CN104446670B - C/SiC composite material surface coating system and preparation method thereof - Google Patents
C/SiC composite material surface coating system and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of C/SiC composite material surface coating system and preparation method thereof.This lacquer systems is located at C/SiC composite substrate surface, including the mullite coating laid the most successively and iridium silicate coating layer.Preparation method includes that (1) prepares Al2O3‑SiO2Complex sol；(2) the mud raw material of iridium silicate coating layer is prepared；(3) mullite coating is prepared；(4) yttrium silicate signal layer coating or yttrium silicate laminated coating are prepared.The C/SiC composite material surface coating system of the present invention has high feature fine and close, resistant to elevated temperatures, and its preparation method has engineer applied universality.
Description
Technical field
The invention belongs to high-temperature fibre and strengthen ceramic matric composite field; relate to a kind of C/SiC composite material surface coating system and preparation method thereof, be specifically related to a kind of novel in order to double-deck fire-resistant oxidation resistant coating protecting C/SiC composite and preparation method thereof.
Background technology
Carbon fibre reinforced silicon carbide (C/SiC) composite has high specific strength and specific modulus, high temperature resistant, high damage tolerance, the excellent specific property such as corrosion-resistant, it is considered as a kind of strategic thermal structure material, all has broad application prospects in fields such as Aero-Space, traffic, the energy, chemical industry.As a kind of thermal structure material, C/SiC composite faces, when application, the problem that high-temperature oxydation lost efficacy, and it main reason is that carbon fiber also exists a large amount of hole and crackle in meeting severe oxidation and composite more than 400 DEG C.
The coating preparing fire-resistant oxidation resistant at composite material surface is presently the most effective anti-oxidation method, and coating composition and structure are then the key factors affecting antioxidant effect.Yttrium silicate has Y2SiO5、Y2Si2O7、Y4Si3O12Three kinds of crystal phase structures, wherein most commonly seen with first two, fusing point is respectively 1980 DEG C, 1775 DEG C.In addition to high-melting-point, yttrium silicate also has the characteristics such as low thermal coefficient of expansion, low high-temperature oxygen permeability, low modulus, low vaporization at high temperature rate, lower thermal conductivity, chemically and thermally good stability, one of optimal candidate material making it high-temperature oxidation resistant coating.As the ORC of C/C, C/SiC composite, yttrium silicate has caused the extensive concern of people and has obtained more research.
Iridium silicate coating layer is prepared at C/SiC composite material surface, current most common way is, first pass through chemical vapour deposition technique and prepare SiC undercoating, purpose is to alleviate the thermal mismatching degree between composite substrate and iridium silicate coating layer to improve bond strength, then utilizes hot isostatic pressing method, mud brushing sintering process, electrophoretic deposition, plasma spraying method, sol-gel process etc. to prepare yttrium silicate external coating.The deficiency that these schemes exist has: the consistency of (1) iridium silicate coating layer self is inadequate, and oxygen is at Y2O3And SiO2In diffusion coefficient be all low-down, if but coating itself is the finest and close, this advantage is just lost a lot.Improve sintering temperature simply to differ and reach effect surely, composite substrate can be caused damage on the contrary.Though consistency can be improved by adding glass phase outermost layer, but the temperature resistant capability of glass phase is limited, and the performance in aggressive atmosphere is not ideal enough；(2) as time went on, SiC undercoating can gradually be oxidized to SiO2, the gaseous by-product of generation can cause iridium silicate coating layer cracking when external diffusion or come off, thus affecting the long-time antioxidant effect of coating；(3) some preparation methoies such as hot isostatic pressing method, chemical vapour deposition technique, electrophoretic deposition etc. is difficult to be applicable to the preparation of complex shaped components face coat.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that a kind of high C/SiC composite material surface coating system fine and close, resistant to elevated temperatures, provides the preparation method with engineer applied universality of this lacquer systems simultaneously.
For solve above-mentioned technical problem, the present invention by the following technical solutions:
A kind of C/SiC composite material surface coating system, described lacquer systems is located at C/SiC composite substrate surface, and described lacquer systems includes that (chemical formula is 3Al for the mullite laid the most successively2O3·2SiO2) coating and iridium silicate coating layer.
In above-mentioned C/SiC composite material surface coating system, it is preferred that described iridium silicate coating layer is yttrium silicate signal layer coating or yttrium silicate laminated coating；Described yttrium silicate signal layer coating is by Y2Si2O7And Y2SiO5Mixed coating, Y2SiO5Single-phase coating, Y2Si2O7One layer of composition in single-phase coating；Described yttrium silicate laminated coating is by Y2Si2O7And Y2SiO5Mixed coating, Y2SiO5Single-phase coating, Y2Si2O7Multilamellar (more than two-layer or two-layer) in single-phase coating is constituted.
In above-mentioned C/SiC composite material surface coating system, it is preferred that the thickness of described mullite coating is 10 μm～30 μm；The thickness of described yttrium silicate signal layer coating is 30 μm～100 μm, and the thickness in monolayer of described yttrium silicate laminated coating is 30 μm～100 μm.
