CN113087530A - ZrB-based2Nonequilibrium state alloying modified high oxygen resistant coating and preparation method thereof - Google Patents

ZrB-based2Nonequilibrium state alloying modified high oxygen resistant coating and preparation method thereof Download PDF

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CN113087530A
CN113087530A CN202110416686.2A CN202110416686A CN113087530A CN 113087530 A CN113087530 A CN 113087530A CN 202110416686 A CN202110416686 A CN 202110416686A CN 113087530 A CN113087530 A CN 113087530A
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powder
zrb
precursor
alloying
high oxygen
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任宣儒
张盟林
冯培忠
杨青青
阚腾飞
陈跃星
吴彬彬
王炜光
王乐雨
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China University of Mining and Technology CUMT
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Abstract

The invention discloses a ZrB-based optical fiber cable2The non-equilibrium alloying modified high oxygen resistant coating and the preparation method are suitable for the technical field of carbon materials. According to mass fraction: 5-30 percent of zirconium powder, 5-30 percent of molybdenum powder, 10-60 percent of silicon powder and 10-60 percent of boron powder are mixed and made into a cylindrical blank, and a nonequilibrium alloying precursor ZrB with alloying characteristics is prepared and obtained in a combustion synthesis reaction kettle by a self-propagating high-temperature synthesis method2‑MoSi2A mixture of ZrB2‑MoSi2Crushing and drying the mixture, wrapping the nonequilibrium alloying precursor outside a carbon substrate needing to prepare the high oxygen resistant coating by using a mould, and then coating the carbon substratePerforming spark plasma SPS sintering to finally generate ZrB on the surface of the carbon matrix2‑MoSi2High oxygen barrier coating. The method is simple and practical, and ZrB can be remarkably improved2‑MoSi2The oxidation resistance of the coating improves the oxidation protection of the carbon substrate, and the coating has excellent comprehensive performance and wide development prospect.

Description

ZrB-based2Nonequilibrium state alloying modified high oxygen resistant coating and preparation method thereof
Technical Field
The invention relates to a high oxygen barrier coating and a preparation method thereof, in particular to a ZrB-based coating which is suitable for the technical field of carbon materials2A non-equilibrium alloying modified high oxygen resistant coating and a preparation method thereof.
Background
The carbon structural material (C/C composite material or graphite) is used as an indispensable structural material in the fields of national defense and civil use and widely applied to aerospace high-temperature components due to the advantages of low density, high specific strength, good mechanical property, good thermal shock resistance and the like. However, the characteristic of easy oxidation in air at a temperature of above 400 ℃ severely restricts the application of the carbon structure material. Therefore, the coating technology is the best choice for improving the high-temperature performance of the carbon structure material.
In recent years ZrB2High melting point and chemical stability make it of great interest in the field of oxidation resistant coatings, however, ZrB2Oxidation product B2O3The release of the organic silicon compound can lead the coating to be loose and porous, the oxygen-blocking structure of the coating is lost, and defects such as air holes, cracks and the like are generated. At present, to promote ZrB2Due to MoSi2The ZrB is prepared by researchers at home and abroad by coating preparation processes such as an embedding method, an in-situ reaction method, a spraying method, a slurry method and the like2-MoSi2Coating by MoSi2Glass film pair ZrB formed by oxidation2The sealing protection can obviously reduce the oxidation loss.
Document 1 "y.jiang, d.feng, h.q.ru, et.al.oxidation protective ZrB2-MoSi2-SiC-Si coating for graphite materials prepared by slurry dipping and vapor silicon infiltration[J].Surface&Coatings Technology,2018,339:91-100 ", reported the preparation of dense monolayer ZrB on the surface of a graphite substrate using slurry and gas phase siliconizing2-MoSi2-SiC-Si coating. After the coating is oxidized in air at 1600 ℃ for 150 hours, the weight loss rate of the coating is only 0.21 percent, and the weight gain is 0.11 percent after 100 cycles of thermal shock between room temperature and 1200 ℃.
