CN116573953B - Carbon/carbon composite material surface grid structure enhanced ablation-resistant coating, preparation method and application - Google Patents
Carbon/carbon composite material surface grid structure enhanced ablation-resistant coating, preparation method and application Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 135
- 239000011248 coating agent Substances 0.000 title claims abstract description 133
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 238000002679 ablation Methods 0.000 title claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000004372 laser cladding Methods 0.000 claims abstract description 38
- 239000011159 matrix material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 230000003628 erosive effect Effects 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 53
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 16
- 238000009991 scouring Methods 0.000 claims description 14
- 239000011863 silicon-based powder Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000006255 coating slurry Substances 0.000 claims description 8
- 230000001680 brushing effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 230000004907 flux Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011010 flushing procedure Methods 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 4
- 238000005253 cladding Methods 0.000 description 3
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- 230000001678 irradiating effect Effects 0.000 description 3
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- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 230000003014 reinforcing effect Effects 0.000 description 1
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- 230000003746 surface roughness Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
- C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention relates to a carbon/carbon composite material surface grid structure reinforced anti-ablation coating, a preparation method and application thereof, wherein a laser selective melting technology is adopted to manufacture a metal W grid on the carbon/carbon composite material surface in an additive manner, and chemical combination is formed at the interface of the metal W grid and the metal W grid through in-situ reaction between W and C, so that the interface combination strength is improved; the Si-SiC coating is prepared on the surfaces of the W grid structure and the carbon/carbon composite material matrix by utilizing a laser cladding method, the coating structure is compact, the barrier effect of external oxygen and the grid and matrix can be realized, and the high-temperature aerobic protection function is realized. The invention effectively improves the stability of the coating sample under the high Wen Yanliu flushing by means of the strong interface combination, extreme high temperature resistance and melt flow resistance of the high-melting-point grid structure, and the anti-ablation performance of the coating is enhanced. The feasibility of the W grid reinforced Si-SiC laser cladding layer applied to an aircraft engine is provided, and the W grid reinforced Si-SiC laser cladding layer has important reference significance and practical value for high-temperature aerobic protection of structural components in a thermal erosion environment.
Description
Technical Field
The invention belongs to the technical field of protective coatings, and relates to a carbon/carbon composite material surface grid structure reinforced ablation-resistant coating, a preparation method and application thereof.
Background
The C/C composite material is regarded as a thermal structure candidate material with excellent hot end components of aircrafts in the aerospace field due to the characteristics of light weight, high strength and excellent high-temperature mechanical properties. However, in the face of extreme thermal corrosion conditions, severe oxide etching of the fully carbonaceous C/C composite occurs, causing dramatic strength degradation and structural failure. An effective way to avoid this phenomenon is a coating technique, wherein a Si-SiC coating with good physicochemical compatibility with a C/C composite is an outstanding oxidation-protecting material, and a laser cladding method with near net-shape forming characteristics is an ideal preparation means for Si-SiC coatings.
Compared with metallurgical bonding formed by inter-diffusion of atoms at the interface between the substrate and the coating, the C/C composite material which is not easy to melt can only form mechanical bonding with the Si-SiC coating, has low bonding strength, and is difficult to resist flame flow scouring in a service environment. Therefore, how to prevent the ablation scour failure of the Si-SiC laser cladding layer is one of the important points of current research.
A "Liu Teng,Xiao-Hong Shi,Han-Hui Wang,et al.A new method to improve the laser-ablation resistance of Si-SiC coating on C/C composites:Laser cladding[J].Journal of the European Ceramic Society,2022,42(14):6425-6434." Si-SiC coating prepared on the surface of the C/C composite material by comparing a laser cladding method with an embedding method proves that the laser cladding method can obviously reduce the surface roughness of the coating and avoid the damage to the mechanical property of a matrix, and the prepared coating has outstanding high temperature resistance, thus being an ideal coating preparation method.
The document two "Han-Hui Wang,He-Jun Li,Xiao-Hong Shi,et al.Repair of SiC coating on carbon/carbon composites by laser cladding technique[J].Ceramics International,2020,46:19537-19544." proposes that the Si-SiC coating prepared by using the laser cladding technology can successfully provide high-temperature aerobic protection for the C/C composite material matrix, but the C/C composite material matrix always maintains a solid phase state in the laser irradiation process, and has lower mechanical bonding strength with the Si-SiC coating, so that the coating is difficult to resist ablation scouring of oxyacetylene flame flow under the bonding strength.
Document three "Fujun Wang,Huaidong Mao,Dawei Zhang,et al.The crack control during laser cladding by adding the stainless steel net in the coating[J].Applied Surface Science,2009,255(21):8846-8854." discloses a method for suppressing the generation of cracks in the laser cladding process by adding a stainless steel mesh to the inside of the coating, and the study proves that the introduction of the lattice structure can reduce the brittleness of the coating and exert the reinforcing effect. However, the method for manufacturing the stainless steel mesh is not clear, and annealing treatment and acid washing treatment are required before actual use, which increases technical difficulty. One-step formed mesh preparation technology is yet to be developed.