As total technology design, the present invention also provides for the preparation method of a kind of above-mentioned C/SiC composite material surface coating system, comprises the following steps:
(1) preparation Al2O3-SiO2Complex sol: by Al2O3Colloidal sol and SiO2Colloidal sol mixes, and obtains Al2O3-SiO2Complex sol；
(2) the mud raw material of iridium silicate coating layer is prepared: by silicones and Y2O3Powder adds to organic solvent, and silicon yttrium atom ratio is 1: 1～2, obtains the mud raw material of iridium silicate coating layer；
(3) mullite coating is prepared: C/SiC composite substrate is immersed the Al that step (1) is prepared2O3-SiO2In complex sol, prepare mullite coating by dip-coating method on C/SiC composite substrate surface, obtain the C/SiC composite substrate with mullite coating；
(4) iridium silicate coating layer is prepared: immersed by the C/SiC composite substrate with mullite coating in the mud raw material of the iridium silicate coating layer that step (2) is prepared, iridium silicate coating layer is prepared on mullite coating surface by dip-coating method, this iridium silicate coating layer is yttrium silicate signal layer coating, obtains C/SiC composite material surface coating system.
As total technology design, the present invention also provides for the preparation method of a kind of above-mentioned C/SiC composite material surface coating system, comprises the following steps:
(1) preparation Al2O3-SiO2Complex sol: by Al2O3Colloidal sol and SiO2Colloidal sol mixes, and obtains Al2O3-SiO2Complex sol；
(2) the mud raw material of iridium silicate coating layer is prepared: by silicones and the Y of two or more different silicon yttrium atom ratios2O3Powder is added separately in organic solvent, is prepared as the mud raw material with different silicon yttrium atom ratio, and in each mud raw material, silicon yttrium atom ratio is all in the range of 1: 1～2；
(3) mullite coating is prepared: C/SiC composite substrate is immersed the Al that step (1) is prepared2O3-SiO2In complex sol, prepare mullite coating by dip-coating method on C/SiC composite substrate surface, obtain the C/SiC composite substrate with mullite coating；
(4) yttrium silicate signal layer coating is prepared: immersed in the one of which mud raw material that step (2) is prepared by the C/SiC composite substrate with mullite coating, prepare yttrium silicate signal layer coating by dip-coating method on mullite coating surface；
(5) iridium silicate coating layer is prepared: repeat the operational approach of step (4), the yttrium silicate signal layer coating that step (4) prepares is sequentially prepared the yttrium silicate signal layer coating with different silicon yttrium atom ratios from the bottom to top, form iridium silicate coating layer, this iridium silicate coating layer is yttrium silicate laminated coating, finally gives C/SiC composite material surface coating system.
In above-mentioned preparation method, it is preferred that in described step (1), described Al2O3-SiO2Al in complex sol2O3With SiO2Mass ratio be 1～2: 1, described Al2O3-SiO2The solid content of complex sol is 20wt%～40wt%；In described step (2), described organic solvent is ethanol (more preferably dehydrated alcohol).
In above-mentioned preparation method, it is preferred that the detailed process that described mullite coating is prepared by dip-coating method is: C/SiC composite substrate is immersed in Al by (a)2O3-SiO2In complex sol and keep, pulling film forming is placed after taking out, and is then dried；B () is repeated the Best-Effort request of step (a) and is placed dry run (can improve coating layer thickness and consistency), be then warming up to 1200 DEG C～1400 DEG C in vacuum or inert atmosphere and carry out being incubated (i.e. calcining)；C () is a circulation with step (a) and step (b), repeat this cyclic process, make mullite coating reach preset thickness densification, obtain the C/SiC composite substrate with mullite coating.
In above-mentioned preparation method, it is preferred that the design parameter that described mullite coating is prepared by dip-coating method is: in described step (a), and described C/SiC composite substrate is immersed in Al2O3-SiO2The time kept in complex sol is 2min～20min, and the speed of described lifting is 5cm/min～20cm/min, and the time of described placement is 10min～120min, and described dry temperature is 60 DEG C～200 DEG C, and the described dry time is 0.5h～4h；In described step (b), it is 4～10 times that described Best-Effort request places the number of repetition of dry run, and the speed of described intensification is 2 DEG C/min～10 DEG C/min, and the time of described insulation is 1h～4h；In described step (c), the number of repetition of described cyclic process is 4～8 times.
In above-mentioned preparation method, preferably, the detailed process that described yttrium silicate signal layer coating is prepared by dip-coating method is: the described C/SiC composite substrate with mullite coating is immersed in the mud raw material of iridium silicate coating layer and keeps by (a), and pulling film forming is placed after taking out；B () repeats the Best-Effort request placement process (can improve coating layer thickness and consistency) of step (a), then cross-linked at 200 DEG C～300 DEG C in atmosphere by gained sample；C () repeats the process of step (b), crack the most in atmosphere, make silicones change into SiO at 600 DEG C～1000 DEG C2, then in vacuum or inert atmosphere, it is warming up to 1200 DEG C～1400 DEG C insulations (i.e. calcining)；D () is a circulation with step (a) and (b) and (c), repeat this cyclic process, make coating reach preset thickness densification, obtain yttrium silicate signal layer coating.