Document 2 "W.Z.Zhang, Y.Zeng, L.Gblogah, et.al.preparation and oxidation property of ZrB2-MoSi2/SiC coating on carbon/carbon composites[J]Transactions of non-ferrous Metals societyofChina, 2011, 21:1538-2-MoSi2And (4) an outer coating. The results show that ZrB was obtained after oxidation at 1000 ℃ and 1500 ℃ for 30h and 10h2-MoSi2The mass loss of the/SiC-coated samples was 5.3% and 3.0%, respectively.
Document 3 "y.r.niu, h.y.wang, z.w.liu, et al2-MoSi2composite coatings atmiddle andhightemperatures[J].Surface&Coatings Technology,2015,273:30-38 ", reported the preparation of different MoSi using low pressure plasma spray Technology2Content ZrB2And (3) base composite coating. The result shows that ZrB2-40vol.％MoSi2The total oxide layer thickness of the coating after being oxidized for 6h at 1200 ℃ is about 17-22 μm, and the total oxide layer thickness after being oxidized for 6h at 1500 ℃ is about 264-270 μm. Thus, ZrB2Phase and MoSi2The composition of the phases can make full use of MoSi2Film forming ability of (2) with ZrB2Oxidation products of phases of transition metal oxides and B2O3Fusing to form a complex phase glass layer, reducing oxygen permeability and improving ZrB2Antioxidant protection of the phases.
However, in the current preparation method, the raw materials of the coating are mainly mechanically mixed, so that the phases in the coating are difficult to uniformly mix, and ZrB in the coating is greatly influenced2Phase and MoSi2Uniformity of distribution of the phases. Non-uniform distribution of MoSi once oxygen has entered the interior of the coating2It is difficult to provide ZrB in the first time2Thereby weakening ZrB2Relative MoSi2The protection of the phase greatly influences the deep promotion of the oxygen resistance of the coating.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a ZrB-based material2The preparation method of the nonequilibrium alloying modified high oxygen resistant coating is simple, and the MoSi is strengthened by combining the self-propagating high-temperature synthesis and the SPS hot-pressing sintering2And ZrB2The chemical bond of (1) overcomes the non-uniformity of the traditional mechanical mixing mode and improves the MoSi2To ZrB2The oxidation resistance of the coating to the carbon matrix is enhanced.
The technical scheme adopted by the invention is as follows: ZrB-based alloy material of the invention2A non-equilibrium state alloying precursor, which comprises the following components in percentage by mass: 5-30 percent of zirconium, 5-30 percent of molybdenum, 10-60 percent of silicon and 10-60 percent of boron are mixed to prepare a cylindrical blank, and a non-equilibrium alloying precursor ZrB with alloying characteristics is prepared in a combustion synthesis reaction kettle by a self-propagating high-temperature synthesis method2-MoSi2A mixture of (a).
Use based on ZrB2The preparation method of the modified high oxygen barrier coating of the nonequilibrium alloying precursor comprises the following steps: the non-equilibrium alloyed precursor ZrB obtained by preparation2-MoSi2Crushing and drying the mixture, wrapping the nonequilibrium alloying precursor outside a carbon substrate needing to prepare the high oxygen resistance coating by using a mold, performing Spark Plasma (SPS) sintering on the carbon substrate, and finally generating ZrB on the surface of the carbon substrate2-MoSi2High oxygen barrier coating.
