CN110304946B - Wide-temperature-range antioxidant coating on surface of ceramic matrix composite and preparation method thereof - Google Patents
Wide-temperature-range antioxidant coating on surface of ceramic matrix composite and preparation method thereof Download PDFInfo
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
Abstract
The invention relates to a wide-temperature-range antioxidant coating on the surface of a ceramic matrix composite and a preparation method thereof. The method comprises the following steps: depositing a SiC layer on the surface of the ceramic matrix composite material by a CVD method; preparing phenolic resin slurry containing mixed nano powder filler, curing agent and diluent; the mass ratio of the mixed nano powder filler to the phenolic resin is 1: (0.8-1.2), wherein the mass ratio of the curing agent to the diluent to the phenolic resin is (0.05-0.1): (1-1.5): 1; coating the slurry on the surface of the SiC layer to form a coating, and curing and sintering the ceramic matrix composite material coated with the coating to obtain the wide-temperature-range antioxidant coating. The invention can effectively improve the wide temperature range oxidation resistance of the coating and play an effective protection role on the ceramic matrix composite; the coating prepared by the invention has excellent oxidation resistance in a wide temperature range environment, and has important significance for prolonging the service life of the ceramic matrix composite.
Description
Technical Field
The invention belongs to the technical field of high-temperature protective coatings and preparation, and particularly relates to a wide-temperature-range antioxidant coating on the surface of a ceramic matrix composite and a preparation method thereof.
Background
Nowadays, the fields of aerospace technology and the like are developing towards the direction of ultra-high sound velocity, and the demand for high-temperature protective materials is increasingly urgent. At present, carbides, borides, nitrides and the like are used as ultrahigh-temperature ceramic materials with high frequency in high-temperature protective materials, and the materials generally have high melting points (over 2500 ℃) and stable crystal structures, such as ZrB2、ZrC、HfB2And HfC, which makes them widely used under extreme conditions of high temperature. The study shows that the surfaceThe preparation of the ultrahigh-temperature ceramic coating is an effective way for improving the oxidation resistance and the ablation resistance of the ceramic matrix composite. Because the difference between the thermal expansion coefficients of the ultrahigh-temperature ceramic coating and the matrix is large, a SiC transition layer needs to be added to relieve the thermal stress generated during working. In addition, due to the problem that the ultrahigh-temperature ceramic coating has poor oxidation resistance in a medium-low temperature (500-1200 ℃) environment, research and preparation of a wide-temperature-range oxidation resistant coating from low temperature to high temperature are very necessary.
The main methods for preparing the thermal protection coating are as follows: slurry brush coating-sintering, chemical vapor deposition, embedding infiltration, plasma spraying and the like. The slurry brushing-sintering method has the advantages of simple process, low requirement on the surface of a prepared coating substrate, low requirement on equipment and the like, and can be used for preparing coatings on workpieces with complex shapes, thereby meeting the requirements of many fields. However, the structure and performance of the thermal protective coating prepared by the brush coating method depend on many factors, including slurry component ratio, slurry stirring time, brushing mode, curing temperature, curing time, sintering temperature, sintering time, substrate type and other factors, and the selection of these parameters, especially the improper ratio of the slurry components, the improper selection of the curing and sintering parameters, is not favorable for obtaining the thermal protective coating with excellent performance.
An invention patent CN102010231A published in 2011, 4 and 13 discloses a method for coating the surface of a low-density carbon/carbon composite material, which is used for hole sealing and coating treatment of the surface of a low-density C/C material in a crystalline silicon high-temperature furnace to solve the problem of surface erosion of the low-density carbon material, and the coating is very thin (2-50 microns), so that the low-density carbon/carbon composite material with the surface coating can be suitable for a monocrystalline silicon furnace or a polycrystalline silicon furnace in a vacuum environment with the working temperature of more than 1500 ℃, but the coating prepared by the patent has poor oxidation resistance, cannot be used in a high-temperature aerobic environment and is not suitable for a thermal protection coating on the surface of a ceramic matrix composite material.
