CN108516833B - High-temperature oxidation-resistant powder and coating for ceramic matrix composite and preparation method thereof - Google Patents

High-temperature oxidation-resistant powder and coating for ceramic matrix composite and preparation method thereof Download PDF

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CN108516833B
CN108516833B CN201810350882.2A CN201810350882A CN108516833B CN 108516833 B CN108516833 B CN 108516833B CN 201810350882 A CN201810350882 A CN 201810350882A CN 108516833 B CN108516833 B CN 108516833B
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sintering
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于月光
贾芳
章德铭
彭浩然
冀晓鹃
张鑫
高丽华
张康
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Bgrimm Advanced Materials Science & Technology Co ltd
BGRIMM Technology Group Co Ltd
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Abstract

Powder and coating for high-temperature oxidation resistance of ceramic matrix composite and a preparation method thereof, belonging to the field of high-temperature protective coatings. The B, Ta, B, La or B, Mo co-doped compact SiC coating with a certain content of free silicon, which is suitable for the C/C or C/SiC ceramic matrix composite, is prepared by a high-temperature solid infiltration process. The coating contains 3-25 wt% of free silicon, 0.1-2 wt% of B, 0.1-2.5 wt% of Ta, La or Mo, and the balance of SiC. Formation of B during oxidation by addition of B2O3The Ta, La or Mo which has a lower melting point (450 ℃) and good fluidity and realizes self-healing oxidation resistance of the material, and the Ta, La or Mo which is added with a refractory phase and is refractory to the corresponding oxide can reduce the diffusion speed of oxygen in an oxide film and inhibit the inward diffusion of the oxygen. The novel co-doping method obviously improves the high-temperature oxidation resistance of the SiC coating.

Description

High-temperature oxidation-resistant powder and coating for ceramic matrix composite and preparation method thereof
Technical Field
The invention belongs to the field of high-temperature protective coatings, and relates to powder and a coating for high-temperature oxidation resistance of a ceramic matrix composite and a preparation method thereof, in particular to the powder and the coating which are prepared by a powder high-temperature solid infiltration sintering process and are suitable for high-temperature oxidation resistance of a C/SiC or C/C ceramic matrix composite and the preparation method thereof.
Background
The ceramic matrix composite has the characteristics of high hardness, small density, low thermal expansion coefficient and excellent high-temperature mechanical property, but the ceramic matrix composite is very easy to oxidize in a high-temperature aerobic environment, so that the application of the ceramic matrix composite as a high-temperature structural material is severely limited. The preparation of the high-temperature oxidation-resistant coating on the surface of the composite material is an effective method for improving the high-temperature oxidation resistance of the composite material. SiC has good chemical stability, excellent high-temperature oxidation resistance and relatively good physical and chemical compatibility with C/SiC and C/C composite materials, and is an ideal coating material for ceramic matrix composite materials.
The Li Hegjun et al adopts an embedding method to prepare the SiC high-temperature oxidation-resistant coating on the surface of the C/C composite material, but tiny cracks exist on the surface of the prepared coating, the width of the cracks is 1-3 microns, and the coating has penetrating cracks. Many small air holes are formed in the oxide film generated after the oxidation at 1500 ℃, and the air holes are main channels for oxygen to enter the C/C composite material under the high-temperature environment. (see reference 1: Sun China, Li Hello, Pay just before, Zhang Yu Lei, Likezhi, Oxidation behavior of SiC-coated C/C composites solid rocket technology, 2010,33(1): 91-94).
Yulei Zhang et al studied a method of adding a pre-carbon layer to prepare a gradient transition SiC coating, which reduced the thermal expansion mismatch between the coating and the substrate to a certain extent, but the high temperature oxidation resistance of the coating was not significantly improved. (see reference 2: Yulei Zhang, Hejun Li, Kezhi Li. A C/SiC gradientoxidation protective coating for carbon/carbon composition. surface and coatings Technology,2006(201): 3491-.
