CN107382379A - The preparation method of ceramic fibre with aluminum phosphate coatings - Google Patents
The preparation method of ceramic fibre with aluminum phosphate coatings Download PDFInfo
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- CN107382379A CN107382379A CN201710628944.7A CN201710628944A CN107382379A CN 107382379 A CN107382379 A CN 107382379A CN 201710628944 A CN201710628944 A CN 201710628944A CN 107382379 A CN107382379 A CN 107382379A
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- fiber
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- ceramic fibre
- aluminum phosphate
- polyelectrolyte
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a kind of preparation method of the ceramic fibre with aluminum phosphate coatings, comprise the following steps (1) pre-treatment step：Pretreatment of fiber is obtained using polyelectrolyte coated ceramic fiber, described polyelectrolyte is polyethyleneimine or cationic-type polyacrylamide；(2) coating forming step：The pretreatment of fiber is coated using aluminium phosphate sol, and in 500~900 DEG C of heat treatments；(3) step (1) and (2) are repeated 1~6 time, so as to form aluminum phosphate coatings on the ceramic fibre surface.Present invention decreases the heat treatment number required for formation coating, heat treatment temperature is suitably reduced.
Description
Technical field
The present invention relates to a kind of preparation method of the ceramic fibre with aluminum phosphate coatings.
Background technology
Improved constantly with the flight Mach number of aircraft, aircraft is compound to high-temperature structural material, particularly ceramic base
The performance of material proposes higher requirement.FRCMC needs to form a weak interface in fiber surface
Coating, when the crackle in matrix is conducted to fiber, weak interface is advantageous to spike protein gene and sliding, so that fiber plays increasing
Potent fruit.
Aluminum phosphate (AlPO4) there is high-melting-point, anti-oxidant, relatively low dielectric constant and dielectric loss, and with
The ceramic materials such as aluminum oxide, mullite have the advantages of chemistry matches and be thermally matched well.As ceramic base composite wood
The weak interface material of material has good effect.
AlPO is formed on a ceramic substrate4The method of coating has chemical vapour deposition technique, atomic layer deposition method, liquid phase method
Deng.AlPO is formed in substrate using chemical vapour deposition technique and atomic layer deposition method4Coating, cost height be present, form coating
The shortcomings of coating nonstoichiometry that speed is small, is formed is than P/Al=1.In contrast, using low concentration colloidal sol combination electrostatic
The liquid phase method of attraction forms AlPO4Coating can then reduce cost, and form more uniform coating.For example, utilize polydiene
Diallyidimethylammonium chloride (PDADMA) pretreatment of fiber, makes fiber positively charged, so as to adsorb in electronegative AlPO4Nanometer
Particle shape is into uniform coating.But forming preferable coating using this method needs the repeated impregnations process of up to 8~10 times,
And the processing at a high temperature of 1100 DEG C is needed to obtain ideal coating.But be heat-treated by multiple high temp, will
Fibre strength is caused to decline serious, so that the intensity of composite declines.
The content of the invention
The defects of in order to overcome prior art, present inventor have made intensive studies.It is an object of the invention to
A kind of preparation method of the ceramic fibre with aluminum phosphate coatings is provided, that is, a kind of ceramic fibre surface is provided and forms AlPO4
The method of coating, it can reduce the heat treatment number to be formed required for coating, suitably reduce heat treatment temperature.It can so make
The intensity for obtaining fiber is farthest retained.
The present invention provides a kind of preparation method of the ceramic fibre with aluminum phosphate coatings, comprises the following steps：
(1) pre-treatment step：Pretreatment of fiber is obtained using polyelectrolyte coated ceramic fiber, described polyelectrolyte is
Polyethyleneimine or cationic-type polyacrylamide；
(2) coating forming step：The pretreatment of fiber is coated using aluminium phosphate sol, and at 500~900 DEG C of heat
Reason；
(3) step (1) and (2) are repeated 1~6 time, so as to form aluminum phosphate coatings on the ceramic fibre surface.
In the present invention, due to use polyelectrolyte polyethyleneimine (PEI) or cationic-type polyacrylamide, rather than
Diallyl dimethyl ammoniumchloride (PDADMA), is pre-processed to ceramic fibre surface, so as to increase aluminum phosphate
Electrostatic Absorption effect, and then vacuum-impregnated number is reduced, while reduce heat treatment temperature.Step is formed in the coating of the present invention
In rapid, the temperature of heat treatment can be 500~900 DEG C, preferably 500~800 DEG C.By reducing heat treatment number and heat treatment
Temperature, the excessive reduction of fibre strength can be avoided.Using the method for the present invention, the phosphorus on the ceramic fibre surface can be caused
The thickness of sour aluminized coating reaches more than 1 μm, preferably 1~5 μm, more preferably 2~3 μm.