Disclosure of Invention
In order to solve the defects of the existing ultrahigh-temperature ceramic coating and slurry brushing-sintering technology, the invention provides a wide-temperature-range antioxidant coating on the surface of a ceramic matrix composite and a ceramic matrix compositeA preparation method and application thereof. The wide temperature range antioxidant coating prepared by the invention comprises a SiC transition layer and a B4C-SiC-ZrB2A surface layer; the wide-temperature-range antioxidant coating prepared by the invention has excellent antioxidant performance in a wide-temperature-range environment, and has important significance for prolonging the service life of the ceramic matrix composite; the method has simple process, and can prepare uniform coating on the workpiece with complex shape surface; the coating has low surface roughness, low porosity, small shrinkage and high bonding strength with the substrate.
In order to achieve the above object, the present invention provides in a first aspect a method for preparing a wide temperature range oxidation resistant coating on a surface of a ceramic matrix composite, the method comprising the steps of:
(1) depositing a SiC transition layer on the surface of the ceramic matrix composite material by a chemical vapor deposition method;
(2) uniformly mixing the mixed nano powder filler with phenolic resin to obtain a mixture, adding a curing agent and a diluent into the mixture, and uniformly mixing to obtain slurry; the mixed nano powder filler comprises, by mass, 40-50% of B powder, 25-35% of Si powder and ZrB220-30% of powder; the mass ratio of the mixed nano powder filler to the phenolic resin is 1: (0.8-1.2), wherein the mass ratio of the usage amounts of the curing agent, the diluent and the phenolic resin is (0.05-0.1): (1-1.5): 1;
(3) coating the slurry obtained in the step (2) on the surface of the SiC transition layer obtained in the step (1) to form a coating;
(4) sequentially curing and sintering the ceramic matrix composite coated with the coating in the step (3), thereby preparing the wide-temperature-range antioxidant coating on the surface of the ceramic matrix composite; the wide temperature range anti-oxidation coating comprises the SiC transition layer and B4C-SiC-ZrB2And (6) a surface layer.
Preferably, in step (4): the curing temperature is 100-130 ℃, and the curing time is 2-5 h; and/or the sintering temperature is 1400-1700 ℃, and the sintering time is 2-4 h.
Preferably, in step (4): the curing is carried out in an atmospheric environment; and/or the sintering is performed under an argon or nitrogen atmosphere.
Preferably, the curing agent is selected from the group consisting of hexamethylenetetramine and triethylenetetramine; the diluent is selected from the group consisting of ethylene glycol, ethanol, and butyl acetate; the phenolic resin is selected from the group consisting of an organosilicon phenolic resin, a titanium-modified phenolic resin, and a silicon-titanium-modified phenolic resin; and/or the particle size of the B powder is 50-100 nm, the particle size of the Si powder is 100-300 nm, and/or the ZrB powder2The particle size of the powder is 300-500 nm.
Preferably, in the step (1), trichloromethylsilane is used as a raw material for depositing the SiC transition layer, the deposition temperature of the SiC transition layer is 900-1000 ℃, and the deposition time of the SiC transition layer is 20-40 h.
Preferably, in the step (2), adding a curing agent and a diluent into the mixture, and then uniformly mixing the mixture by adopting an ultrasonic dispersion mode, wherein the ultrasonic dispersion time is 1-2 h; and/or in the step (3), coating the slurry obtained in the step (2) on the surface of the SiC transition layer obtained in the step (1) by brushing or spraying to form a coating.
Preferably, the ceramic matrix composite is a carbon fiber reinforced silicon carbide ceramic matrix composite, a carbon fiber reinforced carbon-silicon carbide ceramic matrix composite, a carbon fiber reinforced silicon carbide-zirconium carbide ceramic matrix composite or a carbon fiber reinforced silicon carbide-zirconium diboride ceramic matrix composite.
Preferably, the thickness of the SiC transition layer is 20-40 μm; and/or said B4C-SiC-ZrB2The thickness of the surface layer is 80-120 μm.
In a second aspect, the invention provides a wide temperature range anti-oxidation coating on the surface of the ceramic matrix composite material prepared by the preparation method in the first aspect, wherein the wide temperature range anti-oxidation coating comprises the SiC transition layer and B4C-SiC-ZrB2And (6) a surface layer.
