CN105967755B - A kind of crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite and preparation method thereof - Google Patents
A kind of crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite and preparation method thereof Download PDFInfo
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- CN105967755B CN105967755B CN201610298083.6A CN201610298083A CN105967755B CN 105967755 B CN105967755 B CN 105967755B CN 201610298083 A CN201610298083 A CN 201610298083A CN 105967755 B CN105967755 B CN 105967755B
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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
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
- C04B41/5089—Silica sols, alkyl, ammonium or alkali metal silicate cements
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- 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
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Abstract
The invention discloses crystal whisker toughened mullite antioxidant coatings of a kind of carbon/carbon composite mullite and preparation method thereof, belong to antioxidant coating preparing technical field.The present invention is prepared for the crystal whisker toughened mullite compound anti-oxidation external coating of carbon/carbon composite mullite using molten-salt growth method combination in-situ reaction, first, with simple process for preparing mullite crystal whisker by molten salt buffer layer, on the one hand the wetability between inside and outside coating can be improved, on the other hand improves the inside and outside bond strength with layer；Secondly, in-situ reaction is selected, in-situ preparation antioxygenic property is good, oxygen permeability is low, heat safe silicate external coating.The present invention prepares external coating using high temperature oxidative atmosphere, not only cost-effective, has also started a new road.This method easily controls the component of coating, can prepare a variety of silicate coatings, adapts to different temperatures section coating needs.The method of the present invention short preparation period, technical process are simple, at low cost, have broad application prospects.
Description
Technical field
The invention belongs to antioxidant coating preparing technical field, it is related to a kind of preparing the compound external coating of carbon/carbon compound material
Method, and in particular to a kind of crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite and preparation method thereof.
Background technology
C/C composite materials are otherwise known as carbon fiber carbon based composites, since it is only made of single carbon, not only
With the ablation resistance that charcoal and graphite material are excellent, the advantages such as low-density, coefficient of thermal expansion are low, and also it is also excellent under high temperature
Mechanical property.The performance that especially its intensity goes up not down with the increase of temperature, becomes most promising high skill
One of art new material is widely used as the ablator and thermal structure material of aerospace technical field.But C/C is compound
Material in temperature more than rapid oxidation under 500 DEG C of oxidizing atmosphere, which greatly limits its application, therefore C/C composite materials
Oxidation protection problem becomes one of research hotspot in recent years.High-temperature oxidation resistant protection is carried out to it simultaneously to its high temperature application
Have great importance.
Antioxidant coating is considered as to solve the problems, such as the effective ways of carbon/carbon compound material oxidant protection under high temperature.To prevent
C/C composite materials aoxidize at high temperature, and domestic and international researcher has carried out a large amount of theoretical and experimental study, develop a variety of anti-
Oxide covering system.
At present, the coating system developed has glass, metal, ceramics and composite coating.Glass coating can be with material for repairing
The crackle generated during military service due to deformation, but Conventional glass mobility at high temperature and volatility limit it at higher temperature
Use under degree and air-flow Scouring Condition.Precious metal alloys coating such as Ir-Al-Si etc. is demonstrated by preferable inoxidizability, but its
Of high cost and oxidation protection ability is limited.Ceramic coating is the hot spot studied at present, and generally using silicon based ceramic.Its skill
Art key is to utilize SiO under high temperature2Or the SiO of reaction generation2Come the defects of filling the crackle in coating, as sealing substance
Stop the infiltration of oxygen.It is silicon based ceramic coating to study at present more.In order to combine the advantage of a variety of materials, researcher also develops
Using SiC as the composite coating of transition zone, such as SiC/MoSi2[J.F.Huang,B.Wang,H.J.Li,M.Liu,L.Y.Cao,
C.Y.Yao.A MoSi2/SiC oxidation protective coating for carbon/carbon
composites,Corros.Sci.53(2011)834-839.]、SiC/Mullite[K.T.Wang,L.Y.Cao,
J.F.Huang,J.Fei,A mullite/SiC oxidation protective coating for carbon/carbon
composites,J.Eur.Ceram.Soc.33(2013)191-198.]、SiC/Yttrium silicate[M.Huang,
K.Z.Li,H.J.Li,J.F.Huang,,Yttrium silicate coatings for SiC coated C/C
composites prepared by atmospheric plasma spraying,Carbon.48(2010)3974-3977.]