In above-mentioned preparation method, preferably, the design parameter that described yttrium silicate signal layer coating is prepared by dip-coating method is: in described step (a), the described C/SiC composite substrate with mullite coating be immersed in the mud raw material of iridium silicate coating layer keep time be 2min～20min, the speed of described lifting is 5cm/min～20cm/min, and the time of described placement is 10min～120min；In described step (b), the number of repetition of described Best-Effort request placement process is 4～10 times, and the time of described crosslinking is 1h～4h；In described step (c), the number of times repeating step (b) is 4～8 times, and the time of described cracking is 1h～4h, and the speed of described intensification is 2 DEG C/min～10 DEG C/min, and the time of described insulation is 1h～4h；In described step (d), the number of repetition of described cyclic process is 4～8 times.
The technical scheme is that with C/SiC composite as substrate, first with high solid loading Al2O3-SiO2Complex sol is the raw material of mullite coating, prepares fine and close mullite coating by dip-coating method at substrate surface, then with silicones+Y2O3The mud that powder is configured in ethanol is raw material, is prepared the iridium silicate coating layer of densification on mullite coating surface by dip-coating method.Wherein, can be by change silicones and Y2O3The ratio of powder, it is thus achieved that different phase composition (Y2Si2O7、Y2Si2O7+Y2SiO5、Y2SiO5) yttrium silicate signal layer coating, it is possible to be prepared as yttrium silicate laminated coating, such as from the Y of nexine2Si2O7Y to outer layer2SiO5Gradient iridium silicate coating layer.
The performance parameter of the C/SiC composite material surface bilayer ORC system of the present invention, can be determined by the following method: by oxidation 0.5h～1h in 1400 DEG C～1600 DEG C of air ambients (Muffle furnace) of the C/SiC composite with duplex coating, then measure the weight rate before and after oxidation, strength retention ratio.
In the preparation method of the present invention, at preparation Al2O3-SiO2During complex sol, a kind of mode preferably used is: the Al that will buy2O3Colloidal sol and SiO2Colloidal sol is mixed in required ratio, is poured slowly in another colloidal sol by one colloidal sol, is aided with stirring simultaneously during mixing.
In the preparation method of the present invention, when the C/SiC composite substrate with mullite coating is immersed the mud raw material of iridium silicate coating layer, for ensureing stability and the uniformity of mud raw material, before using, mud raw material is stirred and sonic oscillation processes, to avoid Y2O3The sedimentation of powder.
In the preparation method of the present invention, Y2O3The mean diameter of powder is preferably 2 μm～10 μm.
In the preparation method of the present invention, when preparing the mud raw material of iridium silicate coating layer, preferably press silicon yttrium atom than 1: 1～2 by silicones and Y2O3Powder is blended, and is that medium carries out ball milling dispersion mixing with ethanol (preferably dehydrated alcohol).Silicon yttrium atom is than 1: 2 corresponding Y2SiO5Phase, silicon yttrium atom is than 1: 1 corresponding Y2Si2O7Phase, can get Y between2SiO5+ Y2Si2O7Mixed phase.
Compared with prior art, it is an advantage of the current invention that:
(1) the C/SiC composite material surface coating system of the present invention includes mullite coating and iridium silicate coating layer.Mullite is about the same with the thermal coefficient of expansion of the SiC in C/SiC composite, chemical compatibility is the most fine, itself there is good antioxygenic property and oxidation reaction will not occur again, thus avoiding SiC undercoating voloxidation in traditional method and cause yttrium silicate external coating cracking or the problem come off.Owing to mullite and yttrium silicate are all oxides, composition has SiO2, this is conducive to forming strong combination between the two, thus improves antioxidation and the resistance to erosion ability of coating.
(2) in the preparation method of the present invention, by high solid loading Al2O3-SiO2Complex sol mullite synthesizing avoids from the shortcoming on the low side containing Al and the efficiency of route containing Si compound solution, and maintaining again sol-gel can be with the advantage of low temperature mullite synthesizing.Silicones is as SiO2While raw material, there is again good caking property, so " silicones+Y2O3Powder " mud is not only easy in composite material surface film forming, but also avoid outer adding additives and need to get rid of and totally prepare, to coating, the adverse effect brought with performance.By change silicones and Y2O3The ratio of powder, prepares Y2SiO5、Y2Si2O7Single-phase coating or Y2SiO5+Y2Si2O7Mixed coating.