In a third aspect, the present invention provides a composite material comprising the broad temperature range antioxidant coating on the surface of the ceramic matrix composite material prepared by the preparation method of the first aspect of the present invention or the broad temperature range antioxidant coating on the surface of the ceramic matrix composite material of the second aspect of the present invention.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the multi-component nano powder filler is introduced into the phenolic resin, the reaction activity of the nano powder is high, the nano powder and the cracked carbon in the resin are utilized to react in situ at high temperature to generate the multi-phase ceramic heat-proof layer, the wide-temperature-range oxidation resistance of the coating can be effectively improved, and the ceramic matrix composite material can be effectively protected.
(2) The invention adopts the nano-scale powder as the filler, and the coating has low shrinkage and less cracks after sintering.
(3) The invention adopts the slurry components with proper proportion to prepare the B through the slurry brushing-sintering technology4C-SiC-ZrB2The surface layer, the inventor finds that when the slurry comprises the following components: the mixed nano powder filler comprises, by mass, 40-50% of B powder, 25-35% of Si powder and ZrB220-30% of powder, and the mass ratio of the mixed nano powder filler to the phenolic resin is 1: (0.8-1.2), wherein the mass ratio of the usage amounts of the curing agent, the diluent and the phenolic resin is (0.05-0.1): (1-1.5): 1, the wide temperature range antioxidant coating with excellent antioxidant performance in wide temperature range environment is ensured to be prepared.
(4) The invention discovers parameters more suitable for curing and sintering the coating through a large number of tests on the basis of adopting slurry components with proper proportion, and discovers that the invention is more favorable for ensuring the preparation of the wide-temperature-range antioxidant coating with excellent oxidation resistance in the wide-temperature-range environment when the curing temperature is 100-130 ℃, the curing time is 2-5h, the sintering temperature is 1400-1700 ℃ and the sintering time is 2-4 h on the basis of the slurry components.
(5) The wide-temperature-range antioxidant coating prepared by the invention has excellent antioxidant performance in a wide-temperature-range environment, and has important significance for prolonging the service life of the ceramic matrix composite.
(6) The invention has simple process and good repeatability, and can prepare the coating on the workpiece with the complex shape surface; the coating is uniform, the surface roughness is low, the porosity is low, the shrinkage rate is small, and the bonding strength with the matrix is high.
Drawings
FIG. 1 is a schematic cross-sectional view of the wide temperature range oxidation resistant coating formed on the surface of a ceramic matrix composite according to an embodiment of the present invention.
FIG. 2 is a cross-sectional micro-topography (SEM) of the wide temperature range oxidation resistant coating on the surface of the ceramic matrix composite according to example 1 of the present invention. In the figure, epoxy was used to inlay the wide temperature range oxidation resistant coating during testing.
FIG. 3 shows that the anti-oxidation coating with wide temperature range prepared on the surface of the ceramic matrix composite in example 1 of the present invention includes B4C-SiC-ZrB2X-ray diffraction pattern of the surface layer. In the figure, the abscissa 2Theta represents twice the diffraction angle in degrees (deg.), and the ordinate intensity (cps) represents the number of photons collected per second (cps) as the diffraction intensity, wherein cps is an abbreviation for counts per second, and sic (cubic) represents cubic silicon carbide.
In fig. 1:1: a ceramic matrix composite; 2: a SiC transition layer; 3: b is4C-SiC-ZrB2And (6) a surface layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of a wide-temperature-range antioxidant coating on the surface of a ceramic matrix composite material, which comprises the following steps:
(1) depositing a SiC transition layer (SiC ceramic transition layer) on the surface of the ceramic matrix composite material by a chemical vapor deposition method (CVD method);
