CN103936465A - Anti-oxidation coating of carbon/carbon composite material and preparation method of anti-oxidation coating - Google Patents
Anti-oxidation coating of carbon/carbon composite material and preparation method of anti-oxidation coating Download PDFInfo
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Abstract
The invention relates to an anti-oxidation coating of a carbon/carbon composite material and a preparation method of the anti-oxidation coating, and belongs to the technical field of medium or low-temperature anti-oxidation coatings. The anti-oxidation coating of the carbon/carbon composite material sequentially comprises SiC, ZrO2 and glass ceramic from inside to outside. The preparation method comprises the following steps: preparing an internal SiC coating by utilizing an embedding and siliconizing process; coating slurry formed by ZrO2 powder and water on the surface of the internal SiC coating and then drying a ZrO2 coating; mixing MgO powder, CaO powder, SiO2 powder, Al2O3 powder, BaO powder, B2O3 powder and Cr2O3 powder (abbreviated as MCSA) in certain proportion in a ball grinding manner, sintering at a high temperature and dispersing in a water quenching manner so as to prepare MCSA aqueous slurry; coating the MCSA aqueous slurry on the surface of the ZrO2 coating and then drying and curing at a low temperature; and performing heat treatment on the sample containing three coatings for 5 to 20 minutes within 1100 DEG C to 1400 DEG C so as to prepare the medium or low-temperature anti-oxidation SiC/ZrO2/glass ceramic coating. The method is simple in process and convenient to operate. The anti-oxidation coating is controllable in thickness and firmly and evenly bonded with a carbon/carbon substrate, has good anti-oxidation performance and good thermal shock resistance, and can be suitable for industrial production.
Description
Technical field
The present invention relates to inoxidzable coating of a kind of carbon/carbon composite and preparation method thereof, belong to middle low temperature inoxidzable coating technical field.
Background technology
Carbon/carbon composite is the advanced composite material of a class density low and high temperature mechanical property excellence, is used widely at aerospace field.But char/char compound material antioxygenic property is poor, there are being under oxygen atmosphere 370 DEG C to start to occur oxidizing reaction, 450 DEG C above has a strong impact on its mechanical property and physicals along with the temperature oxidation aggravation that raises, and has limited its long-time application in aerobic environment.
For the carbon/carbon composite of aircraft brake disks, brake temperature can, up to 900 DEG C, although single braking time is as short as tens seconds, but still need to be taked anti-oxidation measure.Anti-oxidant for carbon/carbon composite, people are that main inoxidzable coating has done a lot of research to adopting phosphoric acid salt, phosphoric acid salt is that the advantage of master's inoxidzable coating is that construction is simple, can be permanently effective be applied to below 800 DEG C, but phosphate coating lost efficacy above very soon at 850 DEG C conventionally, in the preparation simultaneously, generally to adopt resin and poisonous thinner, in construction process, with the smell of intense stimulus, so generally operate under the good operating environment of ventilation effect, but this still can bring harm to environment and personnel's health.
Anti-oxidant for carbon/carbon composite, people have also done more research to SiC coating, conventionally adopt pickling process or chemical Vapor deposition process (CVD) in the oxidation resistant SiC coating of carbon/carbon composite surface preparation.Under high temperature, (be generally greater than 1300 DEG C), SiC coating and oxygen reaction form fine and close SiO
2film, has good protection effect.Show but study, individual layer SiC coating, between 800-1300 DEG C, cracks because the difference of the coefficient of expansion and carbon/carbon composite causes coatingsurface, is not suitable for for a long time for this class temperature environment.
