CN105110817A - Surface coating system of fiber reinforced ceramic matrix composite material and preparation method therefor - Google Patents
Surface coating system of fiber reinforced ceramic matrix composite material and preparation method therefor Download PDFInfo
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- CN105110817A CN105110817A CN201510509547.9A CN201510509547A CN105110817A CN 105110817 A CN105110817 A CN 105110817A CN 201510509547 A CN201510509547 A CN 201510509547A CN 105110817 A CN105110817 A CN 105110817A
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Abstract
The present invention provides a surface coating system of fiber reinforced ceramic matrix composite material, wherein the surface coating system is arranged on the substrate surface of the fiber reinforced ceramic matrix composite material and comprises a Sic coating layer, a mullite coating layer and a yttrium silicate coating layer laid in order from bottom to top. The preparation method comprises the following steps of preparing sludge raw materials of the Sic coating layer, the mullite coating layer and the yttrium silicate coating layer respectively, and preparing the Sic coating layer, the mullite coating layer and the yttrium silicate coating layer. The present invention is used for the surface coating system of the fiber reinforced ceramic matrix composite material, has the advantages of high density, high temperature resistance and anti-oxidation.
Description
Technical field
The present invention relates to high-temperature fibre and strengthen ceramic matric composite field; relate to lacquer systems of a kind of FRCMC and preparation method thereof, be specifically related to a kind of novel in order to three layers of fire-resistant oxidation resistant coating protecting the matrix materials such as C/SiC, SiC/SiC, C/C and preparation method thereof.
Background technology
Be the FRCMC of representative with carbon fibre reinforced silicon carbide (C/SiC), silicon carbide fiber reinforced silicon carbide (SiC/SiC), carbon-fiber reinforced carbon (C/C) matrix material, there is high specific strength and specific modulus, high temperature resistant, high damage tolerance, the excellent specific property such as corrosion-resistant, be considered to strategic thermal structure material, all have broad application prospects in fields such as aerospace, traffic, the energy, chemical industry.
As thermal structure material, C/SiC, SiC/SiC, C/C tri-kinds of matrix materials want to apply under high-temperature oxidation environment, particularly use for a long time, must solve anti-oxidant problem, its reason is: (1) C, SiC two kinds of components in atmosphere more than 400 DEG C and 1000 DEG C can there is obvious oxidation; (2) be subject to the restriction of preparation method, above-mentioned three kinds of matrix materials are difficult to accomplish complete densification all there is certain hole and tiny crack, and this is that oxygen provides passage to composite inner diffusion and then oxidation C, SiC; (3) C oxidation generates CO
2or the SiO that CO and losing efficacy, SiC oxidation generates
2although certain oxidation protection effect can be played, after temperature exceedes threshold value, SiO
2can rapidly volatilization, simultaneously also may and C between there is carbothermic reduction reaction and lose, thus lose provide protection.When drying, normal pressure, this zero point is about 1450 ~ 1600 DEG C, along with pressure reduction, moisture content increase obviously can drop to about 1200 DEG C.
Preparing high temperature resistant, oxidation resistant coating at composite material surface is current the most effective anti-oxidation method, and coated component and structure are then the key factors affecting antioxidant effect.Yttrium silicate has Y
2siO
5, Y
2si
2o
7, Y
4si
3o
12three kinds of crystal phase structures, wherein common with first two, fusing point is respectively 1980 DEG C, 1775 DEG C.Except high-melting-point, yttrium silicate also has the characteristics such as low thermal coefficient of expansion, low high-temperature oxygen rate of permeation, low modulus, low vaporization at high temperature rate, lower thermal conductivity, chemistry and Heat stability is good, makes one of its optimal candidate material becoming high-temperature oxidation resistant coating.As the oxidation resistant coating of C/C, C/SiC and SiC/SiC matrix material, yttrium silicate has caused the extensive concern of people and has obtained more research.
Iridium silicate coating layer is prepared at composite material surfaces such as C/SiC, C/C, SiC/SiC, the most general way is at present, first prepare SiC undercoat by chemical Vapor deposition process (mainly for C/SiC, SiC/SiC) or entrapping method (mainly for C/C), object alleviates thermal mismatching degree between composite substrate and iridium silicate coating layer to improve bonding strength, then utilizes hot isostatic pressing method, mud brushing sintering process, electrophoretic deposition, plasma spraying method, sol-gel method etc. to prepare yttrium silicate external coating (EC).The deficiency that these schemes exist has: the density of (1) iridium silicate coating layer self is inadequate, and oxygen is at Y
2o
3and SiO
2in spread coefficient be all low-down, if but coating itself is fine and close not, this advantage is just lost a lot.Improve sintering temperature simply to differ and be effective surely, can cause damage to composite substrate on the contrary.Though can improve density by adding glassy phase outermost layer, the temperature resistant capability of glassy phase is limited, and performance in aggressive atmosphere is not ideal enough; (2) along with time lengthening, SiC undercoat can be oxidized to SiO gradually
2, the gaseous by-product of generation ftractures to causing iridium silicate coating layer during external diffusion or comes off, thus affects the long-time antioxidant effect of coating; (3) some preparation methods such as hot isostatic pressing method, chemical Vapor deposition process, electrophoretic deposition etc. are difficult to the preparation being applicable to complex shaped components top coat.
For above-mentioned technical problem, application number be 201410701284.7 patent application (horse pine, bang hide, Cai Lihui. C/SiC composite material surface coating system and preparation method thereof) with mullite (3Al
2o
32SiO
2) replace SiC as undercoat, utilize silicone resin and Y
2o
3reactive Synthesis yttrium silicate external coating (EC), with the Al of high solid loading
2o
3-SiO
2colloidal sol, " (silicone resin+Y
2o
3powder)/ethanol " mud is raw material, prepares mullite and iridium silicate coating layer respectively by dip-coating method.Although the program can avoid SiC undercoat to be oxidized the problem causing yttrium silicate external coating (EC) to ftracture or come off, also expose some shortcomings: (1), by the restriction of colloidal sol synthetic technology, current also cannot directly synthesizing meets mullite stoichiometric ratio (Al simultaneously
2o
3/ SiO
2mass ratio is 2.13: 1 ~ 3.55: 1) Al
2o
3-SiO
2colloidal sol, can obtain the Al of colloidal sol at present
2o
3/ SiO
2mass ratio is only up to 2: 1, and that its conversion obtains is SiO more than needed
2mullite, these SiO more than needed
2more than 1450 DEG C can with the free carbon generation carbothermic reduction reaction in matrix material and destroy coating, in the environment having superheated vapor, SiO more than needed
2also can react and generate gaseous state Si (OH)
4and loss rapidly; (2) by Al
2o
3-SiO
2the impact of colloidal sol film-forming properties, cohesiveness, solid content, density, the sticking power of mullite coating are desirable not enough, and preparation efficiency is on the low side.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, a kind of high densification, high temperature resistant, the oxidation resistant lacquer systems being applicable to the matrix materials such as C/SiC, SiC/SiC, C/C are provided, the high efficiency preparation method with engineer applied universality of this lacquer systems is provided simultaneously.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A kind of lacquer systems being applicable to protect FRCMC from high temperature oxidation; described lacquer systems is located at the surface of FRCMC substrate, and described lacquer systems comprises SiC coating, mullite coating and the iridium silicate coating layer laid successively from the bottom to top.Wherein, SiC coating directly and FRCMC substrate contacts, is called undercoat; Mullite coating, between SiC and yttrium silicate, is called middle layer; Outermost layer is iridium silicate coating layer, is called external coating (EC).
In above-mentioned composite material surface coating system, preferably, described FRCMC substrate is one or more in C/SiC composite substrate, SiC/SiC composite substrate and C/C composite substrate.
In above-mentioned composite material surface coating system, preferably, in the chemical constitution of described mullite coating, Al
2o
3with SiO
2mass ratio be 2.13: 1 ~ 3.55: 1.
In above-mentioned composite material surface coating system, preferably, described iridium silicate coating layer is by Y
2si
2o
7and Y
2siO
5mixed coating, Y
2siO
5single-phase coating and Y
2si
2o
7one or more layers in single-phase coating is formed.Preferred further, described iridium silicate coating layer is yttrium silicate single-layer coating or yttrium silicate laminated coating.Described yttrium silicate single-layer coating is by Y
2si
2o
7and Y
2siO
5mixed coating, Y
2siO
5single-phase coating, Y
2si
2o
7one deck in single-phase coating is formed; Described yttrium silicate laminated coating is by Y
2si
2o
7and Y
2siO
5mixed coating, Y
2siO
5single-phase coating, Y
2si
2o
7multilayer (more than two-layer or two-layer) in single-phase coating is formed.Preferred further, in yttrium silicate laminated coating, preferably stacking order is, from being close to the innermost layer in mullite middle layer to outermost layer, Y
2si
2o
7content reduce gradually, Y
2siO
5content raise gradually.
