyl titanate, and continuously stirring for 10min at room temperature to obtain the stable and transparent titanium-lanthanum composite oxide sol.
And soaking the silicon carbide fiber in the titanium lanthanum composite oxide sol, ultrasonically vibrating for 20min, and taking out at a pulling speed of 5 mm/min. And (3) placing the taken silicon carbide fiber in an oven for drying, heating the oven to 70 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 1h, naturally cooling, and taking out to obtain the silicon carbide fiber with the titanium lanthanum composite oxide precursor on the surface. And (3) placing the fiber into a muffle furnace, heating to 700 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 hour, cooling along with the furnace, and taking out to obtain the silicon carbide fiber with the single-layer titanium lanthanum composite oxide coating. FIG. 3 is a scanning electron microscope image of a silicon carbide fiber with a single-layer titanium lanthanum composite oxide coating. The coating prepared by the embodiment has a flat, smooth and compact surface, so that the coating has good adhesion performance on the surface of the silicon carbide fiber and is not easy to fall off.
Example 4
According to the mixture ratio of the embodiment 1, stable and transparent titanium lanthanum composite oxide sol is obtained. Heating at a heating rate of 3 ℃/min, drying the titanium lanthanum composite oxide sol, and respectively heating to 500 ℃, 600 ℃, 700 ℃ and 800 ℃ to obtain four kinds of powder with different treatment temperatures. Analysis of the X-ray diffraction results of these powders revealed that the X-ray diffraction peaks of the powders at 500 c and 600 c were not as significant as those of the powders at 700 c and 800 c shown in fig. 4. Comparing the X-ray diffraction peaks after 700 ℃ and 800 ℃ treatments in fig. 4, the peak value after 800 ℃ treatment was significantly enhanced. The coating mainly comprises lanthanum oxide and LaxTiyOzAnd TimOnAnd (4) forming.
To accurately determine LaxTiyOzThe powder after 800-degree treatment is subjected to X-ray diffraction, and the results of X-ray diffraction of the powder are compared with various standard LaxTiyOzThe relationship between the diffraction peak and the 2-theta angle was compared in detail, and the results are shown in FIG. 5. Ti is calibrated in a similar mannermOnThe results are shown in FIG. 6. The results of FIGS. 4 and 5 demonstrate that the coating material La of the present inventionxTiyOzPresence of complex oxide, LaxTiyOzThe oxide can be LaTi3O49、 La0.66TiO2.993、La2Ti6O5、La2Ti3O9、La5Ti5O17And La2TiO5. Titanium oxide Ti in FIGS. 4 and 6mOnMultiple titanium oxide components are also possible.
According to the X-ray diffraction results, the coating material is obviously crystallized and grows from the amorphous state at 500 ℃ to 800 ℃, and the La in the amorphous state at the lower temperature of 500 ℃ is inferredxTiyOzAnd TimOnThe ratio of the constituent atoms in (a) may deviate from the stoichiometric ratio of the crystal form.
These composite oxides can be inferred from the equilibrium phase diagram of titanium oxide and lanthanum oxide as the treatment temperature continues to rise. FIG. 7 is a chart entitled "Phase stability and equilibria in the La2O3-TiO2The reference to system "(Journal of the European Ceramic Society, 2000, Vol. 20, pp. 1179 to 1185) gives a phase diagram for titanium dioxide and lanthanum oxide. If the titanium dioxide and lanthanum oxide are in strict proportion in the figure, the phase stable at high temperature will be La2O3、TiO2、La2TiO5、La4Ti9O24、La2Ti2O7And La4Ti3O12One or any mixture of several of them. Combining the results of FIGS. 4-7, the coating composite of the present invention comprises lanthanum oxide, titanium oxide, and La depending on the different processing temperaturesxTiyOzOxide of, wherein LaxTiyOzThe oxide is LaTi3O49、La0.66TiO2.993、La2Ti6O5、La2Ti3O9、La5Ti5O17、La2TiO5、La4Ti9O24、 La2Ti2O7And La4Ti3O12The added lanthanum salt solution accounts for more than 0 percent and less than 100 percent of the composite oxide coating precursor sol, the molar ratio of La atoms to Ti atoms is 4: 9 to 2: 1 according to the analysis of figure 7, and under the condition of a theoretical phase diagram, pure La can be prepared in the range of the ratioxTiyOzOxide, no lanthanum oxide and no titanium oxide residue.