ZrB-based2Nonequilibrium state alloying modified high resistanceThe preparation method of the oxygen coating comprises the following specific steps:
s1 batching and mixing: zirconium powder, silicon powder, molybdenum powder and boron powder are used as raw materials, and the mass fraction is as follows: weighing raw material powder of 5-30% of zirconium, 5-30% of molybdenum, 10-60% of silicon and 10-60% of boron, and mixing the raw material powder by using a ball mill to fully and uniformly mix the powder;
s2 press forming: drying the uniformly mixed powder, pouring the dried powder into a steel mould, pressurizing the powder in the steel mould under the conditions that the pressure is 20-200 MPa and the pressure maintaining time is 5-60 s, and performing cold pressing molding on the powder by a tablet press to form a cylindrical blank which is used as a precursor required by combustion synthesis;
s3 synthesis of non-equilibrium alloyed precursors: firstly, putting a pressed cylindrical blank into a combustion synthesis reaction kettle, and attaching an upper column cap of a pressed blank to a molybdenum resistance wire; then filling Ar gas into the reaction kettle to perform inert protection on the mixed material in the cylindrical blank; preheating the cylindrical blank by electrically heating the molybdenum wire until the self-propagating reaction of the cylindrical blank is initiated; turning off the resistance wire power supply after the cylindrical blank begins to burn and synthesize the reaction, waiting for the reaction to be complete and cooling to obtain a completely reacted nonequilibrium precursor ZrB2-MoSi2A mixture of (1);
s4, crushing the obtained non-equilibrium state precursor after combustion synthesis for 5-200 min by adopting a crusher, and then putting the precursor into an oven for drying;
s5, treating the surface of the carbon matrix to which the high oxygen resistant coating is to be added: polishing the carbon substrate by using 400-mesh sand paper until the surface is smooth, then ultrasonically cleaning by using alcohol, and finally drying in an oven;
s6 die filling: fully wrapping the carbon matrix treated in the step (5) by using the non-equilibrium precursor obtained in the step (3) in a graphite mold, specifically, firstly filling a layer of non-equilibrium precursor in the graphite mold, then putting the carbon matrix, and then refilling a layer of non-equilibrium precursor to realize that the carbon matrix is uniformly wrapped by precursor powder; the thickness of the wrapping layer is set according to the requirement;
s7, performing spark plasma SPS sintering: putting the graphite mould into an SPS sintering furnace for sintering treatmentThe temperature is 1200-1900 ℃, the heating rate is 5-200 ℃/min, the pressure is 5-50 MPa, the heat preservation time is 5-min300min, and finally the ZrB is prepared on the surface of the carbon matrix2-MoSi2High oxygen barrier coating.
Furthermore, the granularity of the zirconium is less than or equal to 45 mu m, the purity is more than or equal to 99.9 percent, the granularity of the molybdenum is less than or equal to 3 mu m, the purity is more than or equal to 99.95 percent, the granularity of the silicon is less than or equal to 40 mu m, the purity is more than or equal to 99.9 percent, the granularity of the boron is less than or equal to 3 mu m, and the purity is more than or equal to.
Further, the carbon matrix is graphite or a C/C composite material.
Further, the zirconium, molybdenum, silicon and boron used in the step S1 are pulverized by a ball mill, the rotation speed of the ball mill is 50-1000r/min, and the ball milling time is 0.5-10 hours.
Further, in step S6, the thickness of the non-equilibrium precursor powder covered around the substrate is controlled by controlling the mass of the filling precursor powder, and is about 0.1 to 3 times the thickness of the carbon substrate.
Compared with the prior art, the invention has the beneficial effects that:
1) one-step synthesis of metallized precursor MoSi with chemical bond by using zirconium powder, silicon powder, molybdenum powder and boron powder2-ZrB2The problem of phase distribution nonuniformity in the coating caused by the traditional mechanical mixing is solved.
2)MoSi2-ZrB2Alloyed ZrB of2Oxidation will generate B2O3Gas, MoSi when gas inside the coating is volatilized outside2Formed SiO2The glass film has the function of sealing and inerting, can block the volatilization of oxygen and prevent the generation of air holes for the external oxygen to enter, thereby realizing the protection effect;
3) the non-equilibrium state of the alloying powder is realized by the rapid synthesis process of self-propagating high-temperature synthesis, the compactness of the coating can be improved, and the oxygen permeation into ZrB is reduced2Oxidation corrosion of (2).
4) MoSi with chemical linkage2-ZrB2The alloying powder strengthens the chemical bond connection of the non-equilibrium alloying precursor in the SPS hot-pressing sintering mode, and further strengthens the chemical bond connection of the non-equilibrium alloying precursorEnhanced MoSi2To ZrB2Phase modification and protection effect, and improvement of ZrB2Antioxidant protection of the phases.