In above-mentioned composite material surface coating system, preferably, described SiC undercoat thickness is 20 μm ~ 60 μm.
In above-mentioned composite material surface coating system, preferably, the thickness in described mullite middle layer is 30 μm ~ 80 μm.
In above-mentioned composite material surface coating system, preferably, the thickness of described iridium silicate coating layer is 20 μm ~ 100 μm.Preferred further, when described iridium silicate coating layer is yttrium silicate single-layer coating, thickness is 30 μm ~ 100 μm; When described iridium silicate coating layer is yttrium silicate laminated coating, the thickness of every layer is 20 μm ~ 50 μm.
As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned composite material surface coating system, comprises the following steps:
The mud raw material of S1, preparation SiC coating: by SiC powder, silicone resin in organic solvent dispersing and mixing obtain SiC mud raw material;
The mud raw material of S2, preparation mullite coating: by Al
2o
3powder, silicone resin in organic solvent dispersing and mixing obtain Al
2o
3mud raw material;
The mud raw material of S3, preparation iridium silicate coating layer: by Y
2o
3powder, silicone resin in organic solvent dispersing and mixing obtain Y
2o
3mud raw material;
S4, preparation SiC coating: FRCMC substrate is immersed in the mud raw material of step S1 preparation, by dip-coating method in composite substrate surface preparation SiC coating, obtain the FRCMC substrate with SiC coating;
S5, prepare mullite coating: immerse in the mud raw material of step S2 preparation by the FRCMC substrate with SiC coating, prepare mullite coating by dip-coating method at SiC coatingsurface, obtain the FRCMC substrate with SiC coating and mullite coating;
S6, prepare iridium silicate coating layer: immerse in the mud raw material of step S3 preparation by the FRCMC substrate with SiC coating and mullite coating, prepare iridium silicate coating layer by dip-coating method on mullite coating surface, complete the preparation of FRCMC lacquer systems.
Above-mentioned preparation method, preferably, described preparation method is further comprising the steps of: the working method of repeating step S6, changes Y at every turn
2o
3silicon yttrium atom ratio in mud raw material, on the mullite coating that step S5 is obtained, prepares silicon yttrium atom successively than the yttrium silicate single-layer coating diminished gradually from the bottom to top, forms yttrium silicate laminated coating.
Above-mentioned preparation method, preferably, in described step S1, the volume ratio of described SiC powder and described silicone resin is 1: 1 ~ 1: 9.Preferred further, the present invention adopts density to be 1.3g/cm
3silicone resin, corresponding SiC powder and the quality of silicone resin are 0.27: 1 ~ 2.46: 1 than scope.
Above-mentioned preparation method, preferably, in described step S2, described Al
2o
3the mass ratio of powder and described silicone resin is 1.4: 1 ~ 2.3: 1.Al
2o
3the mass ratio of powder and silicone resin is according to Al in mullite coating
2o
3/ SiO
2mass ratio is the requirement of 2.13: 1 ~ 3.55: 1, is converted into SiO in conjunction with silicone resin
2transformation efficiency determine; The present invention's silicone resin used is converted into SiO
2transformation efficiency be about 65%, preferred Al
2o
3the quality of powder and silicone resin is 1.4: 1 ~ 2.3: 1 than scope.
Above-mentioned preparation method, preferably, in described step S3, described Y
2o
3the mass ratio of powder and described silicone resin is 1.2: 1 ~ 2.5: 1.Y
2o
3the mass ratio of powder and silicone resin is according to Y
2siO
5, Y
2si
2o
7y corresponding to chemical constitution
2o
3/ SiO
2quality, than scope (namely 1.88: 1 ~ 3.77: 1), is converted into SiO in conjunction with silicone resin
2transformation efficiency determine; The present invention's silicone resin used is converted into SiO
2transformation efficiency be about 65%, preferred Y
2o
3the quality of powder and silicone resin is 1.2: 1 ~ 2.5: 1 than scope.
In above-mentioned preparation method, preferably, the median size of the SiC powder in described step S1 is 0.1 μm ~ 10 μm.
In above-mentioned preparation method, preferably, the Al in described step S2
2o
3the median size of powder is 0.1 μm ~ 10 μm.
In above-mentioned preparation method, preferably, the Y in described step S3
2o
3the median size of powder is 2 μm ~ 10 μm.
In above-mentioned preparation method, preferably, in described step S1, S2, S3, the preferred structure formation of described silicone resin is: with the linear backbone of-Si-O-Si-unit composition, side chain is phenyl and methyl, and end group is-OH group, and it changes into SiO after 800 DEG C of cracking in atmosphere
2productive rate more than 60%.Preferred further, described organic solvent is ethanol (more preferably dehydrated alcohol); When preparing mud raw material, with ethanol (preferred dehydrated alcohol) for medium carries out Ball milling mixing.
In above-mentioned preparation method, preferably, the detailed process that SiC coating described in described step S4 is prepared by dip-coating method is:
S4-1: FRCMC substrate to be impregnated in SiC mud raw material and to keep 2min ~ 20min, pulling film forming places 30min ~ 60min after taking out, and then, carries out crosslinked 2h ~ 4h in atmosphere at 200 DEG C ~ 300 DEG C;
The dipping of S4-2: repeating step S4-1, pulling film forming, placement, cross-linking process 2 ~ 6 times, then carry out cracking 1h ~ 3h in inert atmosphere or vacuum environment at 800 DEG C ~ 1200 DEG C;
The process of S4-3: repeating step S4-2 2 ~ 6 times, then carries out cracking 1h ~ 4h in inert atmosphere or vacuum environment at 1400 DEG C ~ 1600 DEG C;
S4-4: be a circulation with step S4-1, S4-2 and S4-3, repeats this working cycle 2 ~ 4 times, makes SiC coating reach preset thickness and densification, obtain the composite substrate with SiC coating.
In above-mentioned preparation method, preferably, in described step S4-1, the speed of described lift is 5cm/min ~ 20cm/min.
In above-mentioned preparation method, preferably, in described step S4-2, temperature rise rate during described cracking is 2 DEG C/min ~ 10 DEG C/min.
In above-mentioned preparation method, preferably, in described step S4-3, temperature rise rate during described cracking is 5 DEG C/min ~ 15 DEG C/min.
In above-mentioned preparation method, preferably, the detailed process that mullite coating described in described step S5 is prepared by dip-coating method is:
S5-1: the composite substrate with SiC coating is impregnated into Al
2o
3keep 2min ~ 20min in mud raw material, pulling film forming places 30min ~ 60min after taking out, and then at 200 DEG C ~ 300 DEG C, carries out crosslinked 2h ~ 4h in atmosphere;
The dipping of S5-2: repeating step S5-1, pulling film forming, placement, cross-linking process 2 ~ 6 times, then carry out cracking 1h ~ 2h in atmosphere, make silicone resin be converted into SiO at 700 DEG C ~ 900 DEG C
2, then in inert atmosphere or vacuum with 1100 DEG C ~ 1300 DEG C thermal treatment 1h ~ 3h;
The process of S5-3: repeating step S5-2 2 ~ 6 times, then calcines 1h ~ 3h with 1400 DEG C ~ 1600 DEG C, obtains the composite substrate with SiC coating and mullite coating in inert atmosphere or vacuum.
In above-mentioned preparation method, preferably, in described step S5-1, the speed of described lift is 5cm/min ~ 20cm/min.
In above-mentioned preparation method, preferably, in described step S5-2, temperature rise rate during described cracking is 5 DEG C/min ~ 15 DEG C/min, and temperature rise rate during described thermal treatment is 5 DEG C/min ~ 15 DEG C/min.
In above-mentioned preparation method, preferably, in described step S5-3, temperature rise rate during described calcining is 5 DEG C/min ~ 15 DEG C/min.
In above-mentioned preparation method, preferably, the detailed process preparing yttrium silicate external coating (EC) single-layer coating by dip-coating method described in described step S6 is:
S6-1: the composite substrate with SiC coating and mullite coating is impregnated into Y
2o
3keep 2min ~ 20min in mud raw material, pulling film forming places 30min ~ 60min after taking out, and then at 200 DEG C ~ 300 DEG C, carries out crosslinked 2h ~ 4h in atmosphere;
The dipping of S6-2: repeating step S6-1, pulling film forming, placement, cross-linking process 2 ~ 6 times, then carry out cracking 1h ~ 2h in atmosphere, make silicone resin be converted into SiO at 700 DEG C ~ 900 DEG C
2, then in inert atmosphere or vacuum, at 1100 DEG C ~ 1300 DEG C, heat-treat 1h ~ 3h;
The process of S6-3: repeating step S6-2 2 ~ 6 times, then carries out calcining 1h ~ 3h in inert atmosphere or vacuum at 1400 DEG C ~ 1600 DEG C, completes the preparation of composite material surface SiC, mullite and iridium silicate coating layer system.