Comparative example 1
Mixing 0.6g of lanthanum acetate and 20g of deionized water, magnetically stirring for 10min, adding 10g of absolute ethyl alcohol after the solution is clarified, and continuously magnetically stirring for 10min to obtain the dip-coating solution. Soaking the fiber in the dip-coating solution, ultrasonically oscillating for 20min, and taking out at a pulling speed of 5 mm/min. And (3) drying the taken out fiber in an oven, heating the oven to 60 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 20min, then continuously heating to 80 ℃ and preserving the heat for 20min, naturally cooling and then taking out the fiber to obtain the fiber with lanthanum acetate on the surface. And (3) placing the fiber with lanthanum acetate on the surface into a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min, preserving heat for 1 hour, cooling along with the furnace, and taking out to obtain the silicon carbide fiber with a single-layer lanthanum oxide coating. Fig. 8(a) is an SEM image of a silicon carbide fiber having a single-layer lanthanum oxide coating layer obtained in the present comparative example, and fig. 8(B) is an EDS image of a silicon carbide fiber having a single-layer lanthanum oxide coating layer obtained in the present comparative example. The coating prepared by the comparative example has a flat, smooth and compact surface, so that the coating has good adhesion performance on the surface of the silicon carbide fiber and is not easy to fall off. However, the lanthanum oxide coating has the disadvantage that lanthanum oxide absorbs moisture in air and is dissolved in acid, which affects its wide application.
Comparative example 2
1.2g of lanthanum acetate and 20g of deionized water are taken, mixed and stirred magnetically for 10min to prepare the dip-coating liquid. The silicon carbide fiber is immersed in the dip-coating liquid, and is taken out at a pulling speed of 10mm/min after ultrasonic oscillation for 20 min. And (3) drying the taken out fiber in an oven, heating the oven to 60 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 10min, then continuously heating to 80 ℃ and preserving the heat for 20min, naturally cooling and then taking out the fiber to obtain the fiber with lanthanum acetate on the surface. And (3) placing the fiber with lanthanum acetate on the surface into a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, cooling along with the furnace, and taking out to obtain the fiber A. And in addition, placing the silicon carbide fiber which is not coated into a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, cooling along with the furnace, and taking out to obtain the fiber B.
The fiber A and the fiber B were respectively subjected to a test of tensile strength of a monofilament, the strength of the fiber B was 1.96GPa, and the strength retention of the fiber A was about 100%. Wherein, the strength retention rate is the ratio of the strength of the fiber A to the strength of the fiber B.
Comparative example 3
Mixing 12g of ethanol, 1.05g of glacial acetic acid and 1.2g of tetrabutyl titanate, and magnetically stirring for 10min at room temperature to fully and uniformly mix the three substances to obtain a mixed solution; slowly dripping 1.5g of deionized water into the mixed solution under the condition of magnetic stirring until the dripping of the deionized water is finished, and continuously stirring for 10min at room temperature to fully hydrolyze tetrabutyl titanate to obtain light yellow transparent titanium dioxide sol. And (3) soaking the silicon carbide fiber in the titanium dioxide sol, and taking out at a pulling speed of 5mm/min after ultrasonic oscillation for 20 min. And (3) placing the taken silicon carbide fiber in an oven for drying, heating the oven to 70 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 1h, naturally cooling, and taking out to obtain the silicon carbide fiber with the titanium dioxide precursor on the surface. The fiber is placed in a muffle furnace, heated to 500 ℃ at the heating rate of 3 ℃/min, kept for 1 hour, cooled along with the furnace and taken out, and then the silicon carbide fiber with the single-layer titanium dioxide coating is prepared and is marked as fiber C. And (3) placing the untreated silicon carbide fiber into a muffle furnace, heating to 500 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 hour, cooling along with the furnace, and taking out to obtain the fiber D. The tensile strength of the monofilaments was tested for fiber C and fiber D, with fiber D having a strength of 1.96GPa and fiber C having a strength retention of 98%. Wherein, the strength retention rate is the ratio of the strength of the fiber C to the strength of the fiber D. FIG. 9(A) is a Scanning Electron Microscope (SEM) image of fiber C of this comparative example; FIG. 9(B) is an energy spectrum (EDS) spectrum of fiber C of this comparative example. The coating prepared in this example has a smooth, smooth and dense surface.