The SiC coating prepared by the method has the problems of more defects and insufficient oxidation resistance. Coating cracks and defects are the main cause of poor oxidation resistance of the composite material. The SiC coating has the protection capability of 1700 ℃ to the ceramic matrix composite in theory, but due to the difference of the thermal expansion coefficients between the SiC coating and the matrix of the composite, the coating is easy to crack, the generated cracks can seriously affect the oxidation resistance of the single SiC coating, in addition, the SiC coating can have tiny air holes in an oxidation film generated by gas in the oxidation process, and the micro cracks and the pores provide channels for the diffusion of oxygen, so that the oxidation resistance of the coating is insufficient. Therefore, in order to realize long-life use of the ceramic matrix composite material at 1650 ℃, the high-temperature oxidation resistance of the ceramic matrix composite material must be improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and firstly provides a high-temperature oxidation-resistant powder for a ceramic matrix composite, which comprises the following chemical components: 3-25 wt.% of Si, 0.1-2 wt.% of B, 0.1-2.5 wt.% of Ta or La or Mo, and the balance of SiC.
The invention also provides a method for preparing the powder for the high-temperature oxidation resistance of the ceramic matrix composite, which comprises the steps of proportioning and mixing the high-purity SiC powder, the Si powder, the B powder and the Ta or La or Mo powder in proportion, adding the organic liquid into the mixed powder, carrying out wet ball milling dispersion, and drying slurry after ball milling dispersion to obtain the powder for the high-temperature oxidation resistance of the ceramic matrix composite. The organic liquid is acetone, ethanol and other organic liquid for conventional ball milling, and the ball milling medium and the ball milling pot are made of conventional materials without introducing impurities.
Further, the purity of the SiC powder is more than 99.9%, and the granularity is 30-50 μm; the purity of the Si powder is more than 99.9%, and the granularity is 30-50 mu m; the purity of the powder B is more than 99.9%, and the granularity is 1-30 mu m; the purity of Ta or La or Mo powder is more than 99.9%, and the granularity is 1-30 μm.
The invention also provides a high-temperature oxidation-resistant coating for the ceramic matrix composite, wherein the content of free silicon in the coating is 3-25 wt.%, the content of B is 0.1-2 wt.%, the content of Ta or La or Mo is 0.1-2.5 wt.%, and the balance is SiC.
Further, the thickness of the coating is 50 to 150 μm.
The invention also provides a method for preparing the high-temperature oxidation-resistant coating for the ceramic matrix composite, and more particularly relates to a method for preparing the high-temperature oxidation-resistant coating suitable for the C/SiC or C/C ceramic composite by combining a powder high-temperature solid infiltration sintering process and a plasma sintering process. Firstly, a 50-150 mu m B, Ta or B, La or B, Mo co-doped compact SiC coating with a certain content of free silicon is prepared on the surface of a C/SiC or C/C ceramic composite material matrix by using a powder high-temperature solid infiltration sintering process, and then the prepared coating is subjected to plasma sintering treatment. The preparation method comprises the following steps:
(1) pretreatment of a base material: cutting the ceramic matrix composite substrate into samples, polishing the cut samples, ultrasonically cleaning the polished substrate samples, and drying for later use;
(2) preparing a sintering material: adding the powder for high-temperature oxidation resistance of the ceramic matrix composite material into a sintering vessel, then putting the sample pretreated in the step (1), then adding the powder for high-temperature oxidation resistance of the ceramic matrix composite material into the sintering vessel again to fill the sintering vessel, slightly compacting the powder to remove air in the sintering vessel, and sealing the sintering vessel;
(3) and (3) high-temperature solid infiltration sintering: putting the sintering vessel prepared in the step (2) into a vacuum sintering furnace, and vacuumizing the sintering furnace until the air pressure is 2 multiplied by 10-2Heating to 1700-2100 ℃ below Pa, and keeping the temperature for 1-4 hours; after the temperature of the vacuum sintering furnace is reduced to room temperature, taking out the prepared sample, and drying the sample after ultrasonic cleaning;
(4) plasma sintering: carrying out plasma sintering treatment on the sample coating obtained in the step (3), wherein the plasma sintering process parameters are as follows: the sintering rate is 800-1200 ℃/min, the temperature is raised to 1700-1900 ℃, and then the temperature is preserved for 20-40 min. The purpose is to reduce the defects of the coating, solidify the interface combination, reduce the oxidation of the matrix and obtain the modified SiC coating after the plasma sintering treatment.
Further, the ceramic matrix composite substrate in the step (1) is a C/SiC ceramic composite material or a C/C composite material.
Further, the sintering vessel in the step (3) is a boron nitride crucible.
Further, the amount of the powder added for the first time in the step (3) is 60-80% of the volume of the sintering vessel.
The SiC coating prepared by the method has the oxidation weight loss of not more than 4.9% after high-temperature cyclic oxidation for 10 hours in the atmospheric environment at 1500 ℃.