(2) uniformly mixing the mixed nano powder filler with phenolic resin to obtain a mixture, adding a curing agent and a diluent into the mixture, and uniformly mixing to obtain slurry; the mixed nano powder filler comprises, by mass, 40-50% (e.g., 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49% or 50%) of B powder (boron powder), 25-35% (e.g., 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% or 35%) of Si powder (silicon powder), and ZrB220-30% (e.g., 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%) of a powder (zirconium diboride powder); the mass ratio of the mixed nano powder filler to the phenolic resin is 1: (0.8-1.2) (e.g., 1:0.8, 1:0.9, 1:1, 1:1.1, or 1:1.2), wherein the mass ratio of the curing agent, the diluent, and the phenolic resin is (0.05-0.1): (1-1.5): 1 (e.g., 0.05:1:1, 0.05:1.1:1, 0.05:1.2:1, 0.05:1.3:1, 0.05:1.4:1, 0.05:1.5:1, 0.08:1:1, 0.08:1.1:1, 0.08:1.2:1, 0.08:1.3:1, 0.08:1.4:1, 0.08:1.5:1, 0.1:1:1, 0.1:1.1:1, 0.1:1.2:1, 0.1:1.3:1, 0.1:1.4:1, or 0.1:1.5: 1); in the present invention, zirconium diboride (ZrB) is also used2) Recording as zirconium boride;
(3) coating the slurry obtained in the step (2) on the surface of the SiC transition layer obtained in the step (1) to form a coating;
(4) sequentially curing and sintering (high-temperature sintering) the ceramic matrix composite coated with the coating in the step (3), so as to prepare the wide-temperature-range antioxidant coating on the surface of the ceramic matrix composite; the wide temperature range anti-oxidation coating comprises the SiC transition layer (silicon carbide transition layer) and B4C-SiC-ZrB2Surface layer (B)4C-SiC-ZrB2Ceramic top layer or B4C-SiC-ZrB2A complex phase ceramic facing or a boron carbide-silicon carbide-zirconium diboride facing); for example, one embodiment of the present invention provides for the broad temperature range oxidation resistance of the ceramic matrix composite surfaceThe cross-sectional structure of the coating is schematically shown in fig. 1.
In the invention, the wide temperature range antioxidant coating firstly adopts the SiC coating as a transition layer to relieve the thermal stress of the ceramic surface layer and the ceramic matrix composite substrate in high-temperature use, and simultaneously SiC (silicon carbide) generates SiO after high-temperature oxidation2The (silicon dioxide) glass phase is filled in the gaps and the cracks, so that the self-healing function can be realized; secondly, use of B4C-SiC-ZrB2A (boron carbide-silicon carbide-zirconium diboride) complex phase system as a ceramic surface layer, wherein B4C (boron carbide) is an antioxidant component at medium and low temperature (500-1200 ℃), and B is formed after oxidation2O3(diboron trioxide) densifies the glass body, reducing the rate of oxidation; SiC bonded ZrB2(zirconium diboride) (1200-2200 ℃) is a medium-high temperature antioxidant component, and ZrO is formed after oxidation2ZrO with (zirconium dioxide) crystal as skeleton2-SiO2The (zirconium dioxide-silicon dioxide) dense layer reduces the oxidation rate, thereby playing an effective protection role for the ceramic matrix composite material in a wide temperature range environment.
The multi-component nano powder filler is introduced into the phenolic resin, the reaction activity of the nano powder is high, the nano powder and the cracked carbon in the resin are utilized to react in situ at high temperature to generate the multi-phase ceramic heat-proof layer, the wide-temperature-range oxidation resistance of the coating can be effectively improved, and the ceramic matrix composite material can be effectively protected. The B consisting of boron carbide, silicon carbide and zirconium boride is prepared by adopting slurry components with proper proportion through a slurry brushing-sintering in-situ reaction method4C-SiC-ZrB2The inventor finds that when the slurry comprises the following components in proportion: the mixed nano powder filler comprises, by mass, 40-50% of B powder, 25-35% of Si powder and ZrB220-30% of powder, and the mass ratio of the mixed nano powder filler to the phenolic resin is 1: (0.8-1.2), wherein the mass ratio of the usage amounts of the curing agent, the diluent and the phenolic resin is (0.05-0.1): (1-1.5): 1, the wide temperature range antioxidant coating with excellent antioxidant performance in wide temperature range environment is ensured to be prepared. The double-layer composite ceramic of the inventionThe ceramic coating has low porosity and excellent oxidation resistance in a wide temperature range, and the method has the advantages of low cost, high efficiency, simple and controllable operation process and the like, and can quickly prepare a compact oxidation-resistant coating in the wide temperature range on the surface of the ceramic matrix composite substrate.