In above-mentioned preparation method, preferably, in described step S6-1, the speed of described lift is 5cm/min ~ 20cm/min.
In above-mentioned preparation method, preferably, in described step S6-2, temperature rise rate during described cracking is 5 DEG C/min ~ 15 DEG C/min; Temperature rise rate during described thermal treatment is 5 DEG C/min ~ 15 DEG C/min.
In above-mentioned preparation method, preferably, in described step S6-3, temperature rise rate during described calcining is 5 DEG C/min ~ 15 DEG C/min.
In above-mentioned preparation method, preferably, described when preparing yttrium silicate external coating (EC) laminated coating by dip-coating method, the detailed process of each individual layer and the same single-layer coating of design parameter, just Y used
2o
3y in mud
2o
3different from the mass ratio of silicone resin.
In preparation method of the present invention, preferably, by composite substrate, with the internally coated composite substrate of SiC, composite substrate with SiC undercoat and mullite middle layer, SiC mud, Al is immersed respectively
2o
3mud, Y
2o
3time in mud, for ensureing stability and the homogeneity of mud, mud is stirred and sonic oscillation process, to avoid SiC, Al before using
2o
3, Y
2o
3the sedimentation of powder.
The performance perameter of composite material surface refractory oxidation resistant coating system of the present invention, can determine by the following method: by the oxidation 0.5h ~ 10h in 1400 DEG C ~ 1600 DEG C air ambients (retort furnace) of the matrix material with lacquer systems, then measure weight rate, the strength retention ratio before and after oxidation.
Compared with prior art, the invention has the advantages that:
(1) the composite material surface coating system such as C/SiC, SiC/SiC, C/C of the present invention comprises SiC undercoat, mullite middle layer and yttrium silicate external coating (EC).Compared to mullite, the physics between SiC and composite substrate, chemical compatibility are more better, and not only bonding strength is high, and can at high temperature effectively hinder carbon in matrix material to external diffusion.Therefore, compared to patent (the horse pine that application number is 201410701284.7, bang is hidden, Cai Lihui. C/SiC composite material surface coating system and preparation method thereof) in mullite/yttrium silicate two layer coating system, SiC/ mullite/yttrium silicate of the present invention three layers of coating system one to improve the bonding strength between coating and matrix material, and two is can SiO more than needed in anti-blocking and mullite
2carbothermic reduction reaction.
(2) mullite middle layer and the internally coated thermal expansivity of SiC about the same, chemical compatibility is also fine, there is good antioxidant property and itself can not be oxidized again, thus in avoiding traditional method (SiC undercoat/yttrium silicate external coating (EC)), the voloxidation of SiC undercoat causes the problem that yttrium silicate external coating (EC) ftractures or comes off.Meanwhile, because mullite and yttrium silicate are all oxide compounds, in composition, SiO is had
2, this is conducive to forming strong combination between the two, thus improves the anti-oxidant and resistance to erosion ability of coating.In addition, in the present invention, the chemical constitution in mullite middle layer meets stoichiometric ratio, SiO not more than needed
2, thus reduce carbon and SiO further
2between there is the possibility of carbothermic reduction reaction.
(3) in preparation method of the present invention, take liquid mud as the dip-coating method of raw material, there is the advantage that preparation process is simple and easy to control, low for equipment requirements, both large size, complex shaped components had been applicable to, also the component with inner-cavity structure is applicable to, when mass production, there is good consistence and reliability, thus there is on engineer applied good universality.
(4) in preparation method of the present invention, all silicone resin is contained in all mud, its adhesivity, good film-forming property, also be main raw material prepared by coating simultaneously, not only be easy in composite material surface film forming, be conducive to improving bonding strength, and avoid outer adding additives, the clean disadvantageous effect brought to coating fabrication & properties of membrane-forming agent needs eliminating.
(5) in preparation method of the present invention, the mud be made into SiC powder and silicone resin is raw material, SiC coating is prepared by dip-coating method, compared to existing chemical Vapor deposition process, entrapping method, except the advantage described in (3), one is that preparation temperature (1400 DEG C ~ 1600 DEG C) is starkly lower than entrapping method (>1800 DEG C), avoids the damage of high temperature to composite substrate; Two is realize the densification of SiC coating by several times circulation, avoids the problem that coating stress that disposable densification brings is bigger than normal.
(6) in preparation method of the present invention, respectively with Al
2o
3powder and silicone resin, Y
2o
3the mud that powder and silicone resin are made into is raw material, prepares mullite, iridium silicate coating layer by dip-coating method.The SiO that silicone resin changes into
2be amorphous state, reactive behavior is high, has good viscous flow characteristics at 1100 DEG C ~ 1300 DEG C, can impel low temperature (under mullite, the yttrium silicate synthesis temperature) densification of coating, also can with Al
2o
3, Y
2o
3under lesser temps (1400 DEG C ~ 1600 DEG C), reaction generates mullite, yttrium silicate, thus avoids the disadvantageous effect that pyroprocessing is brought matrix material.Compared with the sol-gel method conventional with preparing oxide coating, low-temperature growth and the advantage described in (3) are that two kinds of methods are all owned together, but method of the present invention also has the advantage described in (4), namely in film-forming properties, preparation efficiency, sticking power etc., be better than sol-gel method.
Accompanying drawing explanation
Fig. 1 is the structural representation of the composite material surface coating system of the embodiment of the present invention 1.
Fig. 2 be composite material surface coating system in the embodiment of the present invention respectively at 1400 DEG C, 1500 DEG C, 1600 DEG C cracking generate the XRD figure spectrum of SiC.
Fig. 3 is that the composite material surface coating system in the embodiment of the present invention calcines the XRD figure spectrum generating mullite respectively at 1400 DEG C, 1500 DEG C, 1600 DEG C.
Fig. 4 is the composite material surface coating system calcining generation yttrium silicate (Y at 1400 DEG C, 1500 DEG C, 1600 DEG C respectively in the embodiment of the present invention
2si
2o
7) XRD figure spectrum.
Fig. 5 is the composite material surface coating system calcining generation yttrium silicate (70wt%Y at 1400 DEG C, 1500 DEG C, 1600 DEG C respectively in the embodiment of the present invention
2si
2o
7+ 30wt%Y
2siO
5) XRD figure spectrum.
Fig. 6 is the composite material surface coating system calcining generation yttrium silicate (Y at 1400 DEG C, 1500 DEG C, 1600 DEG C respectively in the embodiment of the present invention
2siO
5) XRD figure spectrum.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
The material adopted in following examples and instrument are commercially available.
embodiment 1:
A kind of fire-resistant oxidation resistant lacquer systems of the present invention, as shown in Figure 1.This lacquer systems is located at C/C composite substrate surface, comprise lay successively from the bottom to top SiC undercoat, mullite middle layer and yttrium silicate external coating (EC).
In the present embodiment, the thickness of SiC coating is 20 μm; In the chemical constitution of mullite coating, Al
2o
3with SiO
2mass ratio is 2.13: 1, and the thickness of mullite coating is 60 μm; Iridium silicate coating layer is Y
2si
2o
7single-phase coating, thickness in monolayer is 80 μm.
A preparation method for the C/C composite material surface coating system of above-mentioned the present embodiment, comprises the following steps:
The mud raw material of S1, preparation SiC coating: the silicone resin density adopted by SiC powder/silicone resin volume ratio 1: 3(the present embodiment is 1.3g/cm
3, the density of SiC is 3.2g/cm
3; Corresponding SiC powder and the mass ratio of silicone resin are 0.82: 1), by SiC powder (median size 0.4 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain SiC mud, for the preparation of SiC undercoat.
The mud raw material of S2, preparation mullite coating: by Al
2o
3al in the corresponding mullite coating of powder/silicone resin mass ratio 1.4: 1(
2o
3/ SiO
2mass ratio is 2.13: 1), by Al
2o
3powder (median size 1 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Al
2o
3mud, for the preparation of mullite middle layer.
The mud raw material of S3, preparation iridium silicate coating layer: by Y
2o
3the corresponding Y of powder/silicone resin mass ratio 1.2: 1(
2si
2o
7phase), by Y
2o
3powder (median size 3 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Y
2o
3mud, for the preparation of Y
2si
2o
7external coating (EC).
S4, preparation SiC undercoat:
S4-1, C/C composite substrate be immersed in SiC mud and keep 5min, after taking out with the speed pulling film forming of 15cm/min, placing 60min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S4-2, repeating step S4-1, pulling film forming, placement, cross-linking process 2 times, then cracking at 1200 DEG C in an inert atmosphere, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h.