Except silicon carbide, molybdenum silicide (MoSi
2), chromium silicide (CrSi
2), tungsten silicide (WSi
2) and silicate ceramic coating research also many.The general form that adopts single-phase, heterogeneous, gradient, crystal whisker toughened and MULTILAYER COMPOSITE.Preparation method is taking entrapping method as main.This class ceramic coating has three open defects in the anti-oxidant application of charcoal charcoal: the one, due to the intrinsic fragility of stupalith, it is too large that thermal expansivity and carbon base body differ, and when cooling, thermal stresses is very large, and easily cracking peels off, thermal shock resistance is very poor, and heat shock resistance and high temperature resistance performance of flushing are bad; The 2nd, due to the existence of open crackle, its oxidation resistance temperature all, more than 1300 DEG C, is not suitable for the anti-oxidant applied environment of middle low temperature; The 3rd, ceramic coating preparation method's limitation, is not suitable for complex large-sized member, is difficult to ensure the stability of technique, the homogeneity of coating and integrity.
Summary of the invention
For the shortcoming existing in prior art, the invention provides a kind of can be at 1300 DEG C of following normal carbon/carbon composite material oxidation-proof coatings that use and preparation method thereof.
A kind of carbon/carbon composite material oxidation-proof coating of the present invention, is made up of undercoat, inter coat, external coating (EC); Described undercoat is SiC coating; Described inter coat is ZrO
2coating; Described external coating (EC) is MCSA glass ceramic coating, and described MCSA glass ceramic coating comprises that following component forms by mass percentage:
SiO
230-65%; Be preferably 35-60%; More preferably 45-55%;
CaO 10-30%; Be preferably 10-25%; More preferably 13-20%;
Al
2o
35-20%; Be preferably 6-18%; More preferably 9-12%;
BaO 5-20%; Be preferably 5-20%; More preferably 6-8%;
B
2o
35-15%; Be preferably 5-15%; More preferably 5-8%;
TiO
21-10%; Be preferably 1-5%; More preferably 1-3%;
MgO 1-5%; Be preferably 1-4%; More preferably 1-3%;
Cr
2o
31-5%; Be preferably 1-5%; More preferably 1-2%;
In described MCSA glass ceramic coating, the mass percent sum of each component equals 100%.
A kind of carbon/carbon composite material oxidation-proof coating of the present invention; Described ZrO
2the thickness of coating is 50-200 μ m.
A kind of carbon/carbon composite material oxidation-proof coating of the present invention; The thickness of described SiC coating is 50-200 μ m.
A kind of carbon/carbon composite material oxidation-proof coating of the present invention; The thickness of described MCSA glass ceramic coating is 10-100 μ m.
The preparation method of a kind of carbon/carbon composite material oxidation-proof coating of the present invention, its embodiment is:
Zirconium white water paste is evenly coated on the carbon/carbon composite that surface uniform is distributed with SiC coating, dry, obtain zirconia coating, then MCSA water-based slip is evenly coated on described zirconia coating, dry, sintering, obtains SiC/ZrO
2/ MCSA inoxidzable coating.
The preparation method of a kind of carbon/carbon composite material oxidation-proof coating of the present invention, the carbon/carbon composite that described surface uniform is distributed with SiC coating is:
Using the carbon/carbon composite of dry cleansing as substrate, substrate landfill, in siliconizing medium, is warming up to 1800 DEG C-2100 DEG C under protective atmosphere, insulation 2-3 hour, obtains surface uniform and is distributed with the carbon/carbon composite of SiC coating; The thickness of described SiC coating is 50-200 μ m; Described siliconizing medium comprises by percentage to the quality
Si powder 80-90%;
C powder 8-15%;
Al
2o
3powder 2-6%;
When insulation, silica flour and carbon/carbon composite generation surface reaction, liquid siliconizing medium permeates in matrix simultaneously, forms the high silicon carbide undercoat of boundary strength.
In actual mechanical process, the carbon/carbon composite of using as substrate is by following pre-treatment:
By the carbon/carbon composite of choosing according to actual needs, be processed into after desired shape, polish with sand paper, then use ultrasonic cleaning, water several times before ultrasonic cleaning liquid, last with using dehydrated alcohol; After cleaning, take out and be positioned over baking 20-28h in loft drier, storing temperature is 80 DEG C～120 DEG C, obtains the substrate of dry cleansing after oven dry.