5) By combining the self-propagating high-temperature synthesis of the non-equilibrium alloying precursor with SPS hot-pressing sintering, the sintering of the coating at a lower temperature can be realized, and the influence of abnormal growth of crystal grains on the performance of the coating is inhibited.
6. The method is simple and practical, and can obviously improve ZrB2-MoSi2The oxidation resistance of the coating improves the oxidation protection of the carbon substrate, and the coating has excellent comprehensive performance and wide development prospect.
Drawings
FIG. 1 is an XRD pattern of a ZM1 non-equilibrium precursor powder prepared in example 1 of the present invention;
FIG. 2 is a high resolution TEM image of a ZM1 non-equilibrium precursor powder prepared in example 1 of the present invention;
FIG. 3 is a cross-sectional SEM photograph of a ZM1 high oxygen barrier coating on the surface of a carbon substrate prepared in example 1 of the present invention after being oxidized at 1700 ℃ for 100 min;
FIG. 4 is an XRD pattern of a ZM2 non-equilibrium precursor powder prepared in example 2 of the present invention;
FIG. 5 is a high resolution TEM image of a ZM2 non-equilibrium precursor powder prepared in example 2 of the present invention;
FIG. 6 is a cross-sectional SEM photograph of a ZM2 high oxygen barrier coating on the surface of a carbon substrate prepared in example 2 of the present invention after being oxidized at 1700 ℃ for 100 min;
FIG. 7 is an XRD pattern of a ZM3 non-equilibrium precursor powder prepared in example 3 of the present invention;
FIG. 8 is a high resolution TEM image of a ZM3 non-equilibrium precursor powder prepared in example 3 of the present invention;
FIG. 9 is a cross-sectional SEM photograph of a ZM3 high oxygen barrier coating on the surface of a carbon substrate prepared in example 3 of the present invention after being oxidized at 1700 ℃ for 100 min;
in the figure: 1-complex phase glass layer, 2-unoxidized coating and 3-carbon substrate.
Detailed Description
For a better understanding of the present invention, reference is made to the following description taken in conjunction with the accompanying drawings and examples in which:
the invention discloses a ZrB-based optical fiber cable2A non-equilibrium state alloying precursor, which comprises the following components in percentage by mass: 5-30 percent of zirconium powder, 5-30 percent of molybdenum powder, 10-60 percent of silicon powder and 10-60 percent of boron powder are mixed and made into a cylindrical blank, and a nonequilibrium alloying precursor ZrB with alloying characteristics is prepared and obtained in a combustion synthesis reaction kettle by a self-propagating high-temperature synthesis method2-MoSi2A mixture of (a).
The invention uses the ZrB-based material as defined in claim 12The preparation method of the modified high oxygen barrier coating of the nonequilibrium alloying precursor comprises the following steps: the non-equilibrium alloyed precursor ZrB obtained by preparation2-MoSi2Crushing and drying the mixture, wrapping the nonequilibrium alloying precursor outside a carbon substrate needing to prepare the high oxygen resistance coating by using a mold, performing Spark Plasma (SPS) sintering on the carbon substrate, and finally generating ZrB on the surface of the carbon substrate2-MoSi2High oxygen barrier coating.