(process of S4-2 is by the dipping of the C/C composite substrate repeating step S4-1 after cracking in step S4-2, pulling film forming, placement, cross-linking process 2 times for the process of S4-3, repeating step S4-2, then cracking at 1200 DEG C in an inert atmosphere, during cracking, temperature rise rate is 10 DEG C/min, soaking time is 1h) 2 times, then cracking at 1600 DEG C in an inert atmosphere, during cracking, temperature rise rate is 15 DEG C/min, and soaking time is 1h.
S4-4, be a circulation with step S4-1, S4-2 and S4-3, repeat this working cycle 2 times, prepare the fine and close SiC coating of thickness 20 μm, obtain with the internally coated composite substrate of SiC.
S5, prepare mullite middle layer:
S5-1, Al will be immersed in the internally coated composite substrate of SiC
2o
3keep 10min in mud, after taking out with the speed pulling film forming of 10cm/min, place 30min, then crosslinked 4h at 200 DEG C in atmosphere.
The dipping of S5-2, repeating step S5-1, pulling film forming, placement, cross-linking process 2 times, then cracking at 800 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h, then heat-treats at 1200 DEG C in an inert atmosphere, and during thermal treatment, temperature rise rate is 15 DEG C/min, and soaking time is 2h.
(process of S5-2 is by the dipping with SiC internally coated composite substrate repeating step S5-1 after cracking in step S5-2, pulling film forming, placement, cross-linking process 2 times for the process of S5-3, repeating step S5-2, then cracking at 800 DEG C in atmosphere, makes silicone resin be converted into SiO
2during cracking, temperature rise rate is 10 DEG C/min, soaking time is 1h, then heat-treats at 1200 DEG C in an inert atmosphere, and during thermal treatment, temperature rise rate is 15 DEG C/min, soaking time is 2h) 4 times, finally calcine at 1400 DEG C in an inert atmosphere, during calcining, temperature rise rate is 15 DEG C/min, and soaking time is 3h, prepare the fine and close mullite coating of thickness 60 μm, obtain the composite substrate with SiC undercoat and mullite middle layer.
S6, prepare iridium silicate coating layer:
S6-1, the composite substrate with SiC undercoat and mullite middle layer is immersed in Y
2o
3keep 20min in mud, after taking out with the speed pulling film forming of 5cm/min, place 45min, then crosslinked 2h at 300 DEG C in atmosphere.
The dipping of S6-2, repeating step S6-1, pulling film forming, placement, cross-linking process 4 times, then cracking at 900 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 15 DEG C/min, and soaking time is 1h, then thermal treatment at 1100 DEG C in a vacuum, and temperature rise rate during thermal treatment is 10 DEG C/min, and soaking time is 3h.
The process of S6-3, repeating step S6-2 (process of S6-2 by after cracking in step S6-2 with SiC undercoat and mullite middle layer the dipping of composite substrate repeating step S6-1, pulling film forming, placement, cross-linking process 4 times, then cracking at 900 DEG C in atmosphere, makes silicone resin be converted into SiO
2during cracking, temperature rise rate is 15 DEG C/min, soaking time is 1h, then thermal treatment at 1100 DEG C in a vacuum, temperature rise rate during thermal treatment is 10 DEG C/min, and soaking time is 3h) 5 times, finally calcine at 1500 DEG C in a vacuum, temperature rise rate during calcining is 15 DEG C/min, and soaking time is 1h, prepares the fine and close Y of thickness 80 μm
2si
2o
7coating, completes the preparation of composite material surface SiC/ mullite/iridium silicate coating layer system.
In this composite material surface coating system at 1600 DEG C cracking generate SiC coating, at 1400 DEG C calcining generate mullite coating, at 1500 DEG C calcining generate yttrium silicate (Y
2si
2o
7) coating XRD figure spectrum respectively see Fig. 2, Fig. 3 and Fig. 4.
Can find in fig. 2, by SiC coating prepared by " silicone resin+SiC powder " mud raw material, after 1400 DEG C of calcinings, there is the diffraction peak of typical b-SiC phase 36 °, 60 °, 72 ° three positions, illustrated that the phase composite of coating is the good b-SiC phase of crystallization degree.Along with the rising of calcining temperature, can see, the diffraction peak intensity of b-SiC phase raises gradually, have also appeared two new diffraction peaks of 42 °, 76 ° positions when 1600 DEG C, shows that the crystallization degree of b-SiC phase is also improving constantly.Can see in figure 3, by " silicone resin+Al
2o
3powder " mullite coating prepared of mud raw material, the phase composite at 1400 DEG C, 1500 DEG C, 1600 DEG C after calcining be all the mullite phase that crystallization degree is very high, not have the SiO that appearance is had more than needed
2or Al
2o
3phase, and along with temperature rising, the diffraction peak of mullite phase does not significantly change, this is because the amorphous Si O that silicone resin changes into
2there is very high activity, at 1400 DEG C just and Al
2o
3reaction generates the very high mullite phase of crystallization degree.Same reason, can see in the diagram, by " silicone resin+Y
2o
3powder " Y for preparing of mud raw material
2si
2o
7coating, the phase composite at 1400 DEG C, 1500 DEG C, 1600 DEG C after calcining is all the Y that crystallization degree is very high
2si
2o
7phase, does not have to occur SiO more than needed
2or Y
2o
3phase, and Y
2si
2o
7the diffraction peak position of phase and intensity also significantly do not change along with calcining temperature raises.
By the matrix material of the lacquer systems with the present embodiment, in 1500 DEG C of air, (retort furnace, lower same) is oxidized 0.5h, and rate of weight loss is 0.56%, and the strength retention ratio of matrix material is 102.4%, and namely after oxidation, intensity does not change.Show: the lacquer systems of embodiment 1 relies on the characteristics such as it is high temperature resistant, anti-oxidant, high-compactness, and and matrix material between good physical chemistry consistency, good oxidation protection effect is served to matrix material.
embodiment 2:
A kind of fire-resistant oxidation resistant lacquer systems of the present invention, as shown in Figure 1.This lacquer systems is located at SiC/SiC composite substrate surface, comprises SiC layer, mullite coating and the iridium silicate coating layer laid successively from the bottom to top.
In the present embodiment, the thickness of SiC coating is 50 μm; In the chemical constitution of mullite coating, Al
2o
3with SiO
2mass ratio is 3.55: 1, and the thickness of mullite coating is 50 μm; Iridium silicate coating layer is Y
2siO
5single-phase coating, thickness in monolayer is 50 μm.
A preparation method for the composite material surface coating system of above-mentioned the present embodiment, comprises the following steps:
The mud raw material of S1, preparation SiC coating: the silicone resin density adopted by SiC powder/silicone resin volume ratio 1: 1.5(the present embodiment is 1.3g/cm
3, the density of SiC is 3.2g/cm
3; Corresponding SiC powder and the mass ratio of silicone resin are 1.64: 1), by SiC powder (median size 2 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain SiC mud, for the preparation of SiC undercoat.
The mud raw material of S2, preparation mullite coating: by Al
2o
3al in the corresponding mullite coating of powder/silicone resin mass ratio 2.3: 1(
2o
3/ SiO
2mass ratio is 3.55: 1), by Al
2o
3powder (median size 10 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Al
2o
3mud, for the preparation of mullite middle layer.
The mud raw material of S3, preparation iridium silicate coating layer: by Y
2o
3the corresponding Y of powder/silicone resin mass ratio 2.5: 1(
2siO
5phase), by Y
2o
3powder (median size 10 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Y
2o
3mud, for the preparation of Y
2siO
5external coating (EC).
S4, preparation SiC undercoat:
S4-1, SiC/SiC composite substrate be immersed in SiC mud and keep 10min, after taking out with the speed pulling film forming of 5cm/min, placing 40min, then crosslinked 4h at 200 DEG C in atmosphere.
The dipping of S4-2, repeating step S4-1, pulling film forming, placement, cross-linking process 3 times, then cracking at 1000 DEG C in an inert atmosphere, during cracking, temperature rise rate is 5 DEG C/min, and soaking time is 3h.
The process of S4-3, repeating step S4-2 2 times, then cracking at 1400 DEG C in a vacuum, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 2h.
S4-4, be a circulation with step S4-1, S4-2 and S4-3, repeat this working cycle 3 times, prepare the fine and close SiC coating of thickness 50 μm, obtain with the internally coated composite substrate of SiC.
S5, prepare mullite middle layer:
S5-1, Al will be immersed in the internally coated composite substrate of SiC
2o
3keep 20min in mud, after taking out with the speed pulling film forming of 20cm/min, place 50min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S5-2, repeating step S5-1, pulling film forming, placement, cross-linking process 3 times, then cracking at 700 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 5 DEG C/min, and soaking time is 2h, then heat-treats at 1300 DEG C in an inert atmosphere, and during thermal treatment, temperature rise rate is 15 DEG C/min, and soaking time is 1h.
