CN108505320A - Composite oxide coating and its preparation method and application - Google Patents
Composite oxide coating and its preparation method and application Download PDFInfo
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- CN108505320A CN108505320A CN201810382636.5A CN201810382636A CN108505320A CN 108505320 A CN108505320 A CN 108505320A CN 201810382636 A CN201810382636 A CN 201810382636A CN 108505320 A CN108505320 A CN 108505320A
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- oxide coating
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- zirconium
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- 238000000576 coating method Methods 0.000 title claims abstract description 99
- 239000011248 coating agent Substances 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 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 abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 12
- 150000001298 alcohols Chemical class 0.000 claims abstract description 10
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 5
- 235000019441 ethanol Nutrition 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical group [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 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
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 64
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 28
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 28
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 63
- 238000000034 method Methods 0.000 description 16
- 238000010792 warming Methods 0.000 description 15
- 238000013019 agitation Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 235000011054 acetic acid Nutrition 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000002356 single layer Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 150000001243 acetic acids Chemical class 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 2
- 229910002230 La2Zr2O7 Inorganic materials 0.000 description 2
- AZJLMWQBMKNUKB-UHFFFAOYSA-N [Zr].[La] Chemical compound [Zr].[La] AZJLMWQBMKNUKB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 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 description 2
- 229960001633 lanthanum carbonate Drugs 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011226 reinforced ceramic Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of composite oxide coatings, including zirconium oxide and lanthana, the preparation method of the composite oxide coating include:1) lanthanum salt is dissolved in the water, is stirred evenly, obtain solution A;2) zirconium precursor body, alcohols and acid are mixed, stirs evenly, obtains B solution;3) solution A is slowly added dropwise into B solution while stirring, obtains composite oxide coating precursor sol;4) carrier is positioned in composite oxide coating precursor sol, is impregnated, dry, heat treatment obtains the composite oxide coating of different-thickness.Preparation process of the present invention is simple, coating raw material easily obtain, convenient for industrialization promotion, the composite oxide coating of preparation is good complete fine and close in the spreadability of fiber surface, effectively improve the high temperature oxidation resistance of silicon carbide fibre, the interface stability that can keep composite material after prepares coating under high temperature, prolonged operating condition on fiber, improves the high-temperature oxidation resistance and high temperature resistant alkali corrosive nature of fiber.
Description
Technical field
The present invention relates to interlayer materials, and in particular to a kind of composite oxide coating and its preparation method and application.
Background technology
Fiber reinforced ceramic matrix composites is due to excellent performances such as corrosion-resistant, high temperature resistants, in aerospace field
It is used widely.In the preparation process of fibre reinforced composites, the interface cohesion of fiber and matrix is to influence composite wood
Expect a key factor of performance.In order to realize the optimized design at interface, coating appropriate is coated as fine in fiber surface
Dimension and the boundary layer of matrix are the most effective means.Interlayer materials itself will have higher inoxidizability;It can prevent outer
Boundary's matrix reacts with fiber;Under the premise of improving material against oxidative performance, the mechanical property of material is kept as much as possible
Energy.
Currently, PyC, BN of fiber surface and the preparation method of oxide coating include mainly chemical vapor deposition (CVD)
Method, magnetron sputtering method and sol-gel method etc..CVD method and magnetron sputtering method prepares coating had it is more and more mature, but
The cost of CVD method and magnetron sputtering method prepares coating is higher, and equipment is expensive, and sample size is limited by settling chamber space;And
Target used in magnetron sputtering is expensive, these techniques are unfavorable for industrialization promotion, these all limit 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
Simplicity, equipment requirement is low and is suitable for large area and prepares film coating, and chemical composition is easier to control.Publication No.