The preparation method of a kind of carbon/carbon composite material oxidation-proof coating of the present invention, described zirconium white water paste is:
ZrO taking granularity as 1-50 μ m
2powder is raw material, in mass ratio, and ZrO
2powder: water=1:3-5 is by ZrO
2powder, water add in ball mill, and ball milling 2-6 hour obtains zirconium white water paste; The processing parameter of ball milling is: rotating speed 150-300r/min, abrading-ball and ZrO
2the mass ratio of powder is that 1:0.1-0.5, abrading-ball are selected from one in zirconium oxide balls, Wimet abrading-ball, polishing stainless steel ball, is preferably zirconium oxide balls.
The preparation method of a kind of carbon/carbon composite material oxidation-proof coating of the present invention, Zirconia Slurry is evenly brushed after surface uniform is distributed with on the carbon/carbon composite of SiC coating, being placed in air dries, then 60-120 DEG C of oven dry, obtain zirconia coating, the thickness of described zirconia coating is 50-200 μ m.In the process of coated with zirconia coating, if slip of coating cannot reach the thickness requirement of coating, can repetitive coatings several.If but coated with zirconia overweight coating can cause ftractureing in the dry or subsequent heat treatment of coating, therefore must control the thickness of coating in coating procedure.
The preparation method of a kind of carbon/carbon composite material oxidation-proof coating of the present invention, described MCSA water-based slip is prepared by following proposal:
By mass percentage, take respectively
SiO
2powder 30-65%; Be preferably 35-60%; More preferably 45-55%;
CaO powder 10-30%; Be preferably 10-25%; More preferably 13-20%;
Al
2o
3powder 5-20%; Be preferably 6-18%; More preferably 9-12%;
BaO powder 5-20%; Be preferably 5-20%; More preferably 6-8%;
B
2o
3powder 5-15%; Be preferably 5-15%; More preferably 5-8%;
TiO
2powder 1-10%; Be preferably 1-5%; More preferably 1-3%;
MgO powder 1-5%; Be preferably 1-4%; More preferably 1-3%;
Cr
2o
3powder 1-5%; Be preferably 1-5%; More preferably 1-2%;
The mass percent sum of the powder of getting is 100%; The granularity of described powder is 0.1-30 μ m;
After got powder is mixed at 1400-1800 DEG C sintering 0.5-3 hour, shrend, fragmentation, obtaining granularity is the MCSA ceramic powder of 0.1-20 μ m; Then in mass ratio, MCSA ceramic powder: water=1:1-10, mixes MCSA ceramic powder with water for ball milling, obtains MCSA water-based slip.The processing parameter of ball mill mixing is: the mass ratio of rotating speed 100-300r/min, ball and MCSA pottery is 1:0.1-0.5, and abrading-ball is aluminum oxide abrading-ball or Wimet abrading-ball.The preferred sintering temperature of the powder of getting is 1650-1750 DEG C.
In actual application, after shrend, conventionally adopt ball milling to carry out fragmentation.
The preparation method of a kind of carbon/carbon composite material oxidation-proof coating of the present invention, prepared SiC/ZrO
2in/MCSA inoxidzable coating, the thickness of MCSA coating is 10-100 μ m.In the time applying MCSA coating, MCSA water-based slip is evenly brushed on zirconia coating, be placed in air and dry, then dry 8-30 hour at 120-300 DEG C.In actual mechanical process, apparent surface coat-thickness situation can repeat to brush, dries, stoving process.