ZrB-based2The preparation method of the nonequilibrium alloying modified high oxygen resistant coating comprises the following specific steps:
s1 batching and mixing: zirconium powder, silicon powder, molybdenum powder and boron powder are used as raw materials, and the mass fraction is as follows: weighing raw material powder of 5-30% of zirconium, 5-30% of molybdenum, 10-60% of silicon and 10-60% of boron, mixing the materials by using a ball mill, wherein the rotating speed of the ball mill is 50-1000r/min, the ball milling time is 0.5-10 hours, and finally fully and uniformly mixing the powder;
s2 press forming: drying the uniformly mixed powder, pouring the dried powder into a steel mould, pressurizing the powder in the steel mould under the conditions that the pressure is 20-200 MPa and the pressure maintaining time is 5-60 s, and performing cold pressing molding on the powder by a tablet press to form a cylindrical blank which is used as a precursor required by combustion synthesis;
s3 synthesis of non-equilibrium alloyed precursors: firstly, putting a pressed cylindrical blank into a combustion synthesis reaction kettle, and attaching an upper column cap of a pressed blank to a molybdenum resistance wire; then filling Ar gas into the reaction kettle to perform inert protection on the mixed material in the cylindrical blank; molybdenum wire preheating cylinder by electric heatingA blank body is formed until the self-propagating reaction of the cylindrical blank body is initiated; turning off the resistance wire power supply after the cylindrical blank begins to burn and synthesize the reaction, waiting for the reaction to be complete and cooling to obtain a completely reacted nonequilibrium precursor ZrB2-MoSi2A mixture of (1);
s4, crushing the obtained non-equilibrium state precursor after combustion synthesis for 5-200 min by adopting a crusher, and then putting the precursor into an oven for drying;
s5, treating the surface of the carbon matrix to which the high oxygen resistant coating is to be added: polishing the carbon substrate by using 400-mesh sand paper until the surface is smooth, then ultrasonically cleaning by using alcohol, and finally drying in an oven;
s6 die filling: fully wrapping the carbon matrix treated in the step (5) by using the non-equilibrium precursor obtained in the step (3) in a graphite mold, specifically, firstly filling a layer of non-equilibrium precursor in the graphite mold, then putting the carbon matrix, and then refilling a layer of non-equilibrium precursor to realize that the carbon matrix is uniformly wrapped by precursor powder; the thickness of the non-equilibrium precursor powder covered on the periphery of the matrix is controlled by controlling the quality of the filled precursor powder, the thickness of the wrapping layer is set according to requirements, and the optimal thickness is about 0.1-3 times of the thickness of the carbon matrix;
s7, performing spark plasma SPS sintering: placing the graphite mold into an SPS sintering furnace for sintering treatment, wherein the sintering temperature is 1200-1900 ℃, the heating rate is 5-200 ℃/min, the pressure is 5-50 MPa, and the heat preservation time is 5-min300min, and finally realizing the preparation of ZrB on the surface of the carbon matrix2-MoSi2High oxygen barrier coating.
Example 1:
XRD for synthesizing non-equilibrium precursor powder by self-propagating is shown in figure 1, high resolution TEM is shown in figure 2, and the cross-sectional morphology of the high oxygen barrier coating after being oxidized at 1700 ℃ for 100min is shown in figure 3.
Step (1): burdening and mixing: zirconium, silicon, molybdenum and boron powder are used as raw materials, the purity of the zirconium, silicon, molybdenum and boron powder is more than or equal to 99.0%, the granularity of the zirconium, silicon, molybdenum and boron powder is less than or equal to 50 microns, the powder is weighed according to the mass fraction of 16.1% of zirconium, 50.5% of molybdenum, 3.8% of boron and 29.6% of silicon and is marked as ZM1, and then the powder is ball-milled for 5 hours at the rotating speed of 300r/min to be fully and uniformly mixed;
step (2): and (3) pressing and forming: drying the uniformly mixed powder, pouring the dried powder into a steel mould, and performing cold press molding on the powder into a cylindrical blank by a tablet press under the conditions that the pressure is about 200MPa and the pressure maintaining time is about 30s, wherein the cylindrical blank is used as a precursor required by combustion synthesis;
and (3): synthesizing a non-equilibrium alloying precursor: firstly, putting a pressed sample into a combustion synthesis reaction kettle, and attaching an upper column cap of a pressed blank to a molybdenum resistance wire; secondly, filling Ar gas to perform inert protection on the powder; again, the sample was preheated by electrically heating the molybdenum wire until it initiated a self-propagating reaction. Then, after the combustion synthesis starts to react, the power supply is turned off, and the reaction is waited to be complete; finally, after the sample is cooled, the designed precursor can be obtained;
and (4): putting the obtained hard sample synthesized by combustion into a crusher to be crushed for 15min, and then putting the crushed hard sample into an oven to be dried;
and (5): surface treatment of the carbon substrate: polishing the carbon substrate by using 400-mesh sand paper until the surface is flat, then ultrasonically cleaning by using alcohol, and finally drying in an oven;
and (6): wrapping the carbon substrate treated in the step (5) by using the non-equilibrium precursor obtained in the step (3) in a graphite mold, and respectively filling a certain amount of non-equilibrium precursor powder on the upper part and the lower part of the substrate to realize that the carbon substrate is uniformly wrapped by the non-equilibrium precursor powder, wherein the thickness of the non-equilibrium precursor powder covered on the periphery of the graphite substrate is about 0.6 time of that of the graphite substrate;
and (7): and (3) SPS sintering: and (3) placing the mold filled with the sample into an SPS sintering furnace for sintering treatment, wherein the sintering parameters are as follows: the sintering temperature is 1500 ℃, the heating rate is 100 ℃/min, the pressure is 30MPa, the heat preservation time is 5min, and the high oxygen resistant coating is obtained on the surface of the carbon matrix.