According to some preferred embodiments, in step (4): the curing temperature is 100-130 ℃ (such as 100 ℃, 110 ℃, 120 ℃ or 130 ℃), and the curing time is 2-5h (such as 2, 2.5, 3, 3.5, 4, 4.5 or 5 h); and/or the sintering temperature is 1400-1700 ℃ (such as 1400 ℃, 1450 ℃, 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃ or 1700 ℃), and the sintering time is 2-4 h (such as 2, 2.5, 3, 3.5 or 4 h). On the basis of adopting slurry components with proper proportion, a large number of tests prove that the coating is more suitable for curing and sintering parameters, and the invention proves that on the basis of the slurry components, when the curing temperature is 100-130 ℃, the curing time is 2-5h, the slurry is more favorably cured, and when the sintering temperature is 1400-1700 ℃, the sintering time is 2-4 h, the wide-temperature-range antioxidant coating with excellent antioxidant performance in the wide-temperature-range environment is more favorably ensured to be prepared; if the sintering temperature is too low, the sintering time is too short, which is not beneficial to the in-situ reaction of the nano powder and the cracked carbon in the resin at high temperature to generate the multiphase ceramic heat-proof layer, while if the sintering temperature is too high, the sintering time is too long, which can cause the waste of resources on one hand and cause the too large thermal stress in the sintering process to easily cause the cracking of the wide-temperature-range oxidation-resistant coating on the other hand.
According to some preferred embodiments, in step (4): the curing is carried out in an atmospheric environment; and/or the sintering is performed under an argon or nitrogen atmosphere.
According to some preferred embodiments, the curing agent is selected from the group consisting of hexamethylenetetramine and triethylenetetramine; the diluent is selected from the group consisting of ethylene glycol, ethanol, and butyl acetate; the phenolic resin is selected from organosilicon phenolic resin (organosilicon modified phenolic resin)) The phenolic resin is one or more of organic silicon phenolic resin, titanium modified phenolic resin and silicon-titanium modified phenolic resin (Si-Ti modified phenolic resin); and/or the particle size of the B powder is 50-100 nm, the particle size of the Si powder is 100-300 nm, and/or the ZrB powder2The particle size of the powder is 300-500 nm. In the present invention, the term "selected from the group consisting of …" means "one or more selected from …".
According to some preferred embodiments, in the step (1), trichloromethylsilane (trichloromethylsilane vapor) is used as a raw material for depositing the SiC transition layer, the deposition temperature of the SiC transition layer is 900-1000 ℃, and the deposition time of the SiC transition layer is 20-40 h.
According to some preferred embodiments, in the step (2), after the curing agent and the diluent are added into the mixture, the mixture is uniformly mixed in an ultrasonic dispersion mode, wherein the ultrasonic dispersion time is 1-2 hours; and/or in the step (3), coating the slurry obtained in the step (2) on the surface of the SiC transition layer obtained in the step (1) by brushing or spraying to form a coating.
According to some preferred embodiments, the ceramic matrix composite is a carbon fiber reinforced silicon carbide ceramic matrix composite (C)fSiC ceramic matrix composite), carbon fiber reinforced carbon-silicon carbide ceramic matrix composite (C)fa/C-SiC ceramic matrix composite), a carbon fiber-reinforced silicon carbide-zirconium carbide ceramic matrix composite (C)f/SiC-ZrC ceramic matrix composite) or carbon fiber reinforced silicon carbide-zirconium diboride ceramic matrix composite (Cf/SiC-ZrB2Ceramic matrix composite).
According to some preferred embodiments, the thickness of the SiC transition layer is 20-40 μm; and/or said B4C-SiC-ZrB2The thickness of the surface layer is 80-120 μm.
According to some specific embodiments, the preparation process of the wide temperature range antioxidant coating of the present invention is as follows:
s1, preparing a SiC ceramic transition layer by adopting chemical vapor deposition (hereinafter referred to as CVD);
s2, slurry preparation: mixing the mixed nano powder filler with phenolic resin according to the proportion of 1: (0.8-1.2), adding a proper amount of hexamethylene tetramine curing agent and glycol diluent, and mixing in an ultrasonic dispersion mode until the powder filler in the slurry is completely dissolved and no obvious bubbles exist; wherein the mixed nano powder filler comprises, by mass, 40-50% of B powder, 25-35% of Si powder and ZrB220-30% of powder; the mass ratio of the usage amounts of the curing agent, the diluent and the phenolic resin is (0.05-0.1): (1-1.5): 1;
s3, coating the coating slurry obtained in the step S2 on the surface of the SiC transition layer in a brush brushing or compressed air spraying mode to form a coating;
s4, placing the sample piece with the coating in the step S3 in an oven, and curing for 2-5 hours at 100-130 ℃ in an atmospheric environment;
and S5, placing the solidified sample piece in the step S4 in a high-temperature furnace, sintering under the protection of inert gases such as argon or nitrogen, cooling along with the furnace, and taking out to obtain the wide-temperature-range antioxidant coating (the wide-temperature-range antioxidant complex phase coating).