The coating for high-temperature oxidation resistance of the ceramic matrix composite material prepared by the invention has the following advantages:
cracks are inevitably generated on the coating due to the difference of the thermal expansion coefficients between the SiC coating and the composite material substrate, and SiC is oxidized to generate SiO2Has a slow speed and poor fluidity, and is difficult to seal cracks in the coating, resulting in easy diffusion of oxygen into the interior of the substrate. Formation of B during oxidation by addition of B2O3The SiC coating has a low melting point (450 ℃) and good fluidity, can heal cracks in the coating, prevents oxygen from diffusing into the material through microcracks, realizes self-healing oxidation resistance of the material, and effectively improves the high-temperature oxidation resistance of the SiC coating. The diffusion rate of oxygen in the oxide film is reduced by adding Ta, La or Mo, which is refractory to the refractory phase and to the corresponding oxide, to the SiC coating, the oxygen in-diffusion is suppressed, and SiO is formed2The protective layer is also more dense. The novel B, Ta or B, La or B, Mo codoped SiC coating has obviously better high-temperature oxidation resistance than the common SiC coating, and effectively prolongs the service life of the coating.
Drawings
FIG. 1 is a surface topography of a modified SiC high temperature oxidation resistant coating provided by the present invention.
FIG. 2 is a sectional morphology diagram of a modified SiC high-temperature oxidation-resistant coating prepared by the invention.
FIG. 3 is a surface topography of the modified SiC high temperature oxidation resistant coating prepared by the invention after being oxidized for 10h at 1500 ℃.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1: preparation of modified SiC high-temperature oxidation-resistant coating on C/SiC composite material substrate
The first step is as follows: preparing a base material
Cutting a ceramic matrix composite substrate into samples with the specification of 10 multiplied by 3mm, then polishing the cut samples by abrasive paper, chamfering 12 edges into round corners, finally ultrasonically cleaning the polished substrate samples by absolute ethyl alcohol and acetone for 15 minutes in sequence, and drying for 2 hours at 120 ℃ for later use. The ceramic matrix composite substrate is made of C/SiC ceramic composite.
The second step is that: preparing penetrant powder
SiC powder (particle size of 30 to 50 μm) having a purity of 99.9%, Si powder (particle size of 30 to 50 μm) having a purity of 99.9%, B powder (particle size of 1 to 10 μm) having a purity of 99.9%, and Ta powder (particle size of 1 to 10 μm) having a purity of 99.9% were used as raw materials. The chemical components of the prepared penetrating agent are that the content of SiC is 84 wt.%, the content of Si is 15 wt.%, the content of B is 0.5 wt.%, and the content of Ta is 0.5 wt.%. And placing the prepared powder into a resin ball milling tank, adding acetone, ball milling for 10 hours, taking out the mixed solution, and drying at 100 ℃ for later use.
The third step: preparation of modified SiC coating on substrate by powder high-temperature solid infiltration sintering process
Firstly, adding 70% of infiltration agent powder into a 5ml boron nitride crucible, then placing the matrix sample prepared in the first step into the middle of the boron nitride crucible added with the infiltration agent powder, then filling the crucible with the infiltration agent powder, wrapping the sample in the middle of the infiltration agent powder, slightly compacting the powder to remove air in the crucible, and tightly covering the crucible. Placing the crucible containing the sample into a vacuum sintering furnace, and vacuumizing the sintering furnace until the vacuum degree is lower than 2 multiplied by 10-2Pa, heatingThe temperature is 1800 ℃, the heat preservation time is 2 hours, and the thickness of a permeable layer is 90 mu m; and (4) taking out the prepared coating sample after the temperature of the vacuum sintering furnace is reduced to room temperature, ultrasonically cleaning the coating sample for 15min by using acetone, and drying the coating sample.
The fourth step: subjecting the prepared coating to plasma sintering treatment
The parameters of the plasma sintering process are as follows: and (3) sintering at the sintering rate of 1100 ℃/min for 30min, and carrying out plasma sintering treatment to obtain the modified SiC coating.
The modified SiC coating prepared by the method has a compact structure, the surface appearance and the cross-sectional appearance of the coating after plasma sintering treatment are shown in attached figures 1 and 2, the surface appearance of a sample is observed after cyclic oxidation is carried out for 10 hours in 1500 ℃, an oxide film generated on the surface of the modified SiC coating is complete and compact, the oxidation weight loss is 4.8% after oxidation for 10 hours, and the modified SiC coating is proved to have good high-temperature oxidation resistance.