Example 2:
XRD for synthesizing non-equilibrium precursor powder by self-propagating is shown in figure 4, high resolution TEM is shown in figure 5, and the cross-sectional morphology of the high oxygen barrier coating after being oxidized at 1700 ℃ for 100min is shown in figure 6.
Step (1): burdening and mixing: zirconium, silicon, molybdenum and boron powder are used as raw materials, the purity of the zirconium, silicon, molybdenum and boron powder is more than or equal to 99.0%, the granularity of the zirconium, silicon, molybdenum and boron powder is less than or equal to 50 microns, the powder is weighed according to the mass fraction of 48.3% of zirconium, 25.4% of molybdenum, 14.8% of silicon and 11.5% of boron, the powder is marked as ZM2, and then the powder is subjected to ball milling for 3 hours at the rotating speed of 400r/min to be fully;
step (2): and (3) pressing and forming: drying the uniformly mixed powder, pouring the dried powder into a steel mould, and performing cold press molding on the powder into a cylindrical blank by a tablet press under the conditions that the pressure is about 210MPa and the pressure maintaining time is about 25s, wherein the cylindrical blank is used as a precursor required by combustion synthesis;
and (3): synthesizing a non-equilibrium alloying precursor: firstly, putting a pressed sample into a combustion synthesis reaction kettle, and attaching an upper column cap of a pressed blank to a molybdenum resistance wire; secondly, filling Ar gas to perform inert protection on the powder; again, the sample was preheated by electrically heating the molybdenum wire until it initiated a self-propagating reaction. Then, after the combustion synthesis starts to react, the power supply is turned off, and the reaction is waited to be complete; finally, after the sample is cooled, the designed precursor can be obtained;
and (4): putting the obtained hard sample synthesized by combustion into a crusher to be crushed for 100min, and then putting the crushed hard sample into an oven to be dried;
and (5): surface treatment of the carbon substrate: polishing the carbon substrate by using 400-mesh sand paper until the surface is flat, then ultrasonically cleaning by using alcohol, and finally drying in an oven;
and (6): wrapping the carbon substrate treated in the step (5) by using the non-equilibrium precursor obtained in the step (3) in a graphite mold, and respectively filling a certain amount of non-equilibrium precursor powder on the upper part and the lower part of the substrate to realize that the carbon substrate is uniformly wrapped by the non-equilibrium precursor powder, wherein the thickness of the non-equilibrium precursor powder covered on the periphery of the graphite substrate is about 0.55 times of the thickness of the graphite substrate;
and (7): and (3) SPS sintering: and (3) placing the mold filled with the sample into an SPS sintering furnace for sintering treatment, wherein the sintering parameters are as follows: sintering temperature is 1600 ℃, heating rate is 150 ℃/min, pressure is 40MPa, heat preservation time is 8min, and high oxygen resistant coating is obtained on the surface of the carbon matrix.
Example 3:
XRD for synthesizing non-equilibrium precursor powder by self-propagating is shown in figure 7, a high resolution TEM image is shown in figure 8, and the cross-sectional morphology of the high oxygen barrier coating after being oxidized at 1700 ℃ for 100min is shown in figure 9.