The process of S5-3, repeating step S5-2 2 times, finally calcine at 1600 DEG C in an inert atmosphere, during calcining, temperature rise rate is 15 DEG C/min, soaking time is 1h, prepare the fine and close mullite coating of thickness 50 μm, obtain the composite substrate with SiC undercoat and mullite middle layer.
S6, prepare iridium silicate coating layer:
S6-1, the composite substrate with SiC undercoat and mullite middle layer is immersed in Y
2o
3keep 2min in mud, after taking out with the speed pulling film forming of 5cm/min, place 30min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S6-2, repeating step S6-1, pulling film forming, placement, cross-linking process 6 times, then cracking at 800 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h, then thermal treatment at 1100 DEG C in a vacuum, and temperature rise rate during thermal treatment is 5 DEG C/min, and soaking time is 3h.
The process of S6-3, repeating step S6-2 4 times, finally calcines in a vacuum at 1500 DEG C, and temperature rise rate during calcining is 15 DEG C/min, and soaking time is 1h, prepares the fine and close Y of thickness 50 μm
2siO
5coating, completes the preparation of composite material surface SiC/ mullite/iridium silicate coating layer system.
In this composite material surface coating system at 1400 DEG C cracking generate SiC coating, at 1600 DEG C calcining generate mullite coating, at 1500 DEG C calcining generate yttrium silicate (Y
2siO
5) coating XRD figure spectrum respectively see Fig. 2, Fig. 3 and Fig. 6.
Can find in fig. 2, by SiC coating prepared by " silicone resin+SiC powder " mud raw material, after 1400 DEG C of calcinings, there is the diffraction peak of typical b-SiC phase 36 °, 60 °, 72 ° three positions, illustrated that the phase composite of coating is the good b-SiC phase of crystallization degree.Along with the rising of calcining temperature, can see, the diffraction peak intensity of b-SiC phase raises gradually, have also appeared two new diffraction peaks of 42 °, 76 ° positions when 1600 DEG C, shows that the crystallization degree of b-SiC phase is also improving constantly.Can see in figure 3, by " silicone resin+Al
2o
3powder " mullite coating prepared of mud raw material, the phase composite at 1400 DEG C, 1500 DEG C, 1600 DEG C after calcining be all the mullite phase that crystallization degree is very high, not have the SiO that appearance is had more than needed
2or Al
2o
3phase, and along with temperature rising, the diffraction peak of mullite phase does not significantly change, this is because the amorphous Si O that silicone resin changes into
2there is very high activity, at 1400 DEG C just and Al
2o
3reaction generates the very high mullite phase of crystallization degree.Same reason, can see in figure 6, by " silicone resin+Y
2o
3powder " Y for preparing of mud raw material
2siO
5coating, the phase composite at 1400 DEG C, 1500 DEG C, 1600 DEG C after calcining is all the Y that crystallization degree is very high
2siO
5phase, and Y
2siO
5the diffraction peak position of phase and intensity also significantly do not change along with calcining temperature raises, due to Y in preparation in mud
2o
3powder is slightly excessive, causes occurring a small amount of Y in figure
2o
3the diffraction peak of phase.
The matrix material of the lacquer systems with the present embodiment is oxidized 3h in 1400 DEG C of air, and rate of weight loss is 0.95%, and the strength retention ratio of matrix material is 99.3%, and namely after oxidation, intensity does not change.Show: the lacquer systems of embodiment 2 relies on the characteristics such as it is high temperature resistant, anti-oxidant, high-compactness, and and matrix material between good physical chemistry consistency, good oxidation protection effect is served to matrix material.
embodiment 3:
A kind of fire-resistant oxidation resistant lacquer systems of the present invention, as shown in Figure 1.This lacquer systems is located at C/SiC composite substrate surface, comprise lay successively from the bottom to top SiC undercoat, mullite middle layer and yttrium silicate external coating (EC).
In the present embodiment, the thickness of SiC coating is 40 μm; In the chemical constitution of mullite coating, Al
2o
3with SiO
2mass ratio is 2.55: 1, and the thickness of mullite coating is 50 μm; Iridium silicate coating layer is 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5mixed phase single-layer coating, thickness in monolayer is 100 μm.
A preparation method for the composite material surface coating system of above-mentioned the present embodiment, comprises the following steps:
The mud raw material of S1, preparation SiC coating: the silicone resin density adopted by SiC powder/silicone resin volume ratio 1: 9(the present embodiment is 1.3g/cm
3, the density of SiC is 3.2g/cm
3; Corresponding SiC powder and the mass ratio of silicone resin are 0.27: 1), by SiC powder (median size 0.1 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain SiC mud, for the preparation of SiC undercoat.
The mud raw material of S2, preparation mullite coating: by Al
2o
3al in the corresponding mullite coating of powder/silicone resin mass ratio 1.66: 1(
2o
3/ SiO
2mass ratio is 2.55: 1), by Al
2o
3powder (median size 2 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Al
2o
3mud, for the preparation of mullite middle layer.
The mud raw material of S3, preparation iridium silicate coating layer: by Y
2o
3the corresponding 70wt%Y of powder/silicone resin mass ratio 1.48: 1(
2si
2o
7+ 30wt%Y
2siO
5phase), by Y
2o
3powder (median size 2 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Y
2o
3mud, for the preparation of 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5external coating (EC).
S4, preparation SiC undercoat:
S4-1, C/SiC composite substrate be immersed in SiC mud and keep 20min, after taking out with the speed pulling film forming of 5cm/min, placing 60min, then crosslinked 4h at 200 DEG C in atmosphere.
The dipping of S4-2, repeating step S4-1, pulling film forming, placement, cross-linking process 6 times, then cracking at 800 DEG C in an inert atmosphere, during cracking, temperature rise rate is 2 DEG C/min, and soaking time is 3h.
The process of S4-3, repeating step S4-2 3 times, then cracking at 1500 DEG C in an inert atmosphere, during cracking, temperature rise rate is 15 DEG C/min, and soaking time is 4h.
S4-4, be a circulation with step S4-1, S4-2 and S4-3, repeat this working cycle 3 times, prepare the fine and close SiC coating of thickness 40 μm, obtain with the internally coated composite substrate of SiC.
S5, prepare mullite middle layer:
S5-1, Al will be immersed in the internally coated composite substrate of SiC
2o
3keep 10min in mud, after taking out with the speed pulling film forming of 20cm/min, place 30min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S5-2, repeating step S5-1, pulling film forming, placement, cross-linking process 3 times, then cracking at 800 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h, then heat-treats at 1200 DEG C in an inert atmosphere, and during thermal treatment, temperature rise rate is 15 DEG C/min, and soaking time is 2h.
The process of S5-3, repeating step S5-2 4 times, finally calcine at 1500 DEG C in a vacuum, during calcining, temperature rise rate is 15 DEG C/min, and soaking time is 3h, prepare the fine and close mullite coating of thickness 50 μm, obtain the composite substrate with SiC undercoat and mullite middle layer.
S6, prepare iridium silicate coating layer:
S6-1, the composite substrate with SiC undercoat and mullite middle layer is immersed in Y
2o
3keep 20min in mud, after taking out with the speed pulling film forming of 5cm/min, place 60min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S6-2, repeating step S6-1, pulling film forming, placement, cross-linking process 6 times, then cracking at 800 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h, then thermal treatment at 1100 DEG C in a vacuum, and temperature rise rate during thermal treatment is 5 DEG C/min, and soaking time is 3h.
The process of S6-3, repeating step S6-2 6 times, finally calcines in an inert atmosphere at 1600 DEG C, and temperature rise rate during calcining is 15 DEG C/min, and soaking time is 1h, prepares the fine and close 70wt%Y of thickness 100 μm
2si
2o
7+ 30wt%Y
2siO
5coating, completes the preparation of composite material surface SiC/ mullite/iridium silicate coating layer system.
In this composite material surface coating system at 1500 DEG C cracking generate SiC coating, at 1500 DEG C calcining generate mullite coating, at 1600 DEG C calcining generate yttrium silicate (70wt%Y
2si
2o
7+ 30wt%Y
2siO
5) coating XRD figure spectrum respectively see Fig. 2, Fig. 3 and Fig. 5.