Principle and advantage
The present invention adopts three coating structures, body material is coated with coat of silicon carbide, zirconia coating, MCSA glass ceramic coating outward successively, its antioxidant property is better than general double-deck sample, its reason is: MCSA glass ceramic coating can stop that with the composition of its uniqueness oxygen contacts with charcoal/carbon matrix, anti-oxidation, at the temperature of 800-1300 DEG C, this glass coating has part self-healing function, micropore and the tiny crack of the coating that can heal itself, effectively stop the erosion of oxygen molecule, there is good oxidation-resistance; Can not only coordinate the thermal expansivity of bottom coat of silicon carbide and MCSA glass ceramic coating using zirconia coating as inter coat, and zirconia coating add the ability that can improve the anti-accidental overtemperature of matrix, itself also has good antioxidant property simultaneous oxidation zirconium coating; The strict thickness of controlling zirconia coating is because zirconia coating is blocked up, can cause ftractureing in the dry or subsequent heat treatment of coating, thereby have a strong impact on antioxidant property and the mechanical property of finished product; Select coat of silicon carbide not only can coordinate the thermal expansivity of charcoal/carbon matrix and zirconia coating as undercoat, and can more effectively carry out three obstructs to entering the oxygen of glass coating and zirconia coating, further increase the antioxidant property of matrix.Coat of silicon carbide is well combined with charcoal/carbon matrix with energy simultaneously, can effectively stop carbon matrix atom to external diffusion; This is also conducive to improve the antioxidant property of matrix.
The present invention, by strict component and the preparation technology who controls each coating, makes the prepared finished product of the present invention have good thermostability, thermal-shock resistance and heat resistanceheat resistant damaging; The thermal shock repeatedly of tens room temperature-middle low temperature, coating is without coming off.
When the present invention prepares zirconia coating and MCSA glass ceramic coating, what all adopt is to apply mode of operation, apply mode of operation and be applicable to the preparation of complex large-sized component surface coating, apply the stability that mode of operation ensured technique to the full extent, homogeneity and the integrity of coating simultaneously.In coating operation process, the present invention has adopted the zirconia slurry of zirconium white and water composition and the MCSA glass-ceramic slurry of MCSA glass-ceramic powder and water composition, does not add poisonous material, and this is conducive to the protection of environment and workmen's health.
Preparation technology of the present invention is simple, easy to operate, can realize the suitability for industrialized production of big area amorphism restriction.In preparation process, there is no poisonous and/or sexual stimulus γ-ray emission, be conducive to environment and workmen's protection.
Brief description of the drawings:
Accompanying drawing 1 is prepared SiC/ZrO for the present invention
2the process flow diagram of/MCSA coating;
What accompanying drawing 2 was prepared for embodiment 1 contains SiC/ZrO
2the optical photograph of/MCSA coating charcoal/charcoal sample;
Accompanying drawing 3 is the SEM photo in the prepared carbon/carbon composite material oxidation-proof coating cross section of embodiment 1;
Accompanying drawing 4 is X diffraction spectra (XRD) figure of embodiment 1 and 2 prepared carbon/carbon composite material oxidation-proof coatings;
Accompanying drawing 5 is embodiment 1 and 2 prepared carbon/carbon composite material oxidation-proof coating sample and the prepared not brushing ZrO of comparative example 1
2/ MCSA coating sample is at the graphic representation of 1000 DEG C of oxidation weight loss;
Accompanying drawing 6 is the three-point bending resistance intensity curve of the prepared carbon/carbon composite material oxidation-proof coating sample of embodiment 3 under different oxidizing temperature conditions;
As can be seen from Figure 2 Watch glass ceramic coating is smooth complete.
As can be seen from Figure 3 coating is SiC, ZrO from inside to outside successively
2with tri-layers of MACS, thickness is about respectively 75 μ m, 80 μ m and 40 μ m.
In Fig. 4:
1# curve is corresponding is the XRD figure of embodiment 1 prepared carbon/carbon composite material oxidation-proof coating;
2# curve is corresponding is the XRD figure of embodiment 2 prepared carbon/carbon composite material oxidation-proof coatings.
As can be seen from Figure 4 the structure of coating is mainly made up of trichroite, silicon carbide, zirconium white, silicon oxide, aluminum oxide, has a small amount of not yet silicon of complete reaction.
In Fig. 5:
Sample 1 is the prepared carbon/carbon composite material oxidation-proof coating sample of embodiment 1, and the corresponding curve of sample 1 is 1000 DEG C of oxidation weight loss curves of this sample;
Sample 2 is the prepared carbon/carbon composite material oxidation-proof coating sample of embodiment 1, and the corresponding curve of sample 2 is 1000 DEG C of oxidation weight loss curves of this sample;
C
f/ C/SiC sample is the prepared carbon/carbon composite material oxidation-proof coating sample of comparative example 1, C
fthe corresponding curve of/C/SiC sample is 1000 DEG C of oxidation weight loss curves of this sample.