The patent application of CN105133291A discloses the method that sol-gel method prepares aluminum oxide coating layer, the covering of prepared coating
Property it is poor, fibre property is promoted little.The patent application of Publication No. CN10133365A and CN102509764A are using molten
Glue-gel method prepares La2Zr2O7Precursor solution, and prepared on alloy and monocrystal chip respectively by the way of spin coating
La2Zr2O7Film, cost of material is high, and the process is more complicated.The patent application of Publication No. CN105175025A is using mixing
The mode of heating reflux reaction prepares colloidal sol, prepares alumina-silica titanium compound coating on silicon carbide fibre surface, prepares work
Device needed for skill is complicated, and coating is poor with fibers adhesion, and resistance to acid and alkali performance is bad.
Invention content
Goal of the invention:The object of the present invention is to provide a kind of composite oxide coating, the advantages of coating, is not only may be used
It preserves the internal structure of coated material, enhance the mechanical performance of coated material, while it is easily cracked, easy to solve coating
The problems such as peeling, improves the high-temperature oxidation resistance of coated material, widens materials'use range.
Another aspect of the present invention is provided in the preparation that a kind of raw material is simple and easy to get, cheap, simple for process, repeatability is high
The method for stating composite oxide coating.
Technical solution:The present invention provides a kind of composite oxide coating, including zirconium oxide and lanthana, the composite oxides
The preparation method of coating includes the following steps:
1) lanthanum salt is dissolved in the water, is stirred evenly, obtain solution A;
2) zirconium precursor body, alcohols and acid are mixed, stirs evenly, obtains B solution;
3) solution A is slowly added dropwise into B solution while stirring, obtains composite oxide coating precursor sol;
4) carrier is positioned in composite oxide coating precursor sol, is impregnated, dry, heat treatment obtains different thickness
The composite oxide coating of degree.
In above-mentioned composite oxide coating, the molar ratio of zirconium oxide and lanthana is 1.5-2.5: 1, preferably 2: 1.
Lanthanum salt is the mixture of one or more of lanthanum acetate, lanthanum nitrate, lanthanum carbonate and lanthanum chloride;Before the zirconium
It is one or both of zirconium-n-butylate and zirconium oxycarbonate to drive body.
Another aspect of the present invention provides the preparation method of above-mentioned composite oxide coating, includes the following steps:
1) lanthanum salt is dissolved in the water, is stirred evenly, obtain solution A;
2) zirconium precursor body, alcohols and acid are mixed, stirs evenly, obtains B solution;
3) solution A is added dropwise in B solution while stirring, obtains composite oxide coating precursor sol;
4) carrier is positioned in composite oxide coating precursor sol, is impregnated, dry, heat treatment obtains different thickness
The composite oxide coating of degree.
Wherein, lanthanum salt is the mixture of one or more of lanthanum acetate, lanthanum nitrate, lanthanum carbonate and lanthanum chloride;Institute
It is one or both of zirconium-n-butylate and zirconium oxycarbonate to state zirconium precursor body.
In step 1), the quality parts ratio of lanthanum salt and water is (2-30): (70-98).
In step 2), the mass ratio of zirconium precursor body, alcohols and acid is (2-30): (10-50): (10-50);Alcohols solvent is
The mixture of one or more of ethyl alcohol, isopropanol and n-butanol, the acid are in nitric acid, acetic acid, hydrochloric acid and sulfuric acid
One or more kinds of mixtures.
In step 3), it is 0.1%- that the solution A of addition, which accounts for the mass fraction of composite oxide coating precursor sol,
99.9%, rate of addition 0.1-5ml/min;Continue magnetic agitation after the completion of dropwise addition until obtaining the forerunner of clear
Body colloidal sol.
Key prepared by composite oxide coating is the selection of zirconium precursor body and the control of hydrolysis rate.Hydrolysis rate
Control method is, during preparing solution B, using excessive alcohols solvent or proper amount of acids hydrolysis inhibitor, and
Solution A is added to the speed control of B solution for 0.1-5ml/min.
Step 4) specifically includes following steps:
A) carrier is positioned in composite oxide coating precursor sol, impregnates 10-20min under ultrasound condition, makes
Precursor sol is uniformly distributed in fiber surface, then puies forward bit rate by carrier from composite oxide coating with 1-15mm/min
Precursor sol takes out, and reduces the precursor accumulation generated during lifting since solution is assembled, and drying obtains combined oxidation
Object coating precursor;
B) composite oxide coating precursor made from step a) is kept the temperature into 1-3h at 500-800 DEG C, it is ensured that obtain it is compound
In the case of oxide, heat treatment damage caused by fiber is reduced, composite oxide coating is obtained.