Comparative example 4
Mixing 12g of ethanol, 1.05g of glacial acetic acid and 0.8g of tetrabutyl titanate, and magnetically stirring for 10min at room temperature to fully and uniformly mix the three substances to obtain a mixed solution; slowly dripping 1.5g of deionized water into the mixed solution under the condition of magnetic stirring until the dripping of the deionized water is finished, and continuously stirring for 10min at room temperature to fully hydrolyze tetrabutyl titanate to obtain light yellow transparent titanium dioxide sol. And (3) soaking the silicon carbide fiber cloth in the titanium dioxide sol, and taking out at a pulling speed of 5mm/min after ultrasonic oscillation for 20 min. And (3) placing the taken silicon carbide fiber cloth in an oven for drying, heating the oven to 70 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 1h, naturally cooling, and taking out to obtain the silicon carbide fiber cloth with the titanium dioxide precursor on the surface. And (3) placing the silicon carbide fiber cloth with the titanium dioxide precursor on the surface into a muffle furnace, heating to 500 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 hour, cooling along with the furnace, and taking out to obtain the silicon carbide fiber cloth with the single-layer titanium dioxide coating. And repeating the steps of dipping, drying and sintering for 2 times to obtain the silicon carbide fiber cloth with the double-layer titanium dioxide coating. And (3) carrying out ultrasonic oscillation on the silicon carbide fiber cloth with the double-layer titanium dioxide coating for 2 minutes. Fig. 10 is a picture of the silicon carbide fiber cloth with the double titanium dioxide coating layer prepared in this example before ultrasonic vibration, fig. 11 is a picture of the silicon carbide fiber cloth with the double titanium dioxide coating layer prepared in this example after ultrasonic vibration for 2 minutes, and comparing fig. 10 and fig. 11, it can be seen that the bonding force between the double titanium dioxide coating layer and the fiber is not strong, and the periphery of the fiber cloth is partially scattered.
As is apparent from the above examples and comparative examples, the lanthanum oxide or titanium oxide coating alone has inherent disadvantages, and as shown by the results under the treatment conditions of the examples, although the treatment conditions do not reach the theoretically ideal conditions for forming the multiple complex oxides, lanthanum oxide and titanium oxide show some residue, but the multiple complex oxides LaxTiyOzLanthanum oxide and titanium oxide can compensate the inherent defects of the lanthanum oxide or titanium oxide coating alone.
Although the specific embodiment only shows the example of the composite oxide coating applied on the silicon carbide fiber, the skilled person will know that the composite oxide coating of the present invention can be used on the common surface needing to be coated with interface layer materials, such as fiber and metal.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (6)
1. A method of producing a composite oxide coating, comprising the steps of:
1) dissolving lanthanum salt in water uniformly to prepare a lanthanum salt solution;
2) uniformly mixing an organic titanium precursor with alcohols and acid to prepare a titanium solution;
3) dropwise adding the lanthanum salt solution into the titanium solution, and uniformly mixing to obtain a precursor sol of the composite oxide coating;
4) dipping the carrier in the composite oxide coating precursor sol for 10-20 min, then taking the carrier out of the composite oxide coating precursor sol at a pulling speed of 1-15 mm/min, drying, and obtaining a composite oxide coating precursor on the surface of the carrier; carrying out heat treatment on the prepared composite oxide coating precursor at 500-1000 ℃ for 1-3 h to obtain a composite oxide coating;
the composite oxide coating comprises lanthanum oxide and TimOnAnd LaxTiyOzOxide of said LaxTiyOzLaTi with crystalline oxide3O49、La0.66TiO2.993、La2Ti6O5、La2Ti3O9、La5Ti5O17、La2TiO5、La4Ti9O24、La2Ti2O7And La4Ti3O12And one or any mixture of several of amorphous oxides, the TimOnCrystalline TiO, TiO2、TiO1.04、Ti4O7、Ti3O5And TiO2And one or any mixture of several of amorphous oxides.
2. The method as claimed in claim 1, wherein in the step 1), the mass percentage of the lanthanum salt to the water in the lanthanum salt solution is (2-30): (70-98); the lanthanum salt is one or a mixture of more of lanthanum acetate, lanthanum nitrate, lanthanum carbonate and lanthanum chloride.
3. The method according to claim 1, wherein in the step 2), the mass percentages of the organic titanium precursor, the alcohol and the acid are (1-20): (40-80): (1-20); the organic titanium precursor is one or a mixture of more of tetraisopropyl titanate, tetrabutyl titanate and titanium alkyl oxide, the alcohol is one or a mixture of more of ethanol, isopropanol and n-butanol, and the acid is one or a mixture of more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid.
4. The method according to claim 1, wherein in the step 3), the dropping speed of the lanthanum salt solution into the titanium solution is 0.1-5 ml/min; the mass fraction of the added lanthanum salt solution in the precursor sol of the composite oxide coating is more than 0% and less than 100%.
5. The method according to claim 1, wherein in step 3), the composite oxide coating precursor sol has a molar ratio of La atoms to Ti atoms of 4: 9 to 2: 1.
6. The method according to claim 1, wherein the step 4) is repeated a plurality of times to obtain a multi-layered composite oxide coating.
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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 |
| CN1394680A (en) * | 2002-02-01 | 2003-02-05 | 重庆大学 | Nano-grade lanthanum titanium compound oxide, its preparation method and application |
| CN105441999A (en) * | 2015-11-03 | 2016-03-30 | 中国第一汽车股份有限公司 | Method for preparing nanometer lanthanum oxide coating on metal carrier |
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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 |
| 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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