As can be seen from Figure 5, and the not sample (C of brush applied coating
f/ C/SiC) compare, obviously reduce the about 15mg/cm of the static oxidation oxidative mass loss of 20 hours at 1000 DEG C containing the sample oxidative mass loss of coating
2, there is good antioxidant property.
In Fig. 6:
No. 1 curve is under room temperature, the three-point bending resistance intensity curve of the prepared carbon/carbon composite material oxidation-proof coating sample of embodiment 3, can find out that from No. 1 curve prepared carbon/carbon composite material oxidation-proof coating sample three-point bending resistance intensity is at room temperature 104Mpa;
No. 2 curves are that the prepared carbon/carbon composite material oxidation-proof coating sample of embodiment 3 is at 850 DEG C of three-point bending resistance intensity curves that are oxidized after 4 hours, from No. 2 curves, can find out 850 DEG C of oxidations after 4 hours, the bending strength of sample is 99Mpa, under room temperature, its flexural strength conservation rate approximately 95%;
No. 3 curves are that the prepared carbon/carbon composite material oxidation-proof coating sample of embodiment 3 is at 1000 DEG C of three-point bending resistance intensity curves that are oxidized after 4 hours, from No. 3 curves, can find out 850 DEG C of oxidations after 4 hours, the bending strength of sample is 73Mpa, under room temperature, its flexural strength conservation rate approximately 70%.
Embodiment:
Embodiment 1:
The three-dimensional acupuncture matrix of carbon/carbon composite materials of chemical vapour deposition is cut into different shapes, the density 1.5g/cm of matrix of carbon/carbon composite materials on request
3.Use respectively 100#-500# sand paper to matrix surface sanding and polishing, then respectively water and dehydrated alcohol ultrasonic cleaning 20 minutes, be placed in loft drier, after 80 DEG C of drying treatment 24h, take out for subsequent use.
Take the Si powder of 80wt.%, the C powder of 15wt.%, the Al of 5wt.%
2o
3powder, mixing and ball milling obtains mixed powder after 5 hours.Mixed powder is put into plumbago crucible; then by complete carbon/carbon composite sample landfill in mixed powder; plumbago crucible is built and be placed in graphite heater High Temperature Furnaces Heating Apparatus again; be evacuated to 0.08Pa backlash Ar gas shield; with the speed of 6 DEG C/min, furnace temperature is risen to 1800 DEG C and be incubated 2 hours; powered-down is lowered the temperature naturally, forms the silicon carbide internal layer of thick approximately 75 μ m on charcoal/carbon matrix surface.
Be the ZrO of 25 microns by granularity
2powder and water in mass ratio, ZrO
2powder: water=1:3 mixing and ball milling obtains Zirconia Slurry for 2 hours, evenly brushes slip and is containing the internally coated charcoal/carbon matrix of SiC material surface, and in air, 60 DEG C of oven dry obtain 80 μ m thick oxidized zirconium layers.
Take respectively 50wt.%SiO
2, 20wt.%CaO, 10wt.%Al
2o
3, 10wt.%BaO, 5wt.%B
2o
3, 2wt.%TiO
2, 1.5wt.%MgO, 1.5wt.%Cr
2o
3powder, sintering shrend after 1 hour at 1700 DEG C after ball mill mixing, fragmentation obtains the MCSA powder that granularity is 10-12 μ m, and in mass ratio, MCSA powder: water=1:3, mixes MCSA powder to obtain MCSA water-based slip through ball milling with water.Then MCSA water-based slip is brushed and contained SiC undercoat and ZrO
2on the charcoal/Carbon Materials of layer, and sample is placed in to 120 DEG C of bakings of air 12 hours, obtains the MCSA surface ceramic coat of thick approximately 40 μ m.