In a second aspect, the invention provides a wide temperature range anti-oxidation coating on the surface of the ceramic matrix composite material prepared by the preparation method in the first aspect, wherein the wide temperature range anti-oxidation coating comprises the SiC transition layer and B4C-SiC-ZrB2And (6) a surface layer. Namely, in the invention, the wide-temperature-range antioxidant coating comprises a SiC transition layer and B consisting of boron carbide, silicon carbide and zirconium boride which are sequentially formed on the surface of the ceramic matrix composite material4C-SiC-ZrB2And (6) a surface layer.
In a third aspect, the present invention provides a composite material comprising the broad temperature range antioxidant coating on the surface of the ceramic matrix composite material prepared by the preparation method of the first aspect of the present invention or the broad temperature range antioxidant coating on the surface of the ceramic matrix composite material of the second aspect of the present invention.
The present invention will be further described with reference to the following examples. These examples are merely illustrative of preferred embodiments of the present invention and the scope of the present invention should not be construed as being limited to these examples.
Example 1
The invention adopts the chemical vapor deposition combined with the slurry brush coating-sintering technology to prepare the SiC transition layer + B on the surface of the ceramic matrix composite material4C-SiC-ZrB2And (3) a ceramic surface layer.
The embodiment provides a preparation method of a wide-temperature-range antioxidant coating on the surface of a ceramic matrix composite, which comprises the following specific steps:
s1, preparation CfThe SiC ceramic matrix composite material substrate original sheet is characterized in that the size of the SiC ceramic matrix composite material substrate original sheet is phi 30 multiplied by 10mm (the diameter is 30mm, the thickness is 10mm), the surfaces of the SiC ceramic matrix composite material substrate original sheet are respectively polished on 400#, 800# and 1200# sandpaper, and the SiC ceramic matrix composite material substrate original sheet is put into acetone to be subjected to ultrasonic cleaning for 10min for later use.
S2, mixing CfAnd placing the/SiC ceramic matrix composite material in a high-temperature furnace, heating to 1000 ℃, taking trichloromethylsilane steam as a raw material for preparing the SiC coating, depositing for 40 hours, and taking out a sample after the temperature in the furnace is reduced to room temperature.
S3, mixing 40 wt.% of B powder, 30 wt.% of Si powder and 30 wt.% of ZrB2After the powders are mixed, 5g of mixed nano powder filler is uniformly mixed with 5g of Si-Ti modified phenolic resin, 0.3g of hexamethylenetetramine curing agent and 5g of ethylene glycol diluent are added, ultrasonic dispersion is carried out for 1h, and the mixed powder filler in the slurry is completely dissolved without obvious bubbles.
And S4, dipping the slurry by using an oil painting brush, and uniformly brushing the slurry on the surface of the SiC transition layer.
And S5, placing the sample piece after being coated by the brush into an oven, and curing for 4 hours at 130 ℃ in an atmospheric environment.
S6, placing the solidified sample in a high-temperature furnace, preserving heat for 2 hours at 1500 ℃ under the protection of argon, cooling the sample along with the furnace, and taking out the cooled sample to obtain the wide-temperature-range antioxidant coating (SiC/B)4C-SiC-ZrB2A coating).
For prepared SiC/B4C-SiC-ZrB2The porosity, bonding strength and high-temperature oxidation resistance of the coating are tested. Measurement of B by mercury intrusion4C-SiC-ZrB2Porosity of the coating<5 percent. According to the determination of G/T8642-2002 thermal spraying and tensile bonding strength, an electronic material testing machine is adopted to test B4C-SiC-ZrB2The bonding strength of the coating is about 8.0 +/-1.0 MPa, which indicates that the coating prepared by the brush coating-sintering method has good bonding force. For coating of SiC/B in the present example4C-SiC-ZrB2C of the coatingfThe high-temperature oxidation resistance test of the/SiC ceramic matrix composite material shows that the mass loss rate of the sample after being oxidized for 10 hours at 1000 ℃ is 1.1 percent, the mass loss rate of the sample after being oxidized for 10 hours at 1500 ℃ is 3.1 percent, and the full description shows that the SiC/B coating is applied4C-SiC-ZrB2After coating, obviously improve CfThe anti-oxidation performance of the/SiC ceramic matrix composite material in a wide temperature range.