(3) in the preparation method of the present invention, the SiO in complex sol2The SiO obtained is converted with the silicones in mud raw material2All there is the highest activity, can respectively with Al2O3、Y2O3Reaction generation mullite or yttrium silicate under lower temperature (≤1400 DEG C), and SiO2Just there is at 1000 DEG C good viscous flow characteristics, can promote the low temperature densification of coating, thus avoid the adverse effect that composite brings by high temperature sintering.
(4), in the preparation method of the present invention, mullite is all based on liquid phase feed with the synthesis of yttrium silicate, can prepare coating by dip-coating method.The method process is simple and easy to control, low for equipment requirements, is not only suitable for large scale, complex shaped components, is also applied for the component with inner-cavity structure, has good universality on engineer applied.
(5) the surface oxidation-resistant coating system that prepared by the present invention also can strengthen the mechanical property of C/SiC composite itself effectively, and used related raw material wide material sources are stable and cheap.
Accompanying drawing explanation
Fig. 1 is the structural representation of the C/SiC composite material surface coating system in the embodiment of the present invention.
Fig. 2 is the C/SiC composite material surface coating system in the embodiment of the present invention 1～3 generates mullite respectively at 1200 DEG C, 1400 DEG C, 1300 DEG C XRD figure spectrum when being incubated calcining.
Fig. 3 is the XRD figure spectrum that the C/SiC composite material surface coating system in the embodiment of the present invention 1～3 generates yttrium silicate respectively when being incubated calcining for 1300 DEG C, 1400 DEG C.
Detailed description of the invention
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.
Material and instrument employed in following example are commercially available.
Embodiment
1
:
The C/SiC composite material surface coating system of a kind of present invention, as it is shown in figure 1, this lacquer systems is located at C/SiC composite substrate surface, this lacquer systems includes the mullite (3Al laid the most successively2O3·2SiO2) coating and iridium silicate coating layer.
In the present embodiment, iridium silicate coating layer is Y2Si2O7Single-phase coating, thickness in monolayer is 30 μm.The thickness of mullite coating is 15 μm.
The preparation method of the C/SiC composite material surface coating system of a kind of above-mentioned the present embodiment, comprises the following steps:
(1) by Al2O3Colloidal sol and SiO2Colloidal sol (the two is commercially available) mixes, Al2O3And SiO2Mass ratio be 1: 1, preparation solid content is the Al of high solid loading of 22wt%2O3-SiO2Complex sol, as the raw material of mullite coating.
(2) the mud raw material of iridium silicate coating layer is prepared: by silicon yttrium atom ratio 1: 1, by silicones and Y2O3Powder (mean diameter 3 μm) is blended, and carries out ball milling dispersion mixing with dehydrated alcohol for medium, obtains mud raw material, is used for preparing iridium silicate coating layer (Y2Si2O7Single-phase coating).
(3) mullite coating is prepared: (a) is with the Al in step (1)2O3-SiO2Complex sol is raw material, is immersed in complex sol by C/SiC composite substrate, lift away with the speed of 15cm/min after dipping 2min, 100 DEG C of dry 0.5h in atmosphere after placement 10min；B the lifting of () repeated impregnations places dry run 6 times, complex sol coating is formed at substrate surface, then the substrate with complex sol coating is placed in inert atmosphere (nitrogen or argon, lower same), rises to 1200 DEG C of insulations (i.e. calcining) 1h with 5 DEG C/min；C () is a circulation with step (a) and step (b), repeat this circulation 4 times, prepares the fine and close mullite coating of thickness 15 μm, obtains the C/SiC composite substrate with mullite coating.
(4) iridium silicate coating layer is prepared: mud (for ensureing stability and uniformity, is stirred before using and sonic oscillation processes to avoid Y by the mud raw material that C/SiC composite substrate immersion step (2) with mullite coating that step (3) is obtained by (a) is prepared2O3The sedimentation of powder) in, lift away with the speed of 15cm/min after keeping 2min and place 10min；B () repeated impregnations lifting placement process 8 times, forms mud raw material coating, then by the 300 DEG C of crosslinking 1h in atmosphere of the substrate with mud raw material coating on mullite coating surface；C, after the process of () repetition step (b) 4 times, 800 DEG C of cracking 1h, make silicones change into SiO in atmosphere2, it is warmed up to 1300 DEG C of insulations (i.e. calcining) 1h with 5 DEG C/min the most in an inert atmosphere；D () is a circulation with step (a) and (b) and (c), repeat this circulation 4 times, prepares the fine and close iridium silicate coating layer (Y of thickness in monolayer 30 μm2Si2O7Single-phase coating), obtain C/SiC composite material surface coating system.The XRD figure spectrum of the mullite coating generated when 1200 DEG C in this C/SiC composite material surface coating system and the iridium silicate coating layer generated when 1300 DEG C sees Fig. 2 and Fig. 3 respectively.