By numerous studies, find above-mentioned ceramic coating there are one it is common the shortcomings that, that is, due to the intrinsic brittleness of ceramic material, very
Easily crack or even come off during thermal shock.The SiO generated due to silicon based ceramic autoxidation2Amount is few, and in high temperature and
It washes away under airflow function and volatilizees seriously, it is difficult to which heal big crackle.Therefore it usually needs to prepare one layer of glassy layer again on surface
Packing crackle.But glassy layer also easily quick volatilization in the case where Fast ion flow washes away environment, reduces packing effect.
In order to improve coating in the antioxygenic property of full warm area and slow down the extension of crackle in the coating, researcher's exploitation
With nanowire-toughened composite coating, SiC nanowire toughening SiC-Si coatings [Y.H.Chu, H.J.Li, L.Li, L.H.Qi,
Oxidation protection of C/C composites by ultra long SiC nanowire-reinforced
SiC-Si coating, Corros.Sci.84 (2014) 204-208.], SiC nanowire toughening MoSi2- SiC-Si coatings [Fu
Qian-Gang,Li He-Jun,Li Ke-Zhi,Shi Xiao-Hong,Hu Zhi-Biao,Huang Min,SiC
whisker-toughened MoSi2-SiC-Si coating to protect carbon/carbon composites
Against oxidation, Carbon.2006,44,1866.] etc..The composite coating of preparation can play C/C composite materials
The protective action of effect.But it also needs constantly to exert in order to which antioxidant coating is made towards directions such as long-life, high temperature resistant, antiscours to develop
Power.(coefficient of thermal expansion is 5.0 × 10 to mullite-6/ DEG C) ceramic material refractoriness height, good thermal shock, chemical resistance of concrete, anti-compacted
Change, refractoriness under load height, volume stability are well ideal high grade refractories, are widely used in each field.Mullite
Whisker with high temperature resistant, wear-resistant, anti-oxidant, coefficient of thermal expansion is smaller, elevated temperature strength is larger, thermal shock resistance is preferable and with
High-temerature creep is small to wait excellent properties, and avoided due to the mismatch of coefficient of thermal expansion and produced with mullite crystal whisker plasticizing mullite
Raw crackle.Therefore, become the effective way for improving mullite ceramic toughness and reliability with mullite crystal whisker enhancing mullite.And
And up to the present, the also rarely found report of research by the use of it as antioxidant coating.
Up to the present the preparation method of external coating is varied, is mainly the following：Supercritical fluid technology is changed
Learn vapor deposition, investment, formed in situ, sol-gel method, molten slurry coating reaction, detonation flame spraying and ultrasonic spray method etc..
Above-mentioned preparation process is there are the production cycle is long, complex process, the problem of coating and poor matrix binding performance, and the system of coating
Standby to complete under the high temperature conditions mostly, preparation process is to equipment requirement height, manufacturing cost height.
At present, the method for the anti-oxidant external coating of mullite crystal whisker plasticizing mullite is prepared also using molten-salt growth method combination in-situ method
It has not been reported.
Invention content
In order to overcome the problems of the above-mentioned prior art, the purpose of the present invention is to provide a kind of carbon/carbon compound materials
Mullite crystal whisker plasticizing mullite antioxidant coating and preparation method thereof, this method is easy to operate, low for equipment requirements, reaction week
Phase is short, at low cost, can prepare that thickness is uniform using the method, and the carbon/carbon composite mullite whisker of compact structure increases
Tough mullite antioxidant coating.
The present invention is to be achieved through the following technical solutions：
The invention discloses a kind of preparation sides of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite
Method includes the following steps：
1) by Al2(SO4)3·18H2O：Na2SO4=9:10 mass ratio, takes Al2(SO4)3·18H2O and Na2SO4, fully
After mixing, mixing double salt A is made；
2) SiC-C/C composite samples (the C/C composite samples for carrying SiC coatings) are cleaned by ultrasonic, dried
After dry, by SiC-C/C composite samples：Mix double salt A=(1~3)：19 mass ratio, by SiC-C/C composite samples
It is embedded in mixing double salt A, at 900~950 DEG C, after heat treatment, cooling；
3) will through step 2), treated that sample is cleaned with boiling water, until cleaning unreacted fused salt, then sample is done
It is dry, the sample (mullite/SiC-C/C) with mullite crystal whisker layer is made；
4) by Si powder and Al2O3The mixed powder of powder composition is scattered in the mixed solution that Ludox is mixed with distilled water
In, the slurry B1 of a concentration of 200~300g/L of mixed powder is made, after slurry B1 ultrasonic vibrations, then through magnetic agitation, is made
Slurry B2；
5) slurry B2 is uniformly painted on the step 3) specimen surface obtained for carrying mullite crystal whisker layer, dried in the air at room temperature
It is dry, after repeating brushings, drying operation 5~10 times, dry；
6) sample for obtaining step 5) drying under protection of argon gas, at 1500 DEG C, keeps the temperature 2~4h, it is multiple that carbon/carbon is made
Condensation material mullite crystal whisker plasticizing mullite antioxidant coating.