Example 2
Example 2 is essentially the same as example 1, except that:
in step S3, 20 wt.% B powder, 40 wt.% Si powder, 40 wt.% ZrB powder2After the powders are mixed, 5g of mixed nano powder filler is uniformly mixed with 5g of Si-Ti modified phenolic resin, 0.3g of hexamethylenetetramine curing agent and 5g of ethylene glycol diluent are added, ultrasonic dispersion is carried out for 1h, and the mixed powder filler in the slurry is completely dissolved without obvious bubbles.
Coated with SiC/B prepared in this example4C-SiC-ZrB2C of the coatingfThe oxidation resistance results of the/SiC ceramic matrix composite material are shown in Table 1.
Example 3
Example 3 is essentially the same as example 1, except that:
in step S3, 40 wt.% B powder, 30 wt.% Si powder, 30 wt.% ZrB powder2After the powders are mixed, 5g of mixed nano powder filler is uniformly mixed with 7.5g of Si-Ti modified phenolic resin, 0.3g of hexamethylenetetramine curing agent and 5g of ethylene glycol diluent are added, ultrasonic dispersion is carried out for 1h, and the mixed powder filler in the slurry is completely dissolved without obvious bubbles.
Coated with SiC/B prepared in this example4C-SiC-ZrB2C of the coatingfThe oxidation resistance results of the/SiC ceramic matrix composite material are shown in Table 1.
Example 4
Example 4 is essentially the same as example 1, except that:
in step S3, 40 wt.% B powder, 30 wt.% Si powder, 30 wt.% ZrB powder2After the powders are mixed, 5g of mixed nano powder filler is uniformly mixed with 3g of Si-Ti modified phenolic resin, 0.3g of hexamethylenetetramine curing agent and 5g of ethylene glycol diluent are added, ultrasonic dispersion is carried out for 1h, and the mixed powder filler in the slurry is completely dissolved without obvious bubbles.
Coated with SiC/B prepared in this example4C-SiC-ZrB2C of the coatingfThe oxidation resistance results of the/SiC ceramic matrix composite material are shown in Table 1.
Example 5
Example 5 is essentially the same as example 1, except that:
in step S5, the sample piece after brush coating is placed in an oven and cured for 2h at 160 ℃ in an atmospheric environment.
In step S6, the solidified sample is placed in a high temperature furnace, heat preservation is carried out for 2 hours at 2000 ℃ under the protection of argon gas, the sample is taken out after being cooled along with the furnace, and SiC/B is obtained4C-SiC-ZrB2Coating of SiC/B4C-SiC-ZrB2The surface of the coating has cracks.
Coated with SiC/B prepared in this example4C-SiC-ZrB2C of the coatingfThe oxidation resistance results of the/SiC ceramic matrix composite material are shown in Table 1.
Comparative example 1
S1, preparation CfThe SiC ceramic matrix composite material substrate original sheet is characterized in that the size of the SiC ceramic matrix composite material substrate original sheet is phi 30 multiplied by 10mm (the diameter is 30mm, the thickness is 10mm), the surfaces of the SiC ceramic matrix composite material substrate original sheet are respectively polished on 400#, 800# and 1200# sandpaper, and the SiC ceramic matrix composite material substrate original sheet is put into acetone to be subjected to ultrasonic cleaning for 10min for later use.
S2, mixing CfAnd placing the/SiC ceramic matrix composite material in a high-temperature furnace, heating to 1000 ℃, taking trichloromethylsilane steam as a raw material for preparing the SiC coating, depositing for 40 hours, and taking out a sample after the temperature in the furnace is reduced to room temperature.
S3, 40 wt.% B powder, 30wt. -%)Si powder and 30 wt.% ZrB2The powder is uniformly mixed to obtain mixed powder, and then 5g of the mixed powder is put into a powder feeder of vacuum plasma spraying equipment for drying treatment.
S4, preparing the complex phase ceramic surface layer by adopting a vacuum plasma spraying method.