By the C/SiC composite of the lacquer systems with the present embodiment, in 1500 DEG C of air, (Muffle furnace, lower same) aoxidizes 0.5h, and weightlessness is only 0.69%, and the strength retention ratio of composite reaches 144.3%, and i.e. after oxidation, intensity improves on the contrary.This is due to Y2Si2O7The phase stability of single-phase coating is high and good with the chemical compatibility of substrate, further densified sintering product can occur in oxidizing process, combination with substrate also can be strengthened, thus causes composite almost without there is oxidation weight loss, and mechanical property has risen.
Embodiment
2
:
The C/SiC composite material surface coating system of a kind of present invention, as it is shown in figure 1, this lacquer systems is located at C/SiC composite substrate surface, this lacquer systems includes mullite coating and the iridium silicate coating layer laid the most successively.
In the present embodiment, iridium silicate coating layer is 30wt%Y2SiO5And 70wt%Y2Si2O7Mixed coating, thickness in monolayer is 75 μm.The thickness of mullite coating is 25 μm.
The preparation method of the C/SiC composite material surface coating system of a kind of above-mentioned the present embodiment, comprises the following steps:
(1) by Al2O3Colloidal sol and SiO2Colloidal sol mixes, Al2O3And SiO2Mass ratio be 2: 1, preparation solid content is the Al of high solid loading of 25wt%2O3-SiO2Complex sol, as the raw material of mullite coating.
(2) the mud raw material of iridium silicate coating layer is prepared: by silicon yttrium atom ratio 1: 1.2, by silicones and Y2O3Powder (mean diameter 5 μm) is blended, and carries out ball milling dispersion mixing with dehydrated alcohol for medium, obtains mud raw material, is used for preparing iridium silicate coating layer and (is 30wt%Y2SiO5And 70wt%Y2Si2O7Mixed coating).
(3) mullite coating is prepared: (a) is with the Al in step (1)2O3-SiO2Complex sol is raw material, is immersed in colloidal sol by C/SiC composite substrate, and after dip-coating 5min, the speed with 10cm/min lifts away, places after 30min 100 DEG C of dry 1h in atmosphere；B the lifting of () repeated impregnations places dry run 8 times, form complex sol coating at substrate surface, be then placed in inert atmosphere by the substrate with complex sol coating, rises to 1400 DEG C of insulation 1h with 5 DEG C/min；C () is a circulation with step (a) and step (b), repeat this circulation 5 times, prepare the fine and close mullite coating of thickness 25 μm, obtain the C/SiC composite substrate with mullite coating.
(4) iridium silicate coating layer is prepared: mud (for ensureing stability and uniformity, is stirred before using and sonic oscillation processes to avoid Y by the mud raw material that C/SiC composite substrate immersion step (2) with mullite coating that step (3) is obtained by (a) is prepared2O3The sedimentation of powder) in, lift away with the speed of 10cm/min after dipping 10min and place 30min；B () repeated impregnations lifting placement process 10 times, forms mud raw material coating, then by the 300 DEG C of crosslinking 2h in atmosphere of the substrate with mud raw material coating on mullite coating surface；C, after the process of () repetition step (b) 6 times, 800 DEG C of cracking 1h, make silicones change into SiO in atmosphere2, it is warmed up to 1400 DEG C of insulation 1h with 5 DEG C/min the most in an inert atmosphere；D () is a circulation with step (a) and (b) and (c), repeat this circulation 5 times, prepares the fine and close iridium silicate coating layer of thickness in monolayer 75 μm, is 30wt%Y2SiO5And 70wt%Y2Si2O7Mixed coating, obtain C/SiC composite material surface coating system.The mullite coating generated when 1400 DEG C in this C/SiC composite material surface coating system and the XRD figure spectrum of iridium silicate coating layer see Fig. 2 and Fig. 3 respectively.
The C/SiC composite of the lacquer systems with the present embodiment aoxidizes in 1600 DEG C of air 0.5h, and weightlessness is only 1.07%, and the strength retention ratio of composite reaches 131.2%, and i.e. after oxidation, intensity improves on the contrary.This is due to 30wt%Y2SiO5And 70wt%Y2Si2O7The phase stability of mixed coating high and good with the chemical compatibility of substrate, oxidizing process can occur further densified sintering product, the combination with substrate also can be strengthened, thus causes the oxidation weight loss of composite the least, and mechanical property has risen.
Embodiment
3
:
The C/SiC composite material surface coating system of a kind of present invention, as it is shown in figure 1, this lacquer systems is located at C/SiC composite substrate surface, this lacquer systems includes mullite coating and the iridium silicate coating layer laid the most successively.
In the present embodiment, in iridium silicate coating layer, (being also from the inside to the outside) is followed successively by 30wt%Y from the bottom to top2SiO5And 70wt%Y2Si2O7Mixed coating, 70wt%Y2SiO5And 30wt%Y2Si2O7Mixed coating, Y2SiO5Single-phase coating, each thickness in monolayer is 35 μm, and the gross thickness of iridium silicate coating layer is 105 μm.The thickness of mullite coating is 21 μm.