Preparation in accordance with the present invention, it is preferable that described ceramic fibre is mullite fiber or alumina fibre.Root
According to an embodiment of the invention, described ceramic fibre is mullite fiber.
Preparation in accordance with the present invention, it is preferable that repeat step (1) and (2) 3~5 times, so as to fine in the ceramics
Dimension table face forms aluminum phosphate coatings.Coating number is reduced, heat treatment number can be reduced simultaneously, so as to prevent that fibre strength is excessive
Reduce.
Preparation in accordance with the present invention, it is preferable that in described pre-treatment step, use pH value for 8~10 it is poly-
Electrolyte aqueous solution is coated to ceramic fibre, so as to obtain pretreatment of fiber.According to an embodiment of the invention,
In described pre-treatment step, pH value is used to be coated for 8~10 aq. polyethyleneimine to ceramic fibre, so as to obtain
Obtain pretreatment of fiber.According to another implementation of the invention, in described pre-treatment step, pH value is used as 8~10
The cationic-type polyacrylamide aqueous solution ceramic fibre is coated, so as to obtain pretreatment of fiber.Preferably, poly- electricity
It is 8.5~9.5 to solve the matter aqueous solution, aq. polyethyleneimine, the pH value of polyacrylamide solution.
Preparation in accordance with the present invention, it is preferable that poly- in the polyelectrolyte aqueous solution in described pre-treatment step
Electrolyte concentration is 0.1wt%~3wt%.It can so ensure that polyelectrolyte is sufficiently adhering on ceramic fibre.According to this hair
A bright embodiment, in described pre-treatment step, the polyethyleneimine concentration of aq. polyethyleneimine is
0.1wt%~3wt%.According to another implementation of the invention, in described pre-treatment step, cationic polypropylene
The cationic-type polyacrylamide concentration of amide aqueous solution is 0.1wt%~3wt%.Preferably, the polyelectrolyte aqueous solution, poly-
The aziridine aqueous solution, polyacrylamide solution are preferably 0.3wt%~2.5wt%.
Preparation in accordance with the present invention, it is preferable that described pre-treatment step is：By ceramic fibre pH value be 8~
10 and concentration be 0.1wt%~3wt% polyelectrolyte 5~60min of aqueous solution vacuum impregnation；Ceramic fibre is taken out, and
Excessive polyelectrolyte is washed with deionized water, so as to obtain pretreatment of fiber.For example, by ceramic fibre pH value be 8~10,
And concentration is 0.1wt%~3wt% 5~60min of aq. polyethyleneimine vacuum impregnation；Ceramic fibre is taken out, is used in combination
Deionized water washes excessive polyethyleneimine off, so as to obtain pretreatment of fiber.And for example, by ceramic fibre pH value be 8~10,
And concentration is 0.1wt%~3wt% 5~60min of polyacrylamide solution vacuum impregnation；Ceramic fibre is taken out, is used in combination
Deionized water washes excessive polyacrylamide off, so as to obtain pretreatment of fiber.The vacuum-impregnated time is preferably 20~
60min。
Preparation in accordance with the present invention, it is preferable that in the coating forming step, the pH value of the aluminium phosphate sol
It is 0.03~0.1mol/L for 7~8 and concentration.Using above-mentioned aluminium phosphate sol, Electrostatic Absorption process can be controlled well,
Allow aluminum phosphate and the abundant electrostatic attraction of polyelectrolyte.The pH value of the aluminium phosphate sol is preferably 7.2~7.8.The aluminum phosphate
The concentration of colloidal sol is preferably 0.03~0.05mol/L.
Preparation in accordance with the present invention, it is preferable that described coating forming step is：The pretreatment of fiber is existed
15~120min of vacuum impregnation in 0.03~0.1mol/L aluminium phosphate sol；Pretreatment of fiber is taken out, and uses deionized water
Wash excessive aluminum phosphate off；In 60~200 DEG C of dryings, then 20~240min is heat-treated at 500~900 DEG C.It is highly preferred that by institute
State pretreatment of fiber 45~90min of vacuum impregnation in 0.03~0.05mol/L aluminium phosphate sol；Pretreatment of fiber is taken
Go out, and excessive aluminum phosphate is washed with deionized water；In 80~110 DEG C of dryings, then it is heat-treated 50 at 500~800 DEG C~
100min.It can so ensure that aluminum phosphate carries out sufficient electrostatic attraction with polyelectrolyte, improve aluminum phosphate adhesion amount, and save
Time.