Step (1): burdening and mixing: zirconium, silicon, molybdenum and boron powder is used as raw materials, the purity of the zirconium, silicon, molybdenum and boron powder is more than or equal to 99.0%, the granularity of the zirconium, silicon, molybdenum and boron powder is less than or equal to 50 microns, the powder is weighed according to the mass fraction of 64.6% of zirconium, 15.3% of boron, 12.7% of molybdenum and 7.4% of silicon, the powder is marked as ZM3, and then the powder is subjected to ball milling for 8 hours at the rotating speed of 200r/min to be;
step (2): and (3) pressing and forming: drying the uniformly mixed powder, pouring the dried powder into a steel mould, and performing cold press molding on the powder into a cylindrical blank by a tablet press under the conditions that the pressure is about 180MPa and the pressure maintaining time is about 40s, wherein the cylindrical blank is used as a precursor required by combustion synthesis;
and (3): synthesizing a non-equilibrium alloying precursor: firstly, putting a pressed sample into a combustion synthesis reaction kettle, and attaching an upper column cap of a pressed blank to a molybdenum resistance wire; secondly, filling Ar gas to perform inert protection on the powder; again, the sample was preheated by electrically heating the molybdenum wire until it initiated a self-propagating reaction. Then, after the combustion synthesis starts to react, the power supply is turned off, and the reaction is waited to be complete; finally, after the sample is cooled, the designed precursor can be obtained;
and (4): putting the obtained hard sample synthesized by combustion into a crusher to be crushed for 200min, and then putting the crushed hard sample into an oven to be dried;
and (5): surface treatment of the carbon substrate: polishing the carbon substrate by using 400-mesh sand paper until the surface is flat, then ultrasonically cleaning by using alcohol, and finally drying in an oven;
and (6): wrapping the carbon substrate treated in the step (5) by using the non-equilibrium precursor obtained in the step (3) in a graphite mold, and respectively filling a certain amount of non-equilibrium precursor powder on the upper part and the lower part of the substrate to realize that the carbon substrate is uniformly wrapped by the non-equilibrium precursor powder, wherein the thickness of the non-equilibrium precursor powder covered on the periphery of the graphite substrate is about 0.65 time of that of the graphite substrate;
and (7): and (3) SPS sintering: and (3) placing the mold filled with the sample into an SPS sintering furnace for sintering treatment, wherein the sintering parameters are as follows: sintering temperature is 1700 ℃, heating rate is 200 ℃/min, pressure is 20MPa, heat preservation time is 10min, and high oxygen resistant coating is obtained on the surface of the carbon matrix.
The embodiments of the present invention are disclosed as the preferred embodiments, but not limited thereto, and those skilled in the art can easily understand the spirit of the present invention and make various extensions and changes without departing from the spirit of the present invention.

Claims (7)

1. ZrB-based2The non-equilibrium alloying precursor is characterized in that: according to mass fraction: 5-30 percent of zirconium powder, 5-30 percent of molybdenum powder, 10-60 percent of silicon powder and 10-60 percent of boron powder are mixed and made into a cylindrical blank, and a nonequilibrium alloying precursor ZrB with alloying characteristics is prepared and obtained in a combustion synthesis reaction kettle by a self-propagating high-temperature synthesis method2-MoSi2A mixture of (a).
2. Use of a ZrB based module as defined in claim 12The preparation method of the modified high oxygen barrier coating of the nonequilibrium alloying precursor is characterized by comprising the following steps: the non-equilibrium alloyed precursor ZrB obtained by preparation2-MoSi2Crushing and drying the mixture, wrapping the nonequilibrium alloying precursor outside a carbon substrate needing to prepare the high oxygen resistance coating by using a mold, performing Spark Plasma (SPS) sintering on the carbon substrate, and finally generating ZrB on the surface of the carbon substrate2-MoSi2High oxygen barrier coating.