The preparation method of the C/SiC composite material surface coating system of a kind of above-mentioned the present embodiment, comprises the following steps:
(1) by Al2O3Colloidal sol and SiO2Colloidal sol mixes, Al2O3And SiO2Mass ratio be 1.8: 1, preparation solid content is the Al of high solid loading of 22.6wt%2O3-SiO2Complex sol, as the raw material of mullite coating.
(2) the mud raw material of iridium silicate coating layer is prepared: be 1: 1.2,1: 1.6,1: 2 by silicones and Y by silicon yttrium atom ratio respectively2O3Powder (mean diameter 2 μm) is blended, and carries out ball milling dispersion mixing with dehydrated alcohol for medium, obtains three kinds of mud raw materials, for preparing the iridium silicate coating layer of different phase composition, respectively 30wt%Y2SiO5And 70wt%Y2Si2O7Mixed coating, 70wt%Y2SiO5And 30wt%Y2Si2O7Mixed coating, Y2SiO5Single-phase coating.
(3) mullite coating is prepared: (a) is with the Al in step (1)2O3-SiO2Complex sol is raw material, is immersed in colloidal sol by C/SiC composite substrate, lift away with the speed of 13cm/min after dipping 10min, 100 DEG C of dry 2h in atmosphere after placement 60min；B the lifting of () repeated impregnations places dry run 4 times, form complex sol coating at substrate surface, be then placed in inert atmosphere by the substrate with complex sol coating, rises to 1300 DEG C of insulation 2h with 5 DEG C/min；C () is a circulation with step (a) and step (b), repeat this circulation 6 times, prepare the fine and close mullite coating of thickness 21 μm, obtain the C/SiC composite substrate with mullite coating.
(4) yttrium silicate signal layer coating is prepared: the C/SiC composite substrate with mullite coating step (3) obtained immerses in the mud raw material of step (2) prepares 1: 1.2 and (for ensureing stability and uniformity, is stirred mud and sonic oscillation processes to avoid Y before using2O3The sedimentation of powder), lift away with the speed of 15cm/min after dipping 8min and place 60min；(b) repeated impregnations lifting placement process 6 times, the most in atmosphere 300 DEG C of crosslinking 4h；C, after the process of () repetition step (b) 5 times, 800 DEG C of cracking 1.5h, make silicones change into SiO in atmosphere2, it is warmed up to 1400 DEG C of insulation 2h with 5 DEG C/min the most in an inert atmosphere；D () is a circulation with step (a) and (b) and (c), repeat this circulation 4 times, prepares the fine and close yttrium silicate signal layer coating of thickness in monolayer 35 μm, and this yttrium silicate signal layer coating is 30wt%Y2SiO5And 70wt%Y2Si2O7Mixed coating.
(5) prepare iridium silicate coating layer: first use the mud raw material of 1: 1.6, repeat the operational approach of step (4), prepare the fine and close 70wt%Y of thickness in monolayer 35 μm2SiO5And 30wt%Y2Si2O7Mixed coating；Then use the mud raw material of 1: 2, repeat the operational approach of step (4), prepare the fine and close Y of thickness in monolayer 35 μm2SiO5Single-phase coating, obtains yttrium silicate laminated coating (i.e. the iridium silicate coating layer of the present embodiment), and gross thickness is 105 μm, and finally gives C/SiC composite material surface coating system.The XRD figure spectrum of the mullite coating generated when 1300 DEG C in this C/SiC composite material surface coating system and the iridium silicate coating layer generated when 1400 DEG C sees Fig. 2 and Fig. 3 respectively.
The C/SiC composite of the lacquer systems with the present embodiment aoxidizes in 1400 DEG C of air 1h, and weight-loss ratio is 0%, has not i.e. measured weight change, and the strength retention ratio of composite reaches 143.4%, and i.e. after oxidation, intensity improves on the contrary.This is owing to the phase stability of the iridium silicate coating layer of different phase compositions itself is high and good with the chemical compatibility of substrate, further densified sintering product can occur in oxidizing process, combination with substrate also can be strengthened, thus causing composite that oxidation weight loss does not occur, mechanical property has risen.
To sum up, as shown in Figure 2, in the lacquer systems of the embodiment of the present invention 1～embodiment 3, from 1200 DEG C of beginnings, mullite coating just there occurs that obvious mullitization is reacted, when 1300 DEG C, mullitization is substantially completely, obtains crystallizing good mullite phase when 1400 DEG C.As shown in Figure 3, in the lacquer systems of the embodiment of the present invention 1～embodiment 3, from 1200 DEG C of beginnings, iridium silicate coating layer yttrium silicateization when 1300 DEG C clearly (just there occurs that yttrium silicateization is reacted), when 1400 DEG C, reaction is completely, generates and crystallizes good yttrium silicate phase.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-described embodiment.All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.Iting is noted that for those skilled in the art, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. a C/SiC composite material surface coating system, it is characterised in that described lacquer systems is located at C/SiC composite substrate surface, described lacquer systems includes mullite coating and the iridium silicate coating layer laid the most successively；In described mullite coating, Al2O3With SiO2Mass ratio be 1～2: 1, the thickness of described mullite coating is 10 μm～30 μm.