Preparation in accordance with the present invention, it is preferable that described aluminium phosphate sol is prepared using following steps：By Al
(NO3)3·9H2O and (NH4)2HPO4It is each configured to molar concentration identical Al (NO3)3·9H2The O aqueous solution and (NH4)2HPO4
The aqueous solution, under lasting stirring action, by (NH4)2HPO4Al (NO are added dropwise in the aqueous solution3)3·9H2In the O aqueous solution, so as to raw
Into the mixture containing aluminum phosphate；Mixture of the gained containing aluminum phosphate centrifuge under 2000~10000r/min to 1~
40min, supernatant is outwelled, add deionized water, eccentric cleaning step repeats 1~6 time；Then adjusted with 3~8wt% ammoniacal liquor
PH value is 7~8,3~30min of ultrasound, obtains the aluminium phosphate sol.Al(NO3)3·9H2The O aqueous solution and (NH4)2HPO4It is water-soluble
The concentration of liquid can be 0.03~0.2mol/L, preferably 0.03~0.05mol/L.Constant flow pump control (NH can be used4)2HPO4The rate of addition of the aqueous solution.Preferably, by mixture of the gained containing aluminum phosphate preferably under 2500~6000r/min from
10~30min of the heart.
Preparation in accordance with the present invention, it is preferable that before pre-treatment step is carried out, the ceramic fibre 400~
1000 DEG C of 20~200min of heat treatment, to remove the organic matter on the ceramic fibre surface.For example, the ceramic fibre is 500
~600 DEG C of 60~120min of heat treatment.
The present invention replaces PDADMA to ceramic fibre using polyelectrolyte polyethyleneimine or cationic-type polyacrylamide
Surface is pre-processed, and so as to increase the Electrostatic Absorption effect of aluminum phosphate, so as to reduce vacuum-impregnated number, is dropped simultaneously
Low heat treatment temperature.
Brief description of the drawings
Fig. 1 is AlPO4The XRD spectrum of the front and rear ceramic fiber blanket of coating.1- is uncoated；2- is by coating.
Fig. 2 is the ceramic fibre surface topography of 1 uncoated aluminum phosphate of embodiment.
Fig. 3 is the ceramic fibre surface topography of the coating aluminum phosphate of embodiment 1.
Fig. 4 is the Cross Section Morphology of the ceramic fibre of the coating aluminum phosphate of embodiment 1.
Embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
The raw material used in example below is described as follows：
Polyethyleneimine PEI：Sigma-Aldrich (Sigma-Aldrich) Products, No. CAS is 26658-46-
8。
The method of testing used in example below is described as follows：
X-ray diffraction analysis (XRD)：Tested using Rigaku D/MAX-2500X x ray diffractometer xs, using Cu-K
Alpha ray, wavelengthScanning angle is 10~60 °, and sweep speed is 6 °/min.
Scanning electron microscope analysis (SEM)：Tested using JSM-7500F field emission scanning electron microscopes, operating voltage 3kV；
Aluminum phosphate coatings thickness is determined by cross-section photograph.
Embodiment 1
By equimolar Al (NO3)3·9H2O and (NH4)2HPO4The 0.1mol/L aqueous solution is each configured to, uses constant current
Pump is by 0.1mol/L (NH4)2HPO40.1mol/L Al (NO are added dropwise in the aqueous solution3)3·9H2In the O aqueous solution, while being added dropwise
One side magnetic agitation, generation is reacted at normal temperatures and contains AlPO4Mixture.This is contained into AlPO with centrifuge4Mixture exist
2500r/min centrifuges 30min, outwells supernatant, adds deionized water.Eccentric cleaning step is repeated 6 times.Then, with 5wt%'s
Ammoniacal liquor regulation pH value is 7.2, and will contain AlPO4Mixture adjust to prescribed concentration 0.03mol/L, last ultrasonic 10min
Obtain AlPO4Colloidal sol.
The organic matter that ceramic fiber blanket (mullite fiber) is heat-treated 60min and removes surface at 600 DEG C.