Can find in fig. 2, by SiC coating prepared by " silicone resin+SiC powder " mud raw material, after 1400 DEG C of calcinings, there is the diffraction peak of typical b-SiC phase 36 °, 60 °, 72 ° three positions, illustrated that the phase composite of coating is the good b-SiC phase of crystallization degree.Along with the rising of calcining temperature, can see, the diffraction peak intensity of b-SiC phase raises gradually, have also appeared two new diffraction peaks of 42 °, 76 ° positions when 1600 DEG C, shows that the crystallization degree of b-SiC phase is also improving constantly.Can see in figure 3, by " silicone resin+Al
2o
3powder " mullite coating prepared of mud raw material, the phase composite at 1400 DEG C, 1500 DEG C, 1600 DEG C after calcining be all the mullite phase that crystallization degree is very high, not have the SiO that appearance is had more than needed
2or Al
2o
3phase, and along with temperature rising, the diffraction peak of mullite phase does not significantly change, this is because the amorphous Si O that silicone resin changes into
2there is very high activity, at 1400 DEG C just and Al
2o
3reaction generates the very high mullite phase of crystallization degree.Same reason, can see in Figure 5, by " silicone resin+Y
2o
3powder " 70wt%Y for preparing of mud raw material
2si
2o
7+ 30wt%Y
2siO
5coating, the phase composite at 1400 DEG C, 1500 DEG C, 1600 DEG C after calcining is all the 70wt%Y that crystallization degree is very high
2si
2o
7+ 30wt%Y
2siO
5phase, and 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5the diffraction peak position of phase and intensity also significantly do not change along with calcining temperature raises.
The matrix material of the lacquer systems with the present embodiment is oxidized 10h in 1600 DEG C of air, and rate of weight loss is 1.92%, and the strength retention ratio of matrix material is 98%, and namely after oxidation, intensity does not change substantially.Show: the lacquer systems of embodiment 3 relies on the characteristics such as it is high temperature resistant, anti-oxidant, high-compactness, and and matrix material between good physical chemistry consistency, good oxidation protection effect is served to matrix material.
embodiment 4:
A kind of fire-resistant oxidation resistant lacquer systems of the present invention, as shown in Figure 1.This lacquer systems is located at C/SiC composite substrate surface, comprise lay successively from the bottom to top SiC undercoat, mullite middle layer and yttrium silicate external coating (EC).
In the present embodiment, the thickness of SiC coating is 60 μm; In the chemical constitution of mullite coating, Al
2o
3with SiO
2mass ratio is 2.13: 1, and the thickness of mullite coating is 80 μm; Iridium silicate coating layer is two layers of coatings, is Y from inside to outside successively
2si
2o
7phase individual layer, 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5mixed phase individual layer, the thickness of two individual layers is all 50 μm.
A preparation method for the composite material surface coating system of above-mentioned the present embodiment, comprises the following steps:
The mud raw material of S1, preparation SiC coating: the silicone resin density adopted by SiC powder/silicone resin volume ratio 1: 1(the present embodiment is 1.3g/cm
3, the density of SiC is 3.2g/cm
3; Corresponding SiC powder and the mass ratio of silicone resin are 2.46: 1), by SiC powder (median size 10 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain SiC mud, for the preparation of SiC undercoat.
The mud raw material of S2, preparation mullite coating: by Al
2o
3al in the corresponding mullite coating of powder/silicone resin mass ratio 1.4: 1(
2o
3/ SiO
2mass ratio is 2.13: 1), by Al
2o
3powder (median size 0.1 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Al
2o
3mud, for the preparation of mullite middle layer.
The mud raw material of S3, preparation iridium silicate coating layer: by Y
2o
3the corresponding Y of powder/silicone resin mass ratio 1.2: 1(
2si
2o
7phase), by Y
2o
3powder (median size 3 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Y
2o
3mud, for the preparation of Y
2si
2o
7individual layer.By Y
2o
3the corresponding 70wt%Y of powder/silicone resin mass ratio 1.48: 1(
2si
2o
7+ 30wt%Y
2siO
5phase), by Y
2o
3powder (median size 3 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Y
2o
3mud, for the preparation of 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5individual layer.
S4, preparation SiC undercoat:
S4-1, C/SiC composite substrate be immersed in SiC mud and keep 2min, after taking out with the speed pulling film forming of 15cm/min, placing 50min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S4-2, repeating step S4-1, pulling film forming, placement, cross-linking process 2 times, then cracking at 1200 DEG C in an inert atmosphere, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h.
The process of S4-3, repeating step S4-2 6 times, then cracking at 1400 DEG C in a vacuum, during cracking, temperature rise rate is 15 DEG C/min, and soaking time is 4h.
S4-4, be a circulation with step S4-1, S4-2 and S4-3, repeat this working cycle 4 times, prepare the fine and close SiC coating of thickness 60 μm, obtain with the internally coated composite substrate of SiC.
S5, prepare mullite middle layer:
S5-1, Al will be immersed in the internally coated composite substrate of SiC
2o
3keep 5min in mud, after taking out with the speed pulling film forming of 15cm/min, place 45min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S5-2, repeating step S5-1, pulling film forming, placement, cross-linking process 6 times, then cracking at 800 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h, then heat-treats at 1100 DEG C in an inert atmosphere, and during thermal treatment, temperature rise rate is 15 DEG C/min, and soaking time is 3h.
The process of S5-3, repeating step S5-2 6 times, finally calcine at 1400 DEG C in a vacuum, during calcining, temperature rise rate is 15 DEG C/min, and soaking time is 3h, prepare the fine and close mullite coating of thickness 80 μm, obtain the composite substrate with SiC undercoat and mullite middle layer.
S6, preparation Y
2si
2o
7individual layer:
S6-1, the composite substrate with SiC undercoat and mullite middle layer to be immersed in for the preparation of Y
2si
2o
7the Y of individual layer
2o
3keep 20min in mud, after taking out with the speed pulling film forming of 5cm/min, place 60min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S6-2, repeating step S6-1, pulling film forming, placement, cross-linking process 2 times, then cracking at 800 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h, then thermal treatment at 1100 DEG C in a vacuum, and temperature rise rate during thermal treatment is 10 DEG C/min, and soaking time is 2h.
The process of S6-3, repeating step S6-2 3 times, finally calcines in an inert atmosphere at 1600 DEG C, and temperature rise rate during calcining is 15 DEG C/min, and soaking time is 1h, prepares the fine and close Y of thickness 50 μm
2si
2o
7individual layer.
S7, preparation 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5individual layer:
S7-1, will with SiC undercoat, mullite middle layer and Y
2si
2o
7the composite substrate of individual layer is immersed in for the preparation of 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5the Y of individual layer
2o
3keep 20min in mud, after taking out with the speed pulling film forming of 5cm/min, place 60min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S7-2, repeating step S7-1, pulling film forming, placement, cross-linking process 2 times, then cracking at 800 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h, then thermal treatment at 1100 DEG C in a vacuum, and temperature rise rate during thermal treatment is 10 DEG C/min, and soaking time is 2h.
The process of S7-3, repeating step S7-2 2 times, finally calcines in an inert atmosphere at 1600 DEG C, and temperature rise rate during calcining is 15 DEG C/min, and soaking time is 1h, prepares the fine and close 70wt%Y of thickness 50 μm
2si
2o
7+ 30wt%Y
2siO
5individual layer, completes the preparation of composite material surface SiC/ mullite/iridium silicate coating layer system.
In this composite material surface coating system at 1400 DEG C cracking generate SiC coating, at 1400 DEG C calcining generate mullite coating, at 1600 DEG C calcining generate Y
2si
2o
7coating, at 1600 DEG C calcining generate 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5the XRD figure spectrum of coating is respectively see Fig. 2, Fig. 3, Fig. 4 and Fig. 5.
Can find in fig. 2, by SiC coating prepared by " silicone resin+SiC powder " mud raw material, after 1400 DEG C of calcinings, there is the diffraction peak of typical b-SiC phase 36 °, 60 °, 72 ° three positions, illustrated that the phase composite of coating is the good b-SiC phase of crystallization degree.Along with the rising of calcining temperature, can see, the diffraction peak intensity of b-SiC phase raises gradually, have also appeared two new diffraction peaks of 42 °, 76 ° positions when 1600 DEG C, shows that the crystallization degree of b-SiC phase is also improving constantly.Can see in figure 3, by " silicone resin+Al
2o
3powder " mullite coating prepared of mud raw material, the phase composite at 1400 DEG C, 1500 DEG C, 1600 DEG C after calcining be all the mullite phase that crystallization degree is very high, not have the SiO that appearance is had more than needed
2or Al
2o
3phase, and along with temperature rising, the diffraction peak of mullite phase does not significantly change, this is because the amorphous Si O that silicone resin changes into
2there is very high activity, at 1400 DEG C just and Al
2o
3reaction generates the very high mullite phase of crystallization degree.Same reason, can see in Fig. 4, Fig. 5, by " silicone resin+Y
2o
3powder " Y for preparing of mud raw material
2si
2o
7coating, 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5coating, the phase composite at 1400 DEG C, 1500 DEG C, 1600 DEG C after calcining is all the Y that crystallization degree is very high
2si
2o
7phase, 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5phase, does not have to occur SiO more than needed
2or Y
2o
3phase, and Y
2si
2o
7phase, 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5the diffraction peak position of phase and intensity also significantly do not change along with calcining temperature raises.