C/SiC composite material surface coating system the most according to claim 1, it is characterised in that described iridium silicate coating layer is yttrium silicate signal layer coating or yttrium silicate laminated coating；Described yttrium silicate signal layer coating is by Y2Si2O7And Y2SiO5Mixed coating, Y2SiO5Single-phase coating, Y2Si2O7One layer of composition in single-phase coating；Described yttrium silicate laminated coating is by Y2Si2O7And Y2SiO5Mixed coating, Y2SiO5Single-phase coating, Y2Si2O7Multilamellar in single-phase coating is constituted.
C/SiC composite material surface coating system the most according to claim 2, it is characterised in that the thickness of described yttrium silicate signal layer coating is 30 μm～100 μm, the thickness in monolayer of described yttrium silicate laminated coating is 30 μm～100 μm.
4. a preparation method for the C/SiC composite material surface coating system as according to any one of claims 1 to 3, comprises the following steps:
(1) preparation Al2O3-SiO2Complex sol: by Al2O3Colloidal sol and SiO2Colloidal sol mixes, and obtains Al2O3-SiO2Complex sol；
(2) the mud raw material of iridium silicate coating layer is prepared: by silicones and Y2O3Powder adds to organic solvent, and silicon yttrium atom ratio is 1: 1～2, obtains the mud raw material of iridium silicate coating layer；
(3) mullite coating is prepared: C/SiC composite substrate is immersed the Al that step (1) is prepared2O3-SiO2In complex sol, prepare mullite coating by dip-coating method on C/SiC composite substrate surface, obtain the C/SiC composite substrate with mullite coating；
(4) iridium silicate coating layer is prepared: immersed by the C/SiC composite substrate with mullite coating in the mud raw material of the iridium silicate coating layer that step (2) is prepared, iridium silicate coating layer is prepared on mullite coating surface by dip-coating method, this iridium silicate coating layer is yttrium silicate signal layer coating, obtains C/SiC composite material surface coating system；
In described step (1), described Al2O3-SiO2Al in complex sol2O3With SiO2Mass ratio be 1～2: 1；Described Al2O3-SiO2The solid content of complex sol is 20wt%～40wt%；
The detailed process that described mullite coating is prepared by dip-coating method is: C/SiC composite substrate is immersed in Al by (a)2O3-SiO2In complex sol and keep, pulling film forming is placed after taking out, and is then dried；B () is repeated the Best-Effort request of step (a) and is placed dry run, be then warming up to 1200 DEG C～1400 DEG C in vacuum or inert atmosphere and be incubated；C () is a circulation with step (a) and step (b), repeat this cyclic process, make mullite coating reach preset thickness densification, obtain the C/SiC composite substrate with mullite coating.
5. a preparation method for the C/SiC composite material surface coating system as according to any one of claims 1 to 3, comprises the following steps:
(1) preparation Al2O3-SiO2Complex sol: by Al2O3Colloidal sol and SiO2Colloidal sol mixes, and obtains Al2O3-SiO2Complex sol；
(2) the mud raw material of iridium silicate coating layer is prepared: by silicones and the Y of two or more different silicon yttrium atom ratios2O3Powder is added separately in organic solvent, is prepared as the mud raw material with different silicon yttrium atom ratio, and in each mud raw material, silicon yttrium atom ratio is all in the range of 1: 1～2；
(3) mullite coating is prepared: C/SiC composite substrate is immersed the Al that step (1) is prepared2O3-SiO2In complex sol, prepare mullite coating by dip-coating method on C/SiC composite substrate surface, obtain the C/SiC composite substrate with mullite coating；
(4) yttrium silicate signal layer coating is prepared: immersed in the one of which mud raw material that step (2) is prepared by the C/SiC composite substrate with mullite coating, prepare yttrium silicate signal layer coating by dip-coating method on mullite coating surface；
(5) iridium silicate coating layer is prepared: repeat the operational approach of step (4), the yttrium silicate signal layer coating that step (4) prepares is sequentially prepared the yttrium silicate signal layer coating with different silicon yttrium atom ratios from the bottom to top, form iridium silicate coating layer, this iridium silicate coating layer is yttrium silicate laminated coating, finally gives C/SiC composite material surface coating system；
In described step (1), described Al2O3-SiO2Al in complex sol2O3With SiO2Mass ratio be 1～2: 1；Described Al2O3-SiO2The solid content of complex sol is 20wt%～40wt%；
The detailed process that described mullite coating is prepared by dip-coating method is: C/SiC composite substrate is immersed in Al by (a)2O3-SiO2In complex sol and keep, pulling film forming is placed after taking out, and is then dried；B () is repeated the Best-Effort request of step (a) and is placed dry run, be then warming up to 1200 DEG C～1400 DEG C in vacuum or inert atmosphere and be incubated；C () is a circulation with step (a) and step (b), repeat this cyclic process, make mullite coating reach preset thickness densification, obtain the C/SiC composite substrate with mullite coating.