Example 2: preparation of modified SiC high-temperature oxidation-resistant coating on C/C composite material substrate
The first step is as follows: preparing a base material
Cutting a ceramic matrix composite substrate into samples with the specification of 10 multiplied by 3mm, then polishing the cut samples by abrasive paper, chamfering 12 edges into round corners, finally ultrasonically cleaning the polished substrate samples by absolute ethyl alcohol and acetone for 15 minutes in sequence, and drying for 2 hours at 120 ℃ for later use. The ceramic matrix composite substrate is made of a C/C ceramic composite material.
The second step is that: preparing penetrant powder
SiC powder (particle size of 30 to 50 μm) having a purity of 99.9%, Si powder (particle size of 30 to 50 μm) having a purity of 99.9%, B powder (particle size of 1 to 30 μm) having a purity of 99.9%, and La powder (particle size of 1 to 30 μm) having a purity of 99.9% were used as raw materials. The chemical components of the prepared penetrating agent are that the content of SiC is 84 wt.%, the content of Si is 15 wt.%, the content of B is 0.5 wt.%, and the content of La is 0.5 wt.%. And placing the prepared powder into a resin ball milling tank, adding acetone, ball milling for 10 hours, taking out the mixed solution, and drying at 100 ℃ for later use.
The third step: preparation of modified SiC coating on substrate by powder high-temperature solid infiltration sintering process
Firstly, adding 70% of infiltration agent powder into a 5ml boron nitride crucible, then placing the matrix sample prepared in the first step into the middle of the boron nitride crucible added with the infiltration agent powder, then filling the crucible with the infiltration agent powder, wrapping the sample in the middle of the infiltration agent powder, slightly compacting the powder to remove air in the crucible, and tightly covering the crucible. Placing the crucible containing the sample into a vacuum sintering furnace, and vacuumizing the sintering furnace until the vacuum degree is lower than 2 multiplied by 10-2Pa, heating to 1900 deg.C, holding for 2 hr, and making the thickness of the penetrated layer be-100 μm; and (4) taking out the prepared coating sample after the temperature of the vacuum sintering furnace is reduced to room temperature, ultrasonically cleaning the coating sample for 15min by using acetone, and drying the coating sample.
The fourth step: subjecting the prepared coating to plasma sintering treatment
The parameters of the plasma sintering process are as follows: and (3) sintering at a sintering rate of 1000 ℃/min, keeping the temperature for 30min after the temperature is raised to 1800 ℃, and performing plasma sintering treatment to obtain the modified SiC coating.
The modified SiC coating prepared by the method has a compact structure, the surface appearance of the sample is observed after the sample subjected to plasma sintering treatment is circularly oxidized for 10 hours in an atmospheric environment at 1500 ℃, an oxidation film generated on the surface of the modified SiC coating is complete and compact, and the oxidation weight loss after the oxidation for 10 hours is 4.9%, which indicates that the modified SiC coating has good high-temperature oxidation resistance.
Example 3: preparation of modified SiC high-temperature oxidation-resistant coating on C/SiC composite material substrate
The first step is as follows: preparing a base material
Cutting a ceramic matrix composite substrate into samples with the specification of 10 multiplied by 3mm, then polishing the cut samples by abrasive paper, chamfering 12 edges into round corners, finally ultrasonically cleaning the polished substrate samples by absolute ethyl alcohol and acetone for 15 minutes in sequence, and drying for 2 hours at 120 ℃ for later use. The ceramic matrix composite substrate is made of a C/C ceramic composite material.
The second step is that: preparing penetrant powder
SiC powder (particle size of 30 to 50 μm) having a purity of 99.9%, Si powder (particle size of 30 to 50 μm) having a purity of 99.9%, B powder (particle size of 1 to 30 μm) having a purity of 99.9%, and La powder (particle size of 1 to 30 μm) having a purity of 99.9% were used as raw materials. The chemical components of the prepared penetrating agent are that the content of SiC is 84 wt.%, the content of Si is 15 wt.%, the content of B is 0.5 wt.%, and the content of Mo is 0.5 wt.%. And placing the prepared powder into a resin ball milling tank, adding acetone, ball milling for 10 hours, taking out the mixed solution, and drying at 100 ℃ for later use.