Step 4) includes:Step a) is repeated as many times, step b) is then carried out;Or be repeated as many times step 4), it obtains
MULTILAYER COMPOSITE oxide coating.
In above-mentioned steps b), composite oxide coating precursor made from step a) is warming up to 500-800 DEG C of heating speed
Degree is 1-20 DEG C/min.
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.
Another aspect of the present invention provides application of the above-mentioned composite oxide coating in boundary layer.
Advantageous effect:Preparation process of the present invention is simple, and coating raw material easily obtain, and is prepared compared to traditional fiber coat
Method, coating cost is relatively low, and geomery is not limited by the size of CVD reative cells, convenient for industrialization promotion, it can be achieved that in fiber
The composite oxide coating of complete densification is prepared to surface fast, economical, this method is also applied for other article surface protective coatings
Preparation.Composite oxide coating prepared by the present invention, it is good complete fine and close in the spreadability of fiber surface, effectively improve carbonization
The high temperature oxidation resistance of silica fibre can keep multiple after prepares coating on fiber under high temperature, prolonged operating condition
The interface stability of condensation material improves the high-temperature oxidation resistance and high temperature resistant alkali corrosive nature of fiber.Prepared by the present invention answers
Oxide coating is closed, even compact, impurity are few, not easily to fall off, and preparation process is simple and thickness accurately controls, and coating layer thickness can
Between 10nm-2 μm.
Description of the drawings
Fig. 1 is that fiber surface coats single layer zirconium lanthanium complex oxide coating scanning electron microscope diagram;
Fig. 2 is the scanning electron microscope diagram that fiber surface coats low concentration single layer zirconium lanthanium complex oxide coating;
Fig. 3 is the XRD spectrum of zirconium lanthanium complex oxide coating material.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.The coating pattern of composite oxide coating is by scanning
Electron microscope (SEM) test characterization, the material composition of composite oxide coating is tested by X-ray diffractometer (XRD) to be characterized.
Embodiment 1
Prepare solution A:0.7g 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, obtains solution A.Prepare B solution:By 8g glacial acetic acids and 0.7g
Zirconium-n-butylate is successively slowly added in 8g ethyl alcohol, and magnetic agitation 30min, makes solution be sufficiently mixed uniformly, obtain B under room temperature
Solution.Solution A is slowly added dropwise with the speed of 2ml/min to B solution under the conditions of magnetic agitation, until solution A is added dropwise,
Continue to stir 10min at room temperature, so that zirconium-n-butylate is fully hydrolyzed, obtain the zirconium lanthanium complex oxide colloidal sol of stable transparent.
Silicon carbide fibre is soaked in above-mentioned zirconium 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 zirconium 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 zirconium lanthanium complex oxide coating.Fig. 1 is with zirconium lanthanium complex oxide coating
Silicon carbide fibre scanning electron microscope diagram piece, fiber coat surface is smooth, and covering is complete.Further with zirconium lanthanum composite oxygen
After the silicon carbide fibre of compound coating is put into the aqueous solution soaking containing a small amount of acetic acid, obviously falling off does not occur in coating.
Zirconium lanthanium complex oxide colloidal sol in the present embodiment is placed in baking oven and evaporates, dry, gained powder passes through 800 DEG C
Muffle furnace after X ray diffracting spectrum it is as shown in Figure 3.The analysis showed that the composite oxides are by La2O3And ZrO2Composition.
Embodiment 2
Prepare solution A:0.5g lanthanum acetate powder is slowly added in 8g water, magnetic agitation 30min at room temperature after adding makes
Lanthanum acetate is completely dissolved, and solution becomes clear, obtains solution A.Prepare B solution:By 8g glacial acetic acids and 0.5g zirconium-n-butylates
It is successively slowly added in 8g ethyl alcohol, magnetic agitation 30min, makes solution be sufficiently mixed uniformly, obtain B solution under room temperature.