By ceramic fiber blanket in the PEI aqueous solution vacuum impregnation 20min that pH value is 8.5 and concentration is 0.3wt%, will make pottery
Porcelain fibrofelt takes out, and excessive PEI is washed with deionized water.The ceramic fiber blanket for impregnating PEI is placed in AlPO4Carried out in colloidal sol
Vacuum impregnation 45min, coating is formed by electrostatic attraction.Ceramic fiber blanket is taken out, excessive AlPO is washed with deionized water4,
It is placed in 80 DEG C of baking oven and dries.Dried sample is heated to 500 DEG C of heat treatment 100min with batch-type furnace, makes fiber with applying
Adhesion is produced between layer.The step is repeated 5 times, so as to form AlPO on ceramic fibre surface4Coating.Gained fibrofelt
XRD is referring to Fig. 1, and stereoscan photograph is referring to Fig. 3.Fig. 2 is uncoated AlPO4The ceramic fibre of coating.As seen from the figure, it is ceramic
Fiber surface forms uniform coating.
Embodiment 2
By equimolar Al (NO3)3·9H2O and (NH4)2HPO4The 0.1mol/L aqueous solution is each configured to, uses constant current
Pump is by 0.1mol/L (NH4)2HPO40.1mol/L Al (NO are added dropwise in the aqueous solution3)3·9H2In the O aqueous solution, while being added dropwise
One side magnetic agitation, generation is reacted at normal temperatures and contains AlPO4Mixture.This is contained into AlPO with centrifuge4Mixture exist
6000r/min centrifuges 20min, outwells supernatant, adds deionized water.Eccentric cleaning step is repeated 3 times.Then, with 5wt%'s
Ammoniacal liquor regulation pH value is 7.6, and is adjusted to prescribed concentration 0.05mol/L, and last ultrasonic 20min obtains AlPO4Colloidal sol.
The organic matter that ceramic fiber blanket (alumina fibre) is heat-treated 120min and removes surface at 500 DEG C.
By ceramic fiber blanket in the PEI aqueous solution vacuum impregnation 30min that pH value is 9.0 and concentration is 2.5wt%, then
Ceramic fiber blanket is taken out, excessive PEI is washed with deionized water.The ceramic fiber blanket for impregnating PEI is placed in AlPO4In colloidal sol
Vacuum impregnation 90min is carried out, coating is formed by electrostatic attraction.Ceramic fiber blanket is taken out, is washed with deionized water excessive
AlPO4, it is placed in 110 DEG C of baking oven and dries.Dried sample is heated to 800 DEG C of heat treatment 50min with batch-type furnace, makes fibre
Adhesion is produced between dimension and coating.The step is repeated 4 times, so as to form AlPO on ceramic fibre surface4Coating.
The section of the ceramic fibre formed using JSM-7500F field emission scanning electron microscopes (operating voltage 3kV) to embodiment 1
Analyzed, as a result as shown in Figure 4.As seen from the figure, the present invention forms the coating that thickness is 2 μm by 5 processing.Document (Bao
Y,Nicholson P S.AlPO4Coating on Alumina/Mullite Fibers as a Weak Interface in
Fiber-Reinforced Oxide Composites[J].Journal of the American Ceramic Society,
2010,89(2):465-470) as a comparison case, it uses PDADMA pretreatment of fiber, by applying thickness after up to 10 times processing
Degree is just close to 2 μm.Experimental result is as shown in table 1.
Table 1
| Numbering | Cycle-index | Heat treatment temperature/DEG C | Aluminum phosphate coatings thickness deg micron |
| Embodiment 1 | 5 | 500 | 2 |
| Embodiment 2 | 4 | 800 | 2 |
| Comparative example 1 | 10 | 1100 | 2 |
The present invention is not limited to above-mentioned embodiment, in the case of without departing substantially from the substantive content of the present invention, this area skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the ceramic fibre with aluminum phosphate coatings, it is characterised in that comprise the following steps：
(1) pre-treatment step：Pretreatment of fiber is obtained using polyelectrolyte coated ceramic fiber, described polyelectrolyte is poly- second
Alkene imines or cationic-type polyacrylamide；
(2) coating forming step：The pretreatment of fiber is coated using aluminium phosphate sol, and in 500~900 DEG C of heat treatments；
Step (1) and (2) are repeated 1~6 time, so as to form aluminum phosphate coatings on the ceramic fibre surface.
2. preparation method according to claim 1, it is characterised in that described ceramic fibre is mullite fiber or oxidation
Aluminum fiber.
3. preparation method according to claim 1, it is characterised in that step (1) and (2) are repeated 3~5 times, so that
The ceramic fibre surface forms aluminum phosphate coatings.
4. according to the preparation method described in any one of claims 1 to 3, it is characterised in that in described pre-treatment step, adopt
Ceramic fibre is coated with the polyelectrolyte aqueous solution that pH value is 8~10, so as to obtain pretreatment of fiber.