Abundant mixing described in step 1) is by Al2(SO4)3·18H2O and Na2SO4It is placed in mortar, is fully ground 30
~60min.
Step 2) is that SiC-C/C composite samples are placed in ethyl alcohol to be cleaned by ultrasonic, and is then dried at 50~80 DEG C.
Step 2) is that mixing double salt A is placed in corundum crucible, and SiC-C/C composite samples are embedded in mixing double salt
In A, then corundum crucible is placed in Muffle furnace, is heat-treated 30~60min.
Step 3) is the sample that will be cleaned dry 1~3h in 60~90 DEG C of electric drying oven with forced convection.
In step 4), in the mixed solution that Ludox is mixed with distilled water, the volume ratio of Ludox and distilled water is
1:3；In mixed powder, Si powder and Al2O3The molar ratio of powder is 2:3.
By slurry B1 10~20min of ultrasonic vibration in step 4), 1~3h is then stirred on magnetic stirring apparatus, obtains slurry
B2。
Drying described in step 5) is dry 1~2h at 50~80 DEG C.
Step 6) is that the sample that drying obtains is carried out isothermal holding in high-temperature atmosphere furnace.
The invention also discloses using the crystal whisker toughened mullite antioxygen of carbon/carbon composite mullite made from the above method
Change coating, the antioxidant coating thickness is uniform, compact structure, surface flawless, and coating is big with substrate combinating strength.
Compared with prior art, the present invention has technique effect beneficial below：
The method of the present invention combines the advantages of both mullite and mullite crystal whisker well, is combined using molten-salt growth method in situ
Reaction method is prepared for the crystal whisker toughened mullite compound anti-oxidation external coating of carbon/carbon composite mullite, first, with simply molten
Salt method prepares mullite crystal whisker buffer layer, on the one hand can improve the wetability between inside and outside coating, on the other hand inside and outside raising
With the bond strength of layer；Secondly, in-situ reaction is selected, in-situ preparation antioxygenic property is good, oxygen permeability is low, heat safe
Silicate external coating.The present invention prepares external coating using high temperature oxidative atmosphere, not only cost-effective, has also started a new road
Road.This method easily controls the component of coating, can prepare a variety of silicate coatings, adapts to different temperatures section coating
It needs.The method of the present invention short preparation period, technical process are simple, at low cost, have broad application prospects.
Through the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite made from the method for the present invention, thickness is equal
Even, compact structure, without apparent hole and crackle, inside and outside coating is tightly combined, without apparent boundary.
Description of the drawings
XRD spectrums of the Fig. 1 for mullite crystal whisker layer prepared under the conditions of embodiment 3；
SEM photographs of the Fig. 2 for mullite crystal whisker layer prepared under the conditions of embodiment 3；Wherein, (a) mullite crystal whisker layer
Surface SEM photograph；(b) it is the section SEM photograph of mullite crystal whisker layer；
XRD spectrums of the Fig. 3 for mullite crystal whisker plasticizing mullite coating prepared under the conditions of embodiment 3；
SEM photographs of the Fig. 4 for mullite crystal whisker plasticizing mullite coating prepared under the conditions of embodiment 3；Wherein, (a)
For surface SEM photograph；(b) it is section SEM photograph.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Embodiment 1
A kind of preparation method of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite, including following step
Suddenly：
(1) it is 9 in mass ratio:10 ratio weighs analytically pure Al respectively2(SO4)3·18H2O and Na2SO4In mortar
In, 60min is fully ground to being uniformly mixed, and obtains the mixing double salt A of the two.
(2) the C/C composite samples (SiC-C/C) with SiC coatings are placed in ethyl alcohol and be cleaned by ultrasonic, then
It takes out sample to dry at 80 DEG C, SiC-C/C sample masses is weighed, using mass ratio as 2:19 ratio weigh above-mentioned double salt A in
In corundum crucible, and SiC-C/C samples are embedded in double salt.