Will be containing SiC undercoat, ZrO
2layer and charcoal/Carbon Materials sample of MCSA surface ceramic coat are put into box-type furnace, and thermal treatment 20 minutes in 1200 DEG C of air makes carbon/carbon composite SiC/ZrO after cooling
2/ MCSA coating.
Will be containing SiC/ZrO
2the sample of/MCSA coating is put into tubular type oxidized still tested static oxidation susceptibility, takes out at set intervals its weight of sample weighing, and its typical oxidative mass loss is shown in Fig. 5 sample 1.
Will be containing SiC/ZrO
2the sample of/MCSA coating, carries out after the thermal shock repeatedly 20 times of room temperature-1000 DEG C, and coating is without obscission, and this can not only prove that coating bonding is good and proved that coating heat-shock resistance is good.
Use X-ray diffractometer to detect sample, obtain the corresponding XRD figure of 1# sample in Fig. 1.
Embodiment 2:
The three-dimensional of chemical vapour deposition is carefully compiled to puncture matrix of carbon/carbon composite materials and cut on request different shapes, the density 1.6g/cm of matrix of carbon/carbon composite materials
3.Use respectively 100#-500# sand paper to its surface finish polishing, then respectively water and dehydrated alcohol ultrasonic cleaning 15 minutes, be placed in loft drier, after 120 DEG C of drying treatment 24h, take out for subsequent use.
Take the Si powder of 90wt.%, the C powder of 8wt.%, the Al of 2wt.%
2o
3powder, mixing and ball milling obtains mixed powder after 5 hours.Mixed powder is put into plumbago crucible; then by complete carbon/carbon composite sample landfill in mixed powder; plumbago crucible is built and be placed in graphite heater High Temperature Furnaces Heating Apparatus again; be evacuated to 0.08Pa backlash Ar gas shield; with the speed of 6 DEG C/min, furnace temperature is risen to 2000 DEG C and be incubated 2 hours; powered-down is lowered the temperature naturally, forms silicon carbide internal layer on charcoal/carbon matrix surface.
Be the ZrO of 2 microns by granularity
2powder and water in mass ratio, ZrO
2powder: water=1:4 mixing and ball milling obtains Zirconia Slurry for 2 hours, evenly brushes slip and is containing the internally coated charcoal/carbon matrix of SiC material surface, and in air, 60 DEG C of oven dry obtain 100 μ m zirconia layers.
Take respectively 55wt.%SiO
2, 17wt.%CaO, 12wt.%Al
2o
3, 6wt.%BaO, 5wt.%B
2o
3, 2wt.%TiO
2, 1.5wt.%MgO, 1.5wt.%Cr
2o
3powder, sintering shrend after 3 hours at 1650 DEG C after ball mill mixing, being crushed to granularity is the MCSA powder of 2-4 μ m, in mass ratio, MCSA powder: water=1:5 mixes MCSA powder and obtains MCSA water-based slip with ball milling.Then MCSA water-based slip is brushed and contained SiC undercoat and ZrO
2on the charcoal/Carbon Materials of layer, and sample is placed in to 180 DEG C of bakings of air 8 hours, obtains MCSA surface ceramic coat, the thickness of MCSA coating approximately 50 μ m.
Will be containing SiC undercoat, ZrO
2layer and charcoal/charcoal sample of MCSA surface ceramic coat are put into box-type furnace, and thermal treatment 20 minutes in 1250 DEG C of air makes carbon/carbon composite SiC/ZrO after cooling
2/ MCSA coating.
Will be containing SiC/ZrO
2the sample of/MCSA coating is put into tubular type oxidized still tested static oxidation susceptibility, takes out at set intervals its weight of sample weighing, and its typical oxidative mass loss is shown in Fig. 5 sample 2.
Will be containing SiC/ZrO
2the sample of/MCSA coating, carries out after the thermal shock repeatedly 20 times of room temperature-1000 DEG C, and coating is without obscission, and this can not only prove that coating bonding is good and proved that coating heat-shock resistance is good.
Use X-ray diffractometer to detect sample, obtain the corresponding XRD figure of 2# sample in Fig. 1.