5. preparation method according to claim 4, it is characterised in that in described pre-treatment step, polyelectrolyte water
Polyelectrolyte Concentration in solution is 0.1wt%~3wt%.
6. preparation method according to claim 5, it is characterised in that in the coating forming step, the aluminum phosphate
The pH value of colloidal sol is 7~8 and concentration is 0.03~0.1mol/L.
7. preparation method according to claim 1, it is characterised in that described pre-treatment step is：Ceramic fibre is existed
5~the 60min of aqueous solution vacuum impregnation for the polyelectrolyte that pH value is 8~10, concentration is 0.1wt%~3wt%；By ceramic fibre
Take out, and excessive polyelectrolyte is washed with deionized water, so as to obtain pretreatment of fiber.
8. preparation method according to claim 7, it is characterised in that described coating forming step is：By the pre- place
Manage fiber 15~120min of vacuum impregnation in the aluminium phosphate sol that pH value is 7~8 and concentration is 0.03~0.1mol/L；Will
Pretreatment of fiber takes out, and excessive aluminum phosphate is washed with deionized water；In 60~200 DEG C of dryings, then in 500~900 DEG C of heat
Handle 20~240min.
9. preparation method according to claim 8, it is characterised in that described aluminium phosphate sol uses following steps system
It is standby：By Al (NO3)3·9H2O and (NH4)2HPO4It is each configured to molar concentration identical Al (NO3)3·9H2The O aqueous solution and
(NH4)2HPO4The aqueous solution, under lasting stirring action, by (NH4)2HPO4Al (NO are added dropwise in the aqueous solution3)3·9H2The O aqueous solution
In, so as to generate the mixture containing aluminum phosphate；By the mixture containing aluminum phosphate under 2000~10000r/min from
1~40min of the heart, supernatant is outwelled, add deionized water, eccentric cleaning step repeats 1~6 time；Then with 3~8wt% ammonia
Water regulation pH value is 7~8,3~30min of ultrasound, obtains the aluminium phosphate sol.
10. preparation method according to claim 9, it is characterised in that before pre-treatment step is carried out, the ceramics are fine
Dimension is heat-treated 20~200min at 400~1000 DEG C, to remove the organic matter on the ceramic fibre surface.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115417683A (en) * | 2022-07-11 | 2022-12-02 | 东华大学 | Preparation method of oxide continuous filament reinforced oxide ceramic matrix composite |
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|---|---|---|---|---|
| US5716671A (en) * | 1994-06-02 | 1998-02-10 | The Babcock & Wilcox Company | Continuous deposition of bridge free interfacial coatings on multifilamentary ceramic fiber tows |
| CN1443147A (en) * | 2000-05-19 | 2003-09-17 | 英属哥伦比亚大学 | Process for making chemically bonded composite hydroxide ceramics |
| CN101343193A (en) * | 2008-08-15 | 2009-01-14 | 昆明理工大学 | High-temperature oxidation resistant porous ceramic paint and manufacture method thereof |
| CN102924122A (en) * | 2012-11-14 | 2013-02-13 | 陕西科技大学 | Method for preparing mullite-C-AlPO4 external coating for carbon/carbon composite material |
-
2017
- 2017-07-28 CN CN201710628944.7A patent/CN107382379A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716671A (en) * | 1994-06-02 | 1998-02-10 | The Babcock & Wilcox Company | Continuous deposition of bridge free interfacial coatings on multifilamentary ceramic fiber tows |
| CN1443147A (en) * | 2000-05-19 | 2003-09-17 | 英属哥伦比亚大学 | Process for making chemically bonded composite hydroxide ceramics |
| CN101343193A (en) * | 2008-08-15 | 2009-01-14 | 昆明理工大学 | High-temperature oxidation resistant porous ceramic paint and manufacture method thereof |
| CN102924122A (en) * | 2012-11-14 | 2013-02-13 | 陕西科技大学 | Method for preparing mullite-C-AlPO4 external coating for carbon/carbon composite material |
Non-Patent Citations (1)
| Title |
|---|
| YAHUA BAO ET AL: "AlPO4 Coating on Alumina/ Mullite Fibers as a Weak Interface in Fiber-Reinforced Oxide Composites", 《THE AMERICAN CERAMIC SOCIETY》 * |
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| CN115417683A (en) * | 2022-07-11 | 2022-12-02 | 东华大学 | Preparation method of oxide continuous filament reinforced oxide ceramic matrix composite |
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Application publication date: 20171124 |