(3) crucible for having embedded SiC-C/C samples is placed in Muffle furnace and reacts 40min in 925 DEG C.
(4) it after reaction finishes furnace cooling to room temperature, takes out；It is washed in 100 DEG C of boiling water, until cleaning not
The fused salt of reaction, then by sample, dry 2h obtains the sample with mullite crystal whisker layer in 80 DEG C of electric drying oven with forced convection
(mullite/SiC-C/C)。
(5) it is 2 by molar ratio:3 Si powder and nanometer Al2O3The mixed powder of powder composition is scattered in 20mL distilled water and silicon
Colloidal sol is using volume ratio as 3:The slurry of a concentration of 200g/L of mixed powder is configured in the mixed solution that 1 ratio is composed
B1 by slurry B1 ultrasonic vibration 10min, 1h is then stirred on magnetic stirring apparatus, obtains slurry B2.
(6) the slurry B2 obtained by (5) is equably painted on as the mullite/SiC-C/C samples obtained by (4) with paintbrush
Surface, and dry at room temperature, dry 2h is put into baking oven at 50 DEG C after being repeated 10 times.
(7) sample obtained by (6) is put in high-temperature atmosphere furnace, under protection of argon gas at 1500 DEG C keep the temperature 2h to get
The crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite.
Embodiment 2
A kind of preparation method of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite, including following step
Suddenly：
(1) it is 9 in mass ratio:10 ratio weighs analytically pure Al respectively2(SO4)3·18H2O and Na2SO4In mortar
In, 50min is fully ground to being uniformly mixed, and obtains the mixing double salt A of the two.
(2) the C/C composite samples (SiC-C/C) with SiC coatings are placed in ethyl alcohol and be cleaned by ultrasonic, then
It takes out sample to dry at 70 DEG C, SiC-C/C sample masses is weighed, using mass ratio as 3:19 ratio weigh above-mentioned double salt A in
In corundum crucible, and SiC-C/C samples are embedded in double salt.
(3) crucible for having embedded SiC-C/C samples is placed in Muffle furnace and reacts 30min in 950 DEG C.
(4) it after reaction finishes furnace cooling to room temperature, takes out；It is washed in 100 DEG C of boiling water, until cleaning not
The fused salt of reaction, then by sample, dry 1h obtains the sample with mullite crystal whisker layer in 90 DEG C of electric drying oven with forced convection
(mullite/SiC-C/C)。
(5) it is 2 by molar ratio:3 Si powder and nanometer Al2O3The mixed powder of powder composition is scattered in 30mL distilled water and silicon
Colloidal sol is using volume ratio as 3:The slurry of a concentration of 250g/L of mixed powder is configured in the mixed solution that 1 ratio is composed
B1 by slurry B1 ultrasonic vibration 15min, 2h is then stirred on magnetic stirring apparatus, obtains slurry B2.
(6) the slurry B2 obtained by (5) is equably painted on as the mullite/SiC-C/C samples obtained by (4) with paintbrush
Surface, and dry at room temperature, dry 2h is put into baking oven at 60 DEG C after being repeated 8 times.
(7) sample obtained by (6) is put in high-temperature atmosphere furnace, under protection of argon gas at 1500 DEG C keep the temperature 3h to get
The crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite.
Embodiment 3
A kind of preparation method of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite, including following step
Suddenly：
(1) it is 9 in mass ratio first:10 ratio weighs analytically pure Al respectively2(SO4)3·18H2O and Na2SO4Yu Yan
In alms bowl, 30min is fully ground to being uniformly mixed, obtains the mixing double salt A of the two.
(2) the C/C composite samples (SiC-C/C) with SiC coatings are placed in ethyl alcohol and be cleaned by ultrasonic, then
It takes out sample to dry at 60 DEG C, SiC-C/C sample masses is weighed, using mass ratio as 1:19 ratio weigh above-mentioned double salt A in
In corundum crucible, and SiC-C/C samples are embedded in double salt.
(3) crucible for having embedded SiC-C/C samples is placed in Muffle furnace and reacts 60min in 900 DEG C.