Solution A is slowly added dropwise with the speed of 1ml/min into B solution under the conditions of magnetic agitation, until solution A is added dropwise, room temperature
Under continue stir 10min, so that zirconium-n-butylate is fully hydrolyzed, obtain the zirconium lanthanium complex oxide colloidal sol of stable transparent.
Silicon carbide fibre is soaked in above-mentioned zirconium 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 zirconium 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 low concentration single layer zirconium lanthanium complex oxide coating.Fig. 2 is with low concentration single layer zirconium lanthanum
The silicon carbide fibre scanning electron microscope diagram piece of composite oxide coating.As seen from Figure 2, manufactured in the present embodiment to have
Composite oxide coating surface is smooth, and covering is complete.
Embodiment 3
Prepare four parts of solution As:The deionized water of 4 parts of every part of 8g is taken, respectively by 0.3g, 0.5g, 0.7g and 0.9g lanthanum acetate
Powder is slowly added in 8g deionized waters, and magnetic agitation 30min at room temperature after adding makes lanthanum acetate be completely dissolved, solution becomes
Clear.
Prepare four parts of B solutions:The mixed liquor of 4 parts of 8g ethyl alcohol and 8g glacial acetic acids is taken, respectively by 0.3g, 0.5g, 0.7g, 0.9g
Zirconium-n-butylate is added in the mixed liquor of 8g ethyl alcohol and 8g glacial acetic acids, and magnetic agitation 30min, makes solution be sufficiently mixed under room temperature
Uniformly;Lanthanum acetate identical in quality and the corresponding A of zirconium-n-butylate and B solution are taken, under the conditions of magnetic agitation by solution A with 5ml/
The speed of min is slowly added dropwise into B solution, until solution A is added dropwise, continues to stir 10min at room temperature, zirconium-n-butylate is made to fill
Divide hydrolysis, obtains the zirconium lanthanium complex oxide colloidal sol of four parts of stable transparents.
Silicon carbide fibre is soaked in above-mentioned four parts of zirconiums lanthanium complex oxide colloidal sol after ultrasonic vibration 20min, with 5mm/
The pull rate of min is taken out.The silicon carbide fibre placement of taking-up is dried in an oven, baking oven is with the heating rate of 5 DEG C/min
1h is kept the temperature after being warming up to 70 DEG C, is taken out after Temperature fall, and it is fine to obtain silicon carbide of the surface with zirconium lanthanium complex oxide presoma
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 zirconium lanthanium complex oxide coating silicon carbide fibre.
Will not pretreated fiber (not having zirconium lanthanium complex oxide coating), be placed into Muffle furnace, be rapidly heated to
500 DEG C and keep the temperature 1 hour, taken out after furnace cooling.The test of monofilament tensile strength, uncoated fiber are carried out to above-mentioned fiber
Mean intensity is 1.96GPa, and the fiber handled by above-mentioned 4 kinds of colloidal sol is fine relative to uncoated and not thermally treated silicon carbide
The strength retention ratio of dimension is all 90% or more.
Above-described embodiment 1-3 proves that not only surface is smooth for zirconium lanthanium complex oxide coating of the invention, covering is complete, and
And treated object is not obviously corroded, the proper property and surface state of treated object are remained substantially.Comparative example 1
Silicon carbide fibre is soaked in the solution A in embodiment 1, after ultrasonic vibration 20min, with the lifting of 5mm/min
Speed is taken out.The silicon carbide fibre placement of taking-up is dried in an oven, baking oven is warming up to 70 DEG C with the heating rate of 5 DEG C/min
After keep the temperature 1h, take out, be placed into Muffle furnace after Temperature fall, with the heating rate of 3 DEG C/min be warming up to 500 DEG C and keep the temperature 1
Hour, it is taken out after furnace cooling, obtains fiber A.