Embodiment 3:
Matrix of carbon/carbon composite materials adopts web of staple fibers tire Nomex, and chemical vapour deposition, in conjunction with the preparation of dipping charing thickening technology, cuts into different shapes, matrix density 1.7g/cm on request
3.Use respectively 100#-500# sand paper to its surface finish polishing, then respectively water and dehydrated alcohol ultrasonic cleaning 25 minutes, be placed in loft drier, after 120 DEG C of drying treatment 24h, take out for subsequent use.
Take the Si powder of 85wt.%, the C powder of 10wt.%, the Al of 5wt.%
2o
3powder, mixing and ball milling obtains mixed powder after 5 hours.Mixed powder is put into plumbago crucible; then by complete carbon/carbon composite sample landfill in mixed powder; plumbago crucible is built and be placed in graphite heater High Temperature Furnaces Heating Apparatus again; be evacuated to 0.08Pa backlash Ar gas shield; with the speed of 6 DEG C/min, furnace temperature is risen to 1900 DEG C and be incubated 2 hours; powered-down is lowered the temperature naturally, forms silicon carbide internal layer on charcoal/carbon matrix surface.
Be the ZrO of 35 microns by granularity
2powder and water in mass ratio, ZrO
2powder: water=1:5 mixing and ball milling obtains Zirconia Slurry for 2 hours, evenly brushes slip and is containing the internally coated charcoal/carbon matrix of SiC material surface, and in air, 60 DEG C of oven dry obtain the thick zirconia layer of 120 μ m.
Take respectively 55wt.%SiO
2, 15wt.%CaO, 9wt.%Al
2o
3, 8wt.%BaO, 8wt.%B
2o
3, 2wt.%TiO
2, 1.5wt.%MgO, 1.5wt.%Cr
2o
3powder, sintering shrend after 0.5 hour at 1710 DEG C after ball mill mixing, being crushed to granularity is the MCSA powder of 18-20 μ m, in mass ratio, MCSA powder: water=1:8 mixes MCSA powder and obtains MCSA water-based slip with ball milling.Then MCSA water-based slip is brushed and contained SiC undercoat and ZrO
2on the charcoal/Carbon Materials of layer, and sample is placed in to 200 DEG C of bakings of air 8 hours, obtains the MCSA surface ceramic coat of thick approximately 80 μ m.
Will be containing SiC undercoat, ZrO
2layer and charcoal/Carbon Materials sample of MCSA top coat are put into box-type furnace, and thermal treatment 20 minutes in 1150 DEG C of air makes carbon/carbon composite SiC/ZrO after cooling
2/ MCSA coating.
Will be containing SiC/ZrO
2the sample of/MCSA coating is put into tubular type oxidized still tested static oxidation susceptibility, takes out at set intervals its weight of sample weighing.
Will be containing SiC/ZrO
2the sample of/MCSA coating, carries out after the thermal shock repeatedly 20 times of room temperature-1000 DEG C, and coating is without obscission, and this can not only prove that coating bonding is good and proved that coating heat-shock resistance is good.
Adopt three-point bending test to evaluate the flexural strength conservation rate of sample oxidation front and back, the results are shown in Figure shown in 6.
Comparative example 1
In employing and embodiment 1, prepare same materials and the treatment process of coat of silicon carbide, prepare the silicon carbide internal layer of thick approximately 75 μ m on selected charcoal/carbon matrix surface; Detect its antioxidant property, its antioxidant property is as C in Fig. 5
fthe corresponding 1000 DEG C of oxidation weight loss graphic representations of/C/SiC coating; The about 110mg/cm of the static oxidation oxidative mass loss of 20 hours at 1000 DEG C
2, far away higher than embodiment 1 and the prepared SiC/ZrO of embodiment 2
2the oxidative mass loss of/MCSA coating.
Claims (10)
1. a carbon/carbon composite material oxidation-proof coating, is made up of undercoat, inter coat, external coating (EC); It is characterized in that: described undercoat is SiC coating; Described inter coat is ZrO
2coating; Described external coating (EC) is MCSA glass ceramic coating, and described MCSA glass ceramic coating comprises that following component forms by mass percentage:
In described MCSA glass ceramic coating, the mass percent sum of each component equals 100%.