(4) it after reaction finishes furnace cooling to room temperature, takes out；It is washed in 100 DEG C of boiling water, until cleaning not
The fused salt of reaction, then by sample, dry 3h obtains the sample with mullite crystal whisker layer in 60 DEG C of electric drying oven with forced convection
(mullite/SiC-C/C)。
(5) it is 2 by molar ratio:3 Si powder and nanometer Al2O3The mixed powder of powder composition is scattered in 40mL distilled water and silicon
Colloidal sol is using volume ratio as 3:The slurry of a concentration of 300g/L of mixed powder is configured in the mixed solution that 1 ratio is composed
B1 by slurry B1 ultrasonic vibration 20min, 3h is then stirred on magnetic stirring apparatus, obtains slurry B2.
(6) the slurry B2 obtained by (5) is equably painted on as the mullite/SiC-C/C samples obtained by (4) with paintbrush
Surface, and dry at room temperature, dry 1h is put into baking oven at 80 DEG C after being repeated 5 times.
(7) sample obtained by (6) is put in high-temperature atmosphere furnace, under protection of argon gas at 1500 DEG C keep the temperature 4h to get
The crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite.
Referring to Fig. 1, using the XRD spectrum of mullite crystal whisker layer prepared by molten-salt growth method, as can be seen from Figure using molten-salt growth method
Mullite crystal whisker layer can be successfully prepared on SiC-C/C surfaces.The diffraction peak intensity of mullite is significantly lower than SiC, this illustrates fused salt
Method, to the corrosion of SiC-C/C and little, can play preferable modifying function when preparing mullite crystal whisker layer.
Referring to Fig. 2, it is the SEM photograph of prepared mullite crystal whisker layer, can be seen that from Fig. 2 (a), prepared does not come
Stone crystal whisker layer is formed by uniformly collecting pencil whisker.It can be seen that from the section SEM photograph of Fig. 2 (b), by molten-salt growth method in SiC-C/
Uniformly prepare the mullite crystal whisker layer that thickness is 10~20 μm in C sample surface.
It is the XRD spectrum of prepared mullite crystal whisker plasticizing mullite coating, it is seen that this referring to Fig. 3
Molten-salt growth method combination reaction in-situ can successfully prepare mullite crystal whisker plasticizing mullite coating.In coating using mullite crystalline phase as
It is main, there is a small amount of unreacted Si and SiO2, this antioxygenic property of coating is influenced it is little, can be by antioxidation process
Gradually form glassy state, so as in time heal coating in the presence of the defects of.
Referring to Fig. 4, shone using the SEM of mullite crystal whisker plasticizing mullite coating of the molten-salt growth method with reference to prepared by hot method
Piece.It can be seen that from Fig. 4 (a), the crystal whisker toughened mullite antioxidant coating surface of prepared carbon/carbon composite mullite causes
It is close uniform, without apparent hole and crackle.It can be seen that from Fig. 4 (b), prepared carbon/carbon composite mullite whisker increases
Tough mullite antioxidant coating very dense uniform, due to being prepared for mullite crystal whisker buffer layer, inside and outside coating is tightly combined, and is not had
There is apparent boundary.
In conclusion the present invention prepares the anti-oxidant outer painting of mullite crystal whisker plasticizing mullite using molten-salt growth method combination in-situ method
Layer has following three points advantage：
(1) it can significantly reduce synthesis temperature and shorten the reaction time, be attributed to due to the formation of the melt of salt, make anti-
The mobility enhancing of ingredient in the liquid phase is answered, diffusion rate significantly improves.Simultaneously because fused salt is applied between the particle of generation,
It is interconnected between prevention particle, therefore, material soilless sticking made from molten-salt growth method or only weakly agglomerated；
(2) shape and size of material can more easily be controlled；
(3) in the reaction process of molten-salt growth method and subsequent cleaning process, the elimination of impurity is also beneficial to, is formed high-purity
Reaction product.The basic principle of reaction in-situ is by mixing elemental silicon and soaking good metal oxide with it, be coated on
It is previously prepared to have the internally coated specimen surfaces of SiC, before sintering is pre-formed fine and close Si and metal oxide under atmosphere protection
It drives body coating, a period of time is then pre-oxidized at certain temperature and oxidizing atmosphere, then it can be with in-situ preparation antioxygenic property
It gets well, oxygen permeability is low, heat safe silicate external coating.The method is unique in that courageously using high temperature oxidative atmosphere
External coating is prepared, it is not only cost-effective, also start a new road.This method easily controls the component of coating
System can prepare a variety of silicate coatings, adapt to different temperatures section coating needs.