The matrix material of the lacquer systems with the present embodiment is oxidized 10h in 1600 DEG C of air, and rate of weight loss is 0.87%, and the strength retention ratio of matrix material is 106.8%, and namely after oxidation, intensity does not decline.Show: the lacquer systems of embodiment 4 relies on the characteristics such as it is high temperature resistant, anti-oxidant, high-compactness, and and matrix material between good physical chemistry consistency, good oxidation protection effect is served to matrix material.
embodiment 5:
A kind of fire-resistant oxidation resistant lacquer systems of the present invention, as shown in Figure 1.This lacquer systems is located at C/C composite substrate surface, comprise lay successively from the bottom to top SiC undercoat, mullite middle layer and yttrium silicate external coating (EC).
In the present embodiment, the thickness of SiC coating is 50 μm; In the chemical constitution of mullite coating, Al
2o
3with SiO
2mass ratio is 2.13: 1, and the thickness of mullite coating is 30 μm; Iridium silicate coating layer is three layers of coating, to be thickness from inside to outside be successively the Y of 40 μm
2si
2o
7phase individual layer, thickness are the 70wt%Y of 30 μm
2si
2o
7+ 30wt%Y
2siO
5mixed phase individual layer, thickness are the Y of 20 μm
2siO
5phase individual layer.
A preparation method for the composite material surface coating system of above-mentioned the present embodiment, comprises the following steps:
The mud raw material of S1, preparation SiC coating: the silicone resin density adopted by SiC powder/silicone resin volume ratio 1: 4(the present embodiment is 1.3g/cm
3, the density of SiC is 3.2g/cm
3; Corresponding SiC powder and the mass ratio of silicone resin are 0.62: 1), by SiC powder (median size 1 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain SiC mud, for the preparation of SiC undercoat.
The mud raw material of S2, preparation mullite coating: by Al
2o
3al in the corresponding mullite coating of powder/silicone resin mass ratio 1.4: 1(
2o
3/ SiO
2mass ratio is 2.13: 1), by Al
2o
3powder (median size 1 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Al
2o
3mud, for the preparation of mullite middle layer.
The mud raw material of S3, preparation iridium silicate coating layer: by Y
2o
3the corresponding Y of powder/silicone resin mass ratio 1.2: 1(
2si
2o
7phase), by Y
2o
3powder (median size 3 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Y
2o
3mud, for the preparation of Y
2si
2o
7individual layer.By Y
2o
3the corresponding 70wt%Y of powder/silicone resin mass ratio 1.48: 1(
2si
2o
7+ 30wt%Y
2siO
5phase), by Y
2o
3powder (median size 3 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Y
2o
3mud, for the preparation of 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5individual layer.By Y
2o
3the corresponding Y of powder/silicone resin mass ratio 2.5: 1(
2siO
5phase), by Y
2o
3powder (median size 10 μm) and silicone resin blended, be that medium carries out Ball milling mixing with dehydrated alcohol, obtain Y
2o
3mud, for the preparation of Y
2siO
5individual layer.
S4, preparation SiC undercoat:
S4-1, C/C composite substrate be immersed in SiC mud and keep 15min, after taking out with the speed pulling film forming of 5cm/min, placing 40min, then crosslinked 2h at 300 DEG C in atmosphere.
The dipping of S4-2, repeating step S4-1, pulling film forming, placement, cross-linking process 2 times, then cracking at 1000 DEG C in an inert atmosphere, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h.
The process of S4-3, repeating step S4-2 5 times, then cracking at 1500 DEG C in a vacuum, during cracking, temperature rise rate is 15 DEG C/min, and soaking time is 2h.
S4-4, be a circulation with step S4-1, S4-2 and S4-3, repeat this working cycle 4 times, prepare the fine and close SiC coating of thickness 50 μm, obtain with the internally coated composite substrate of SiC.
S5, prepare mullite middle layer:
S5-1, Al will be immersed in the internally coated composite substrate of SiC
2o
3keep 10min in mud, after taking out with the speed pulling film forming of 10cm/min, place 30min, then crosslinked 4h at 200 DEG C in atmosphere.
The dipping of S5-2, repeating step S5-1, pulling film forming, placement, cross-linking process 3 times, then cracking at 700 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 5 DEG C/min, and soaking time is 2h, then heat-treats at 1100 DEG C in an inert atmosphere, and during thermal treatment, temperature rise rate is 15 DEG C/min, and soaking time is 3h.
The process of S5-3, repeating step S5-2 3 times, finally calcine at 1600 DEG C in an inert atmosphere, during calcining, temperature rise rate is 15 DEG C/min, soaking time is 1h, prepare the fine and close mullite coating of thickness 30 μm, obtain the composite substrate with SiC undercoat and mullite middle layer.
S6, preparation Y
2si
2o
7individual layer:
S6-1, the composite substrate with SiC undercoat and mullite middle layer to be immersed in for the preparation of Y
2si
2o
7the Y of individual layer
2o
3keep 20min in mud, after taking out with the speed pulling film forming of 5cm/min, place 60min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S6-2, repeating step S6-1, pulling film forming, placement, cross-linking process 2 times, then cracking at 900 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h, then thermal treatment at 1100 DEG C in a vacuum, and temperature rise rate during thermal treatment is 10 DEG C/min, and soaking time is 2h.
The process of S6-3, repeating step S6-2 2 times, finally calcines in an inert atmosphere at 1400 DEG C, and temperature rise rate during calcining is 15 DEG C/min, and soaking time is 2h, prepares the fine and close Y of thickness 40 μm
2si
2o
7individual layer.
S7, preparation 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5individual layer:
S7-1, will with SiC undercoat, mullite middle layer and Y
2si
2o
7the composite substrate of individual layer is immersed in for the preparation of 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5the Y of individual layer
2o
3keep 2min in mud, after taking out with the speed pulling film forming of 20cm/min, place 60min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S7-2, repeating step S7-1, pulling film forming, placement, cross-linking process 2 times, then cracking at 800 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h, then thermal treatment at 1100 DEG C in a vacuum, and temperature rise rate during thermal treatment is 10 DEG C/min, and soaking time is 2h.
The process of S7-3, repeating step S7-2 2 times, finally calcines in an inert atmosphere at 1400 DEG C, and temperature rise rate during calcining is 15 DEG C/min, and soaking time is 2h, prepares the fine and close 70wt%Y of thickness 30 μm
2si
2o
7+ 30wt%Y
2siO
5individual layer.
S8, preparation Y
2siO
5individual layer:
S8-1, will with SiC undercoat, mullite middle layer, Y
2si
2o
7individual layer and 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5the composite substrate of individual layer is immersed in for the preparation of Y
2siO
5the Y of individual layer
2o
3keep 2min in mud, after taking out with the speed pulling film forming of 20cm/min, place 60min, then crosslinked 2h at 250 DEG C in atmosphere.
The dipping of S8-2, repeating step S8-1, pulling film forming, placement, cross-linking process 2 times, then cracking at 900 DEG C in atmosphere, makes silicone resin be converted into SiO
2, during cracking, temperature rise rate is 10 DEG C/min, and soaking time is 1h, then thermal treatment at 1100 DEG C in a vacuum, and temperature rise rate during thermal treatment is 10 DEG C/min, and soaking time is 2h.
The process of S8-3, repeating step S8-2 2 times, finally calcines in an inert atmosphere at 1400 DEG C, and temperature rise rate during calcining is 15 DEG C/min, and soaking time is 2h, prepares the fine and close Y of thickness 20 μm
2siO
5individual layer, completes the preparation of composite material surface SiC/ mullite/iridium silicate coating layer system.
In this composite material surface coating system at 1500 DEG C cracking generate SiC coating, at 1600 DEG C calcining generate mullite coating, at 1400 DEG C calcining generate Y
2si
2o
7coating, at 1400 DEG C calcining generate 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5coating, at 1400 DEG C calcining generate Y
2siO
5coating, XRD figure spectrum respectively see Fig. 2, Fig. 3, Fig. 4, Fig. 5 and Fig. 6.