2. a kind of carbon/carbon composite material oxidation-proof coating according to claim 1, is characterized in that,
Described MCSA glass ceramic coating, comprises that following component forms by mass percentage:
In described MCSA glass ceramic coating, the mass percent sum of each component equals 100%.
3. a kind of carbon/carbon composite material oxidation-proof coating according to claim 2, is characterized in that,
Described MCSA glass ceramic coating, comprises that following component forms by mass percentage:
In described MCSA glass ceramic coating, the mass percent sum of each component equals 100%.
4. according to a kind of carbon/carbon composite material oxidation-proof coating described in claim 1-3 any one, it is characterized in that: described ZrO
2the thickness of coating is 50-200 μ m; The thickness of described SiC coating is 50-200 μ m; The thickness of described MCSA glass ceramic coating is 10-100 μ m.
5. the preparation method of a carbon/carbon composite material oxidation-proof coating, it is characterized in that: zirconium white water paste is evenly coated on the carbon/carbon composite that surface uniform is distributed with SiC coating, dry, obtain zirconia coating, then MCSA water-based slip is evenly coated on described zirconia coating, dry, sintering, obtains SiC/ZrO
2/ MCSA inoxidzable coating.
6. the preparation method of a kind of carbon/carbon composite material oxidation-proof coating according to claim 5, is characterized in that, the carbon/carbon composite that described surface uniform is distributed with SiC coating adopts following proposal to prepare:
Using the carbon/carbon composite of dry cleansing as substrate, substrate landfill, in siliconizing medium, is warming up to 1800 DEG C-2100 DEG C under protective atmosphere, insulation 2-3 hour, obtains surface uniform and is distributed with the carbon/carbon composite of SiC coating; The thickness of described SiC coating is 50-200 μ m; Described siliconizing medium comprises by percentage to the quality
Si powder 80-90%;
C powder 8-15%;
Al
2o
3powder 2-6%.
7. the preparation method of a kind of carbon/carbon composite material oxidation-proof coating according to claim 5, is characterized in that, described zirconium white water paste adopts following proposal to prepare:
ZrO taking granularity as 1-50 μ m
2powder is raw material, in mass ratio, and ZrO
2powder: water=1:3-5 is by ZrO
2powder, water add in ball mill, and ball milling 2-6 hour obtains zirconium white water paste; The processing parameter of ball milling is: rotating speed 150-300r/min, abrading-ball and ZrO
2the mass ratio of powder is that 1:0.1-0.5, abrading-ball are selected from the one in zirconium oxide balls, Wimet abrading-ball, Stainless Steel Ball.
8. the preparation method of a kind of carbon/carbon composite material oxidation-proof coating according to claim 5, is characterized in that, described MCSA water-based slip adopts following proposal to prepare:
By following mass percent, take respectively each component powder: SiO
230-65%, CaO10-30%, Al
2o
35-20%, BaO5-20%, B
2o
35-15%, TiO
21-10%, MgO1-5%, Cr
2o
31-5%, after got powder is mixed, sintering 0.5-3 hour at 1400-1800 DEG C, shrend, being crushed to granularity is the MCSA ceramics powder of 0.1-20 μ m; Then in mass ratio, MCSA ceramics powder: water=1:1-10, mixes MCSA ceramics powder with water, obtains MCSA water-based slip; The granularity of described powder is 0.1-30 μ m.
9. the preparation method of a kind of carbon/carbon composite material oxidation-proof coating according to claim 5, is characterized in that: prepared SiC/ZrO
2in/MCSA inoxidzable coating, the thickness of zirconia coating is 50-200 μ m; The thickness of MCSA coating is 10-100 μ m.
10. the preparation method of a kind of carbon/carbon composite material oxidation-proof coating according to claim 5, is characterized in that: the temperature of sintering is that 1100 DEG C-1400 DEG C, time are 5-30 minute.
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