Claims (8)
- A kind of 1. preparation method of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite, which is characterized in that packet Include following steps：1) by Al2(SO4)3·18H2O：Na2SO4=9:10 mass ratio, takes Al2(SO4)3·18H2O and Na2SO4, abundant mixing Afterwards, mixing double salt A is made；2) SiC-C/C composite samples are cleaned by ultrasonic, after drying, by SiC-C/C composite samples：Mix double salt A=(1~3)：SiC-C/C composite samples are embedded in mixing double salt A by 19 mass ratio, at 900~950 DEG C, heat After processing, cooling；3) will through step 2), treated that sample is cleaned with boiling water, until unreacted fused salt is cleaned, then by samples dried, system Obtain the sample with mullite crystal whisker layer；4) by Si powder and Al2O3The mixed powder of powder composition is scattered in the mixed solution that Ludox is mixed with distilled water, system The slurry B1 of a concentration of 200~300g/L of mixed powder is obtained, after slurry B1 ultrasonic vibrations, then through magnetic agitation, slurry is made B2；In the mixed solution that Ludox is mixed with distilled water, the volume ratio of Ludox and distilled water is 1:3；Mixed powder In, Si powder and Al2O3The molar ratio of powder is 2:3；5) slurry B2 is uniformly painted on the step 3) specimen surface obtained for carrying mullite crystal whisker layer, dried at room temperature, After repeating brushing, drying operation 5~10 times, drying；6) sample for obtaining step 5) drying under protection of argon gas, at 1500 DEG C, keeps the temperature 2~4h, carbon/carbon composite wood is made Expect mullite crystal whisker plasticizing mullite antioxidant coating.
- 2. the preparation side of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite according to claim 1 Method, which is characterized in that the abundant mixing described in step 1) is by Al2(SO4)3·18H2O and Na2SO4It is placed in mortar, fully Grind 30~60min.
- 3. the preparation side of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite according to claim 1 Method, which is characterized in that step 2) is that SiC-C/C composite samples are placed in ethyl alcohol to be cleaned by ultrasonic, then in 50~80 DEG C Lower drying.
- 4. the preparation side of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite according to claim 1 Method, which is characterized in that step 2) is that mixing double salt A is placed in corundum crucible, SiC-C/C composite samples is embedded in mixed It closes in double salt A, then corundum crucible is placed in Muffle furnace, be heat-treated 30~60min.
- 5. the preparation side of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite according to claim 1 Method, which is characterized in that step 3) is the sample that will be cleaned dry 1~3h in 60~90 DEG C of electric drying oven with forced convection.
- 6. the preparation side of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite according to claim 1 Method, which is characterized in that by slurry B1 10~20min of ultrasonic vibration in step 4), 1~3h is then stirred on magnetic stirring apparatus, Obtain slurry B2.
- 7. the preparation side of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite according to claim 1 Method, which is characterized in that the drying described in step 5) is dry 1~2h at 50~80 DEG C.
- 8. the preparation side of the crystal whisker toughened mullite antioxidant coating of carbon/carbon composite mullite according to claim 1 Method, which is characterized in that step 6) is that the sample that drying obtains is carried out isothermal holding in high-temperature atmosphere furnace.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1793017A (en) * | 2005-11-22 | 2006-06-28 | 武汉理工大学 | Mullite whisker-mullite composite coating and preparation process thereof |
| JP4076309B2 (en) * | 1999-09-22 | 2008-04-16 | ニチアス株式会社 | Lining material for molten aluminum |
| CN103910532A (en) * | 2013-01-05 | 2014-07-09 | 中国科学院宁波材料技术与工程研究所 | Coating inorganic fiber toughened MAX phase ceramic composite material, preparation method and uses thereof |
| CN104130013A (en) * | 2014-07-10 | 2014-11-05 | 陕西科技大学 | Carbon/carbon composite material SiC whisker toughened mullite composite coating preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4076309B2 (en) * | 1999-09-22 | 2008-04-16 | ニチアス株式会社 | Lining material for molten aluminum |
| CN1793017A (en) * | 2005-11-22 | 2006-06-28 | 武汉理工大学 | Mullite whisker-mullite composite coating and preparation process thereof |
| CN103910532A (en) * | 2013-01-05 | 2014-07-09 | 中国科学院宁波材料技术与工程研究所 | Coating inorganic fiber toughened MAX phase ceramic composite material, preparation method and uses thereof |
| CN104130013A (en) * | 2014-07-10 | 2014-11-05 | 陕西科技大学 | Carbon/carbon composite material SiC whisker toughened mullite composite coating preparation method |
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