C with SiC/Complex phase ceramic Top coat prepared in this comparative examplefThe oxidation resistance results of the/SiC ceramic matrix composite material are shown in Table 1.
Table 1: performance index for examples 1-5 and comparative example 1.
Finally, the description is as follows: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the embodiments can still be modified, or some technical features can be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the present invention in its spirit and scope.
Claims (9)
1. A preparation method of a wide temperature range antioxidant coating on the surface of a ceramic matrix composite is characterized by comprising the following steps:
(1) depositing a SiC transition layer on the surface of the ceramic matrix composite material by a chemical vapor deposition method;
(2) uniformly mixing the mixed nano powder filler with phenolic resin to obtain a mixture, adding a curing agent and a diluent into the mixture, and uniformly mixing to obtain slurry; the mixed nano powder filler comprises, by mass, 40-50% of B powder, 25-35% of Si powder and ZrB220-30% of powderForming; the mass ratio of the mixed nano powder filler to the phenolic resin is 1: (0.8-1.2), wherein the mass ratio of the usage amounts of the curing agent, the diluent and the phenolic resin is (0.05-0.1): (1-1.5): 1; the grain diameter of the B powder is 50-100 nm, the grain diameter of the Si powder is 100-300 nm, and the ZrB powder2The particle size of the powder is 300-500 nm;
(3) coating the slurry obtained in the step (2) on the surface of the SiC transition layer obtained in the step (1) to form B4C-SiC-ZrB2A surface layer;
(4) coating the step (3) with the B4C-SiC-ZrB2Sequentially curing and sintering the ceramic matrix composite material of the surface layer, thereby preparing the wide-temperature-range antioxidant coating on the surface of the ceramic matrix composite material; the wide temperature range anti-oxidation coating comprises the SiC transition layer and the B4C-SiC-ZrB2A surface layer; the curing temperature is 100-130 ℃, and the curing time is 2-5 h; the sintering temperature is 1400-1700 ℃, and the sintering time is 2-4 h.
2. The production method according to claim 1, wherein in step (4):
the curing is carried out in an atmospheric environment; and/or
The sintering is performed under an argon or nitrogen atmosphere.
3. The production method according to claim 1 or 2, characterized in that:
the curing agent is selected from the group consisting of hexamethylenetetramine and triethylenetetramine;
the diluent is selected from the group consisting of ethylene glycol, ethanol, and butyl acetate;
the phenolic resin is selected from the group consisting of an organosilicon phenolic resin, a titanium-modified phenolic resin, and a silicon-titanium-modified phenolic resin.
4. The production method according to claim 1 or 2, characterized in that:
in the step (1), trichloromethylsilane is used as a raw material for depositing the SiC transition layer, the deposition temperature of the SiC transition layer is 900-1000 ℃, and the deposition time of the SiC transition layer is 20-40 h.
5. The production method according to claim 1 or 2, characterized in that:
in the step (2), adding a curing agent and a diluent into the mixture, and then uniformly mixing the mixture by adopting an ultrasonic dispersion mode, wherein the ultrasonic dispersion time is 1-2 h; and/or
In the step (3), the slurry obtained in the step (2) is coated on the surface of the SiC transition layer obtained in the step (1) by brushing or spraying to form a coating.
6. The production method according to claim 1 or 2, characterized in that:
the ceramic matrix composite material is a carbon fiber reinforced silicon carbide ceramic matrix composite material, a carbon fiber reinforced carbon-silicon carbide ceramic matrix composite material, a carbon fiber reinforced silicon carbide-zirconium carbide ceramic matrix composite material or a carbon fiber reinforced silicon carbide-zirconium diboride ceramic matrix composite material.
7. The production method according to claim 1 or 2, characterized in that:
the thickness of the SiC transition layer is 20-40 mu m; and/or
B is4C-SiC-ZrB2The thickness of the surface layer is 80-120 μm.
8. The wide temperature range antioxidant coating on the surface of the ceramic matrix composite prepared by the preparation method of any one of claims 1 to 7 is characterized in that:
the wide temperature range anti-oxidation coating comprises the SiC transition layer and B4C-SiC-ZrB2And (6) a surface layer.
9. Composite material comprising a wide temperature range oxidation resistant coating on the surface of the ceramic matrix composite material prepared by the preparation method according to any one of claims 1 to 7.
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