Can find in fig. 2, by SiC coating prepared by " silicone resin+SiC powder " mud raw material, after 1400 DEG C of calcinings, there is the diffraction peak of typical b-SiC phase 36 °, 60 °, 72 ° three positions, illustrated that the phase composite of coating is the good b-SiC phase of crystallization degree.Along with the rising of calcining temperature, can see, the diffraction peak intensity of b-SiC phase raises gradually, have also appeared two new diffraction peaks of 42 °, 76 ° positions when 1600 DEG C, shows that the crystallization degree of b-SiC phase is also improving constantly.Can see in figure 3, by " silicone resin+Al
2o
3powder " mullite coating prepared of mud raw material, the phase composite at 1400 DEG C, 1500 DEG C, 1600 DEG C after calcining be all the mullite phase that crystallization degree is very high, not have the SiO that appearance is had more than needed
2or Al
2o
3phase, and along with temperature rising, the diffraction peak of mullite phase does not significantly change, this is because the amorphous Si O that silicone resin changes into
2there is very high activity, at 1400 DEG C just and Al
2o
3reaction generates the very high mullite phase of crystallization degree.Same reason, can see in Fig. 4, Fig. 5, Fig. 6, by " silicone resin+Y
2o
3powder " Y for preparing of mud raw material
2si
2o
7coating, 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5coating, Y
2siO
5coating, the phase composite at 1400 DEG C, 1500 DEG C, 1600 DEG C after calcining is all the Y that crystallization degree is very high
2si
2o
7phase, 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5phase, Y
2siO
5phase, and Y
2si
2o
7phase, 70wt%Y
2si
2o
7+ 30wt%Y
2siO
5phase, Y
2siO
5the diffraction peak position of phase and intensity also significantly do not change along with calcining temperature raises.Due to Y in preparation in mud
2o
3powder is slightly excessive, causes Y in Fig. 6
2siO
5a small amount of Y is there is in the diffraction peak of phase
2o
3the diffraction peak of phase.
The matrix material of the lacquer systems with the present embodiment is oxidized 10h in 1400 DEG C of air, and rate of weight loss is 0.74%, and the strength retention ratio of matrix material is 102.5%, and namely after oxidation, intensity does not decline.Show: the lacquer systems of embodiment 5 relies on the characteristics such as it is high temperature resistant, anti-oxidant, high-compactness, and and matrix material between good physical chemistry consistency, good oxidation protection effect is served to matrix material.
Although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention.Any those of ordinary skill in the art, when not departing from technical solution of the present invention scope, can utilize the technology contents of above-mentioned announcement to make many possible variations and modification to technical solution of the present invention, or being revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to the technology of the present invention essence to any simple modification made for any of the above embodiments, equivalent variations and modification, all should drop in the scope of technical solution of the present invention protection.
Claims (10)
1. the lacquer systems of a FRCMC, it is characterized in that, described lacquer systems is located at the surface of FRCMC substrate, and described lacquer systems comprises SiC coating, mullite coating and the iridium silicate coating layer laid successively from the bottom to top.
2. lacquer systems according to claim 1, is characterized in that, described FRCMC substrate is one or more in C/SiC composite substrate, SiC/SiC composite substrate and C/C composite substrate; Described iridium silicate coating layer is by Y
2si
2o
7and Y
2siO
5mixed coating, Y
2siO
5single-phase coating and Y
2si
2o
7one or more layers in single-phase coating is formed.
3. lacquer systems according to claim 1, is characterized in that, in the chemical constitution of described mullite coating, and Al
2o
3with SiO
2mass ratio be 2.13: 1 ~ 3.55: 1.
4. lacquer systems according to any one of claim 1 to 3, is characterized in that, the thickness of described SiC coating is 20 μm ~ 60 μm; The thickness of described mullite coating is 30 μm ~ 80 μm; The thickness of described iridium silicate coating layer is 20 μm ~ 100 μm.
5. a preparation method for the lacquer systems of the FRCMC according to any one of Claims 1-4, is characterized in that, comprises the following steps:
The mud raw material of S1, preparation SiC coating: by SiC powder, silicone resin in organic solvent dispersing and mixing obtain SiC mud raw material;
The mud raw material of S2, preparation mullite coating: by Al
2o
3powder, silicone resin in organic solvent dispersing and mixing obtain Al
2o
3mud raw material;
The mud raw material of S3, preparation iridium silicate coating layer: by Y
2o
3powder, silicone resin in organic solvent dispersing and mixing obtain Y
2o
3mud raw material;
S4, preparation SiC coating: FRCMC substrate is immersed in the mud raw material of step S1 preparation, by dip-coating method in composite substrate surface preparation SiC coating, obtain the FRCMC substrate with SiC coating;
S5, prepare mullite coating: immerse in the mud raw material of step S2 preparation by the FRCMC substrate with SiC coating, prepare mullite coating by dip-coating method at SiC coatingsurface, obtain the FRCMC substrate with SiC coating and mullite coating;
S6, prepare iridium silicate coating layer: immerse in the mud raw material of step S3 preparation by the FRCMC substrate with SiC coating and mullite coating, prepare iridium silicate coating layer by dip-coating method on mullite coating surface, complete the preparation of FRCMC lacquer systems.
6. preparation method according to claim 5, is characterized in that, described preparation method is further comprising the steps of: the working method of repeating step S6, changes Y at every turn
2o
3silicon yttrium atom ratio in mud raw material, on the mullite coating that step S5 is obtained, prepares silicon yttrium atom successively than the yttrium silicate single-layer coating diminished gradually from the bottom to top, forms yttrium silicate laminated coating.
7. the preparation method according to claim 5 or 6, is characterized in that, in described step S1, the volume ratio of described SiC powder and described silicone resin is 1: 1 ~ 1: 9; In described step S2, described Al
2o
3the mass ratio of powder and described silicone resin is 1.4: 1 ~ 2.3: 1; In described step S3, described Y
2o
3the mass ratio of powder and described silicone resin is 1.2: 1 ~ 2.5: 1; Described organic solvent is ethanol.
8. the preparation method according to claim 5 or 6, is characterized in that, the detailed process that SiC coating described in described step S4 is prepared by dip-coating method is:
S4-1: FRCMC substrate to be immersed in SiC mud raw material and to keep 2min ~ 20min, pulling film forming places 30min ~ 60min after taking out, and then, carries out crosslinked 2h ~ 4h in atmosphere at 200 DEG C ~ 300 DEG C;
The Best-Effort request of S4-2: repeating step S4-1 places cross-linking process 2 ~ 6 times, then in inert atmosphere or vacuum environment, carries out cracking 1h ~ 3h at 800 DEG C ~ 1200 DEG C;
The process of S4-3: repeating step S4-2 2 ~ 6 times, then carries out cracking 1h ~ 4h in inert atmosphere or vacuum environment at 1400 DEG C ~ 1600 DEG C;
S4-4: be a circulation with step S4-1, S4-2 and S4-3, repeats this working cycle 2 ~ 4 times, makes SiC coating reach preset thickness and densification, obtain the composite substrate with SiC coating.
9. the preparation method according to claim 5 or 6, is characterized in that, the detailed process that mullite coating described in described step S5 is prepared by dip-coating method is:
S5-1: the composite substrate with SiC coating is immersed in Al
2o
3keep 2min ~ 20min in mud raw material, pulling film forming places 30min ~ 60min after taking out, and then at 200 DEG C ~ 300 DEG C, carries out crosslinked 2h ~ 4h in atmosphere;
The Best-Effort request of S5-2: repeating step S5-1 places cross-linking process 2 ~ 6 times, then at 700 DEG C ~ 900 DEG C, carries out cracking 1h ~ 2h in atmosphere, makes silicone resin be converted into SiO
2, then in inert atmosphere or vacuum with 1100 DEG C ~ 1300 DEG C thermal treatment 1h ~ 3h;
The process of S5-3: repeating step S5-2 2 ~ 6 times, then calcines 1h ~ 3h with 1400 DEG C ~ 1600 DEG C, obtains the composite substrate with SiC coating and mullite coating in inert atmosphere or vacuum.
10. the preparation method according to claim 5 or 6, is characterized in that, the detailed process that yttrium silicate single-layer coating described in described step S6 is prepared by dip-coating method is:
S6-1: the composite substrate with SiC coating and mullite coating is immersed in Y
2o
3keep 2min ~ 20min in mud raw material, pulling film forming places 30min ~ 60min after taking out, and then at 200 DEG C ~ 300 DEG C, carries out crosslinked 2h ~ 4h in atmosphere;
The Best-Effort request of S6-2: repeating step S6-1 places cross-linking process 2 ~ 6 times, then at 700 DEG C ~ 900 DEG C, carries out cracking 1h ~ 2h in atmosphere, makes silicone resin be converted into SiO
2, then in inert atmosphere or vacuum, at 1100 DEG C ~ 1300 DEG C, heat-treat 1h ~ 3h;
The process of S6-3: repeating step S6-2 2 ~ 6 times, then carries out calcining 1h ~ 3h in inert atmosphere or vacuum at 1400 DEG C ~ 1600 DEG C, completes the preparation of composite material surface SiC, mullite and iridium silicate coating layer system.
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