6., according to the preparation method described in claim 4 or 5, it is characterised in that in described step (2), described organic solvent is ethanol.
7. according to the preparation method described in claim 4 or 5, it is characterised in that the design parameter that described mullite coating is prepared by dip-coating method is: in described step (a), and described C/SiC composite substrate is immersed in Al2O3-SiO2The time kept in complex sol is 2min～20min, and the speed of described lifting is 5cm/min～20cm/min, and the time of described placement is 10min～120min, and described dry temperature is 60 DEG C～200 DEG C, and the described dry time is 0.5h～4h；In described step (b), it is 4～10 times that described Best-Effort request places the number of repetition of dry run, and the speed of described intensification is 2 DEG C/min～10 DEG C/min, and the time of described insulation is 1h～4h；In described step (c), the number of repetition of described cyclic process is 4～8 times.
8. according to the preparation method described in claim 4 or 5, it is characterized in that, the detailed process that described yttrium silicate signal layer coating is prepared by dip-coating method is: the described C/SiC composite substrate with mullite coating is immersed in the mud raw material of iridium silicate coating layer and keeps by (a), and pulling film forming is placed after taking out；B () repeats the Best-Effort request placement process of step (a), then cross-linked at 200 DEG C～300 DEG C in atmosphere by gained sample；C () repeats the process of step (b), crack the most in atmosphere, make silicones change into SiO at 600 DEG C～1000 DEG C2, then in vacuum or inert atmosphere, it is warming up to 1200 DEG C～1400 DEG C insulations；D () is a circulation with step (a) and (b) and (c), repeat this cyclic process, make coating reach preset thickness densification, obtain yttrium silicate signal layer coating.
Preparation method the most according to claim 8, it is characterized in that, the design parameter that described yttrium silicate signal layer coating is prepared by dip-coating method is: in described step (a), the described C/SiC composite substrate with mullite coating be immersed in the mud raw material of iridium silicate coating layer keep time be 2min～20min, the speed of described lifting is 5cm/min～20cm/min, and the time of described placement is 10min～120min；In described step (b), the number of repetition of described Best-Effort request placement process is 4～10 times, and the time of described crosslinking is 1h～4h；In described step (c), the number of times repeating step (b) is 4～8 times, and the time of described cracking is 1h～4h, and the speed of described intensification is 2 DEG C/min～10 DEG C/min, and the time of described insulation is 1h～4h；In described step (d), the number of repetition of described cyclic process is 4～8 times.
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| CN105110817B (en) * | 2015-08-19 | 2017-12-15 | 中国人民解放军国防科学技术大学 | Lacquer systems of FRCMC and preparation method thereof |
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| JP6696802B2 (en) * | 2016-03-11 | 2020-05-20 | 一般財団法人ファインセラミックスセンター | Environment-resistant coating material |
| FR3051187B1 (en) | 2016-05-11 | 2018-06-01 | Safran Ceramics | PIECE OF COMPOSITE MATERIAL |
| CN106747670A (en) * | 2016-05-30 | 2017-05-31 | 北京航空航天大学 | A kind of Environmental Barrier Coatings on Si-based Ceramics for polynary carbon and ceramic matric composite and preparation method thereof |
| CN106478153B (en) * | 2016-09-28 | 2019-02-22 | 陕西科技大学 | A kind of carbon/carbon compound material β-Y2Si2O7Nanowire-toughened mullite/silicate glass coating preparation method |
| CN107640976B (en) * | 2016-10-09 | 2019-12-20 | 中国人民解放军国防科学技术大学 | Three-dimensional silicon carbide fiber prefabricated part reinforced yttrium silicate composite material and preparation method thereof |
| CN107640973B (en) * | 2016-10-09 | 2019-12-27 | 中国人民解放军国防科学技术大学 | Three-dimensional carbon fiber prefabricated part reinforced yttrium silicate composite material and preparation method thereof |
| CN107640975B (en) * | 2017-09-01 | 2020-03-17 | 中国人民解放军国防科技大学 | Three-dimensional carbon fiber prefabricated part reinforced yttrium oxide-aluminum oxide composite ceramic composite material and preparation method thereof |
| CN110894164B (en) * | 2018-09-13 | 2021-07-13 | 中国科学院上海硅酸盐研究所 | Rare earth silicate laminar-distributed silicon carbide ceramic matrix composite and preparation method thereof |
| US10927046B2 (en) * | 2018-12-21 | 2021-02-23 | General Electric Company | EBC with mullite bondcoat having a non-oxide silicon ceramic |
| CN113800950B (en) * | 2021-08-27 | 2023-04-07 | 咸阳盈和电子材料有限公司 | Glass coating for surface of silicon carbide rod and preparation method thereof |
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