The third step: preparation of modified SiC coating on substrate by powder high-temperature solid infiltration sintering process
Firstly, adding 70% of infiltration agent powder into a 5ml boron nitride crucible, then placing the matrix sample prepared in the first step into the middle of the boron nitride crucible added with the infiltration agent powder, then filling the crucible with the infiltration agent powder, wrapping the sample in the middle of the infiltration agent powder, slightly compacting the powder to remove air in the crucible, and tightly covering the crucible. Placing the crucible containing the sample into a vacuum sintering furnace, and vacuumizing the sintering furnace until the vacuum degree is lower than 2 multiplied by 10-2Pa, heating to 2000 deg.C, holding for 2 hr, and permeating layer thickness of-120 μm; and (4) taking out the prepared coating sample after the temperature of the vacuum sintering furnace is reduced to room temperature, ultrasonically cleaning the coating sample for 15min by using acetone, and drying the coating sample.
The fourth step: subjecting the prepared coating to plasma sintering treatment
The parameters of the plasma sintering process are as follows: and (3) sintering at a sintering rate of 1000 ℃/min, keeping the temperature for 30min after the temperature is raised to 1800 ℃, and performing plasma sintering treatment to obtain the modified SiC coating.
The modified SiC coating prepared by the method has a compact structure, the surface appearance of the sample is observed after the sample subjected to plasma sintering treatment is circularly oxidized for 10 hours in an atmosphere environment at 1500 ℃, an oxidation film generated on the surface of the modified SiC coating is complete and compact, and the oxidation weight loss after the oxidation for 10 hours is 4.7%, so that the modified SiC coating has good high-temperature oxidation resistance.

Claims (9)

1. The powder for the high-temperature oxidation resistance of the ceramic matrix composite is characterized by comprising the following chemical components: 3-25 wt.% of Si, 0.1-2 wt.% of B, 0.1-2.5 wt.% of Ta or La or Mo, and the balance of SiC.
2. The method for preparing the powder according to claim 1, wherein the high-purity SiC powder, the Si powder, the B powder and the Ta or La or Mo powder are mixed according to a proportion, an organic liquid is added into the mixed powder, then wet ball milling dispersion is carried out, and slurry after ball milling dispersion is dried to obtain the powder for the high-temperature oxidation resistance of the ceramic matrix composite.
3. The method for producing the powder according to claim 2, wherein the purity of the SiC powder is 99.9% or more, and the particle size is 30 to 50 μm; the purity of the Si powder is more than 99.9%, and the granularity is 30-50 mu m; the purity of the powder B is more than 99.9%, and the granularity is 1-30 mu m; the purity of Ta or La or Mo powder is more than 99.9%, and the granularity is 1-30 μm.
4. The coating for the high-temperature oxidation resistance of the ceramic matrix composite is characterized in that the content of free silicon in the coating is 3-25 wt.%, the content of B is 0.1-2 wt.%, the content of Ta or La or Mo is 0.1-2.5 wt.%, and the balance is SiC.
5. The coating of claim 4, wherein the coating thickness is 50 to 150 μm.
6. A method for the preparation of a coating according to claim 4 or 5, characterized in that it comprises the following steps:
(1) pretreatment of a base material: cutting the ceramic matrix composite substrate into samples, polishing the cut samples, ultrasonically cleaning the polished substrate samples, and drying for later use;
(2) preparing a sintering material: adding the powder of claim 1 into a sintering vessel, then putting the sample pretreated in the step (1), then adding the powder of claim 1 again to fill the sintering vessel, compacting the powder to remove air in the sintering vessel, and sealing the sintering vessel;
(3) and (3) high-temperature solid infiltration sintering: putting the sintering vessel prepared in the step (2) into a vacuum sintering furnace, and vacuumizing the sintering furnace until the sintering furnace is exhaustedPressing at 2X 10-2Heating to 1700-2100 ℃ below Pa, and keeping the temperature for 1-4 hours; after the temperature of the vacuum sintering furnace is reduced to room temperature, taking out the prepared sample, and drying the sample after ultrasonic cleaning;
(4) plasma sintering: carrying out plasma sintering treatment on the sample coating obtained in the step (3), wherein the plasma sintering process parameters are as follows: the sintering rate is 800-1200 ℃/min, the temperature is raised to 1700-1900 ℃, and then the temperature is preserved for 20-40 min.
7. The method according to claim 6, wherein the ceramic matrix composite substrate of step (1) is a C/SiC ceramic composite or a C/C composite.
8. The method according to claim 6, wherein the sintering vessel in the step (3) is a boron nitride crucible.
9. The method according to claim 6, wherein the amount of the first powder added in the step (2) is 60 to 80% of the volume of the sintering vessel.
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