Silicon carbide fibre is soaked in the solution B in embodiment 1, after ultrasonic vibration 20min, with the lifting speed of 5mm/min
Degree takes out.The silicon carbide fibre placement of taking-up is dried in an oven, after baking oven is warming up to 70 DEG C with the heating rate of 5 DEG C/min
1h is kept the temperature, takes out, is placed into Muffle furnace after Temperature fall, 500 DEG C is warming up to the heating rate of 3 DEG C/min and heat preservation 1 is small
When, it is taken out after furnace cooling, obtains fiber B.
SEM observations confirm that the coating on surface fiber (i.e. fiber B) that the solution B through containing only zirconium is handled is uneven, apply
Layer is easy to fall off.There is moisture absorption phenomenon in the fiber (i.e. fiber A) that solution A through containing only lanthanum is handled, is put into containing a small amount of
After the aqueous solution soaking of acetic acid, coating falls off, and is consistent with the lanthana moisture absorption and the property for being soluble in acid.
Embodiment 1 and comparative example 1 the result shows that, the performance of zirconium lanthanium complex oxide coating containing zirconium or contains lanthanum better than individually
Oxide coating.By calculating, the molar ratio of zirconium oxide and lanthana is 1.7 in zirconium lanthanium complex oxide coating in embodiment 1.
Embodiment 4
Prepare solution A:By 0.6g La (NO3)3·6H2O powder is slowly added in 3g deionized waters, magnetic at room temperature after adding
Power stirs 30min, so that lanthanum acetate is completely dissolved, solution becomes clear, obtains solution A.
Prepare B solution:5g glacial acetic acids and 0.5g zirconium-n-butylates are successively slowly added in 5g ethyl alcohol, under room temperature magnetic force
30min is stirred, so that solution is sufficiently mixed uniformly, obtains B solution.
Solution A is slowly added dropwise with the speed of 0.1ml/min to B solution under the conditions of magnetic agitation, until solution A is added dropwise
It finishes, continues to stir 10min at room temperature, so that zirconium-n-butylate is fully hydrolyzed, obtain the zirconium lanthanium complex oxide colloidal sol of stable transparent.
Metal alloy is soaked in above-mentioned zirconium lanthanium complex oxide colloidal sol after ultrasonic vibration 10min, with 15mm/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 50 DEG C, is taken out after Temperature fall, and obtaining surface has the silicon carbide fibre of zirconium lanthanium complex oxide presoma.It should
Fiber is placed into Muffle furnace, is warming up to 800 DEG C with the heating rate of 10 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 zirconium lanthanium complex oxide coating.
Zirconium lanthanium complex oxide colloidal sol in the present embodiment is placed in baking oven and evaporates, dry, the analysis showed that, this is compound
Oxide is by La2O3And ZrO2Composition.In composite oxides made from the present embodiment, ZrO2And La2O3The ratio between the amount of substance about
It is 2: 1.
Embodiment 5
Prepare solution A:By 0.6g LaCl3Powder is slowly added in 10g deionized waters, magnetic agitation at room temperature after adding
30min makes lanthanum acetate be completely dissolved, and solution becomes clear, obtains solution A.
Prepare B solution:2g glacial acetic acids and 1.2g zirconium-n-butylates are successively slowly added in 2g ethyl alcohol, under room temperature magnetic force
30min is stirred, so that solution is sufficiently mixed uniformly, obtains B solution.
Solution A is slowly added dropwise with the speed of 0.5ml/min to B solution under the conditions of magnetic agitation, until solution A is added dropwise
It finishes, continues to stir 10min at room temperature, so that zirconium-n-butylate is fully hydrolyzed, obtain the zirconium lanthanium complex oxide colloidal sol of stable transparent.
By ceramic immersion in above-mentioned zirconium lanthanium complex oxide colloidal sol after ultrasonic vibration 20min, with the lifting speed of 1mm/min
Degree takes out.The silicon carbide fibre placement of taking-up is dried in an oven, after baking oven is warming up to 60 DEG C with the heating rate of 5 DEG C/min
1h is kept the temperature, is taken out after Temperature fall, obtaining surface has the silicon carbide fibre of zirconium lanthanium complex oxide presoma.The fiber is put
It sets in Muffle furnace, 600 DEG C are warming up to the heating rate of 10 DEG C/min and keep the temperature 2 hours, taken out after furnace cooling, you can system
Obtain the silicon carbide fibre with single layer zirconium lanthanium complex oxide coating.