3. ZrB-based2The preparation method of the nonequilibrium alloying modified high oxygen resistant coating is characterized by comprising the following specific steps:
s1 batching and mixing: zirconium powder, silicon powder, molybdenum powder and boron powder are used as raw materials, and the mass fraction is as follows: weighing raw material powder of 5-30% of zirconium, 5-30% of molybdenum, 10-60% of silicon and 10-60% of boron, and mixing the raw material powder by using a ball mill to fully and uniformly mix the powder;
s2 press forming: drying the uniformly mixed powder, pouring the dried powder into a steel mould, pressurizing the powder in the steel mould under the conditions that the pressure is 20-200 MPa and the pressure maintaining time is 5-60 s, and performing cold pressing molding on the powder by a tablet press to form a cylindrical blank which is used as a precursor required by combustion synthesis;
s3 synthesis of non-equilibrium alloyed precursors: firstly, putting a pressed cylindrical blank into a combustion synthesis reaction kettle, and attaching an upper column cap of a pressed blank to a molybdenum resistance wire; then filling Ar gas into the reaction kettle to perform inert protection on the mixed material in the cylindrical blank; preheating the cylindrical blank by electrically heating the molybdenum wire until the self-propagating reaction of the cylindrical blank is initiated; turning off the resistance wire power supply after the cylindrical blank begins to burn and synthesize the reaction, waiting for the reaction to be complete and cooling to obtain a completely reacted nonequilibrium precursor ZrB2-MoSi2A mixture of (1);
s4, crushing the obtained non-equilibrium state precursor after combustion synthesis for 5-200 min by adopting a crusher, and then putting the precursor into an oven for drying;
s5, treating the surface of the carbon matrix to which the high oxygen resistant coating is to be added: polishing the carbon substrate by using 400-mesh sand paper until the surface is smooth, then ultrasonically cleaning by using alcohol, and finally drying in an oven;
s6 die filling: fully wrapping the carbon matrix treated in the step (5) by using the non-equilibrium precursor obtained in the step (3) in a graphite mold, specifically, firstly filling a layer of non-equilibrium precursor in the graphite mold, then putting the carbon matrix, and then refilling a layer of non-equilibrium precursor to realize that the carbon matrix is uniformly wrapped by precursor powder; the thickness of the wrapping layer is set according to the requirement;
s7, performing spark plasma SPS sintering: placing the graphite mold into an SPS sintering furnace for sintering treatment, wherein the sintering temperature is 1200-1900 ℃, the heating rate is 5-200 ℃/min, the pressure is 5-50 MPa, and the heat preservation time is 5-min300min, and finally realizing the preparation of ZrB on the surface of the carbon matrix2-MoSi2High oxygen barrier coating.
4. According to claim 3The ZrB base2The preparation method of the nonequilibrium alloying modified high oxygen resistant coating is characterized by comprising the following steps: the granularity of the zirconium is less than or equal to 45 mu m, the purity is more than or equal to 99.9 percent, the granularity of the molybdenum is less than or equal to 3 mu m, the purity is more than or equal to 99.95 percent, the granularity of the silicon is less than or equal to 40 mu m, the purity is more than or equal to 99.9 percent, the granularity of the boron is less than or equal to 3 mu m, and the purity is more than or equal.
5. ZrB-based according to claim 32The preparation method of the nonequilibrium alloying modified high oxygen resistant coating is characterized by comprising the following steps: the carbon substrate is graphite or a C/C composite material.
6. ZrB-based according to claim 32The preparation method of the nonequilibrium alloying modified high oxygen resistant coating is characterized by comprising the following steps: the zirconium, molybdenum, silicon and boron used in the step S1 are crushed by a ball mill, the rotating speed of the ball mill is 50-1000r/min, and the ball milling time is 0.5-10 hours.
7. ZrB-based according to claim 32The preparation method of the nonequilibrium alloying modified high oxygen resistant coating is characterized by comprising the following steps: in step S6, the thickness of the non-equilibrium precursor powder covering the periphery of the substrate is controlled to be 0.1 to 3 times the thickness of the carbon substrate by controlling the mass of the filling precursor powder.
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