Zirconium lanthanium complex oxide colloidal sol in the present embodiment is placed in baking oven and evaporates, dry, the analysis showed that, this is compound
Oxide is by La2O3And ZrO2Composition.In composite oxides made from the present embodiment, ZrO2And La2O3The ratio between the amount of substance be
2.5∶1。
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 composite oxide coating, which is characterized in that the composite oxide coating includes zirconium oxide and lanthana, described
The preparation method of composite oxide coating includes the following steps:
1) lanthanum salt is dissolved in the water, is stirred evenly, obtain solution A;
2) zirconium precursor body, alcohols and acid are mixed, stirs evenly, obtains B solution;
3) solution A is slowly added dropwise into B solution while stirring, obtains composite oxide coating precursor sol;
4) carrier is positioned in composite oxide coating precursor sol, is impregnated, dry, heat treatment obtains composite oxides
Coating.
2. composite oxide coating according to claim 1, which is characterized in that in the composite oxide coating, oxidation
The molar ratio of zirconium and lanthana is 1.5-2.5: 1.
3. composite oxide coating according to claim 1, which is characterized in that the lanthanum salt is lanthanum acetate, lanthanum nitrate, carbon
The mixture of one or more of sour lanthanum and lanthanum chloride;The zirconium precursor body is in zirconium-n-butylate and zirconium oxycarbonate
It is one or two kinds of.
4. the preparation method of the composite oxide coating described in any one of claims 1 to 3, which is characterized in that the system
Preparation Method includes the following steps:
1) lanthanum salt is dissolved in the water, is stirred evenly, obtain solution A;
2) zirconium precursor body, alcohols and acid are mixed, stirs evenly, obtains B solution;
3) solution A is added dropwise in B solution while stirring, obtains composite oxide coating precursor sol;
4) carrier is positioned in composite oxide coating precursor sol, is impregnated, dry, heat treatment obtains composite oxides
Coating.
5. the preparation method of composite oxide coating according to claim 4, which is characterized in that in step 1), lanthanum salt with
The mass ratio of water is (2-30): (70-98).
6. the preparation method of composite oxide coating according to claim 4, which is characterized in that in step 2), zirconium precursor
The mass ratio of body, alcohols and acid is (2-30): (10-50): (10-50);The alcohols solvent is ethyl alcohol, isopropanol and n-butanol
One or more of mixture, the acid is the mixed of one or more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid
Close object.
7. the preparation method of composite oxide coating according to claim 4, which is characterized in that in step 3), the A of addition
The mass fraction that solution accounts for composite oxide coating precursor sol is 2%-98%;The rate of addition is 0.1-5ml/min;
Continue stirring after the completion of dropwise addition until obtaining the precursor sol of clear.
8. the preparation method of composite oxide coating according to claim 4, which is characterized in that step 4) specifically include with
Lower step:
A) carrier is positioned in composite oxide coating precursor sol, 10-20min is impregnated under ultrasound condition, with 1-
The bit rate that carries of 15mm/min takes out carrier from composite oxide coating precursor sol, dry, is answered in carrier surface
Close oxide coating precursor;
B) composite oxide coating precursor made from step a) is kept the temperature into 1-3h at 500-800 DEG C, obtains composite oxide coating.
9. the preparation method of composite oxide coating according to claim 8, which is characterized in that step 4) includes:It will step
It is rapid a) to be repeated as many times, then carry 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 any one of claims 1 to 3 in boundary layer.
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CN112791699A (en) * | 2021-01-20 | 2021-05-14 | 辽宁科技大学 | ZrO (ZrO)2Preparation method of coal tar pitch-based composite activated carbon spheres |
CN114436680A (en) * | 2022-03-02 | 2022-05-06 | 成都理工大学 | Preparation process method of mineral material and ultrahigh-temperature ceramic synergistically modified C/C composite material |
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