Literature IV "Ling-jun Guo,Jian Peng,Chen Guo,et al.Ablation performance of supersonic atmosphere plasma sprayed tungsten coating under oxyacetylene torch and plasma torch[J].Vacuum,2017,143:262-270" demonstrates that the use of W in combination with a SiC coating provides effective oxyacetylene flame ablation protection for the C/C composite matrix, and that the W reacts with the carbon material at high temperatures and generates WC, which chemically enhances the interfacial bond strength of the coating.
Therefore, the patent provides a C/C composite material surface grid structure reinforced anti-ablation coating and a preparation method, wherein a W grid structure is built in a Si-SiC coating, so that the rapid failure of the coating under the ablation and flushing of oxy-acetylene flame flow is relieved, and the protective life of the coating to a C/C composite material substrate is effectively prolonged. Up to now, this study has not been reported.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a carbon/carbon composite material surface grid structure reinforced anti-ablation coating, a preparation method and application thereof, and the protection effect of a Si-SiC coating on a C/C composite material matrix under the ablation of oxy-acetylene flame is optimized.
Firstly, a laser selective melting technology is adopted to prepare a metal W grid on the surface of the C/C composite material, so that the overall bonding strength and the scouring resistance of the coating are improved. And then preparing a Si-SiC coating on the grid structure and the surface of the matrix by a laser cladding method, realizing complete coverage of the W grid and the C/C composite material matrix, and realizing a high-temperature aerobic protection function by isolating the grid structure and the matrix from external oxygen.
In general, the invention ensures the high-temperature oxidation resistance of the Si-SiC coating, and simultaneously introduces a grid structure to improve the overall bonding strength and ablation resistance of the coating, solves the problem of no air flow scouring resistance of the Si-SiC laser cladding layer on the surface of the C/C composite material, avoids the matrix exposure failure phenomenon caused by oxyacetylene flame ablation, expands the practical application range of the Si-SiC laser cladding layer, and has beneficial effects on the development of the protection of the thermal structural components of the aircraft.
Technical proposal
A carbon/carbon composite surface grid structure enhanced anti-ablation coating comprises a Si-SiC coating; the method is characterized in that: the surface of the carbon/carbon composite material is provided with a metal W grid, and the Si-SiC coating is coated on the surface of the matrix of the carbon/carbon composite material through laser cladding; and the high melting point of W and the in-situ reaction between W and C are utilized to enhance the integral scouring resistance and interface bonding strength of the coating, so that the ablation resistance of the Si-SiC coating is enhanced by the W grid structure.
The metal W grid adopts a square grid structure.
The grid spacing of the square grid structure is 0.4-1 mm.
A method for preparing the carbon/carbon composite material surface grid structure reinforced ablation-resistant coating by adopting a laser cladding method is characterized by comprising the following steps:
Step 1: processing the surface to be prepared of the coating of the C/C composite material into a flat surface so as to facilitate powder spreading by a machine in a subsequent laser selective melting link;
Step 2, manufacturing a W grid structure:
Taking spherical W powder as a raw material, and adopting laser selective melting equipment to perform additive manufacturing of a grid structure along the flat surface of the C/C composite material;
The melting parameter of the selected laser area is 250-350W, the laser scanning speed is 200-350mm/s, and the spot diameter is 50-80 mu m.
Step 3, preparation of Si-SiC coating:
Dispersing raw material powder obtained by mixing Si powder, siC powder and C powder in an absolute ethyl alcohol solvent, magnetically stirring for 1-3 hours to prepare Si-SiC coating slurry, brushing the slurry on the surfaces of a W grid and a C/C composite material matrix, and then placing a sample after brushing the slurry in an environment of 60-100 ℃ for drying treatment for 0.5-1.5 hours to remove the solvent;
Under argon atmosphere, using a fiber laser to irradiate surface powder, completing laser cladding treatment and obtaining a W grid structure reinforced Si-SiC coating, wherein the laser cladding parameters are 300-400W, the scanning speed is 2-4mm/s, and the spot diameter is 4-5mm;
obtaining the carbon/carbon composite material surface grid structure reinforced anti-ablation coating.
The particle size of the W powder is 100-300 meshes of spherical W powder.
The ratio of Si powder, siC powder to C powder is 50-70wt.% of Si powder, 15-30wt.% of SiC powder and 5-15wt.% of C powder.
The particle sizes of the Si powder, the SiC powder and the C powder are all 100-300 meshes.
And mixing the Si powder, the SiC powder and the C powder by ball milling for 1-3h.
The ablation assessment method for the carbon/carbon composite material surface grid structure enhanced ablation resistant coating is characterized by comprising the following steps of: and carrying out oxyacetylene flame ablation test on the Si-SiC coating and the W grid structure reinforced Si-SiC coating, wherein the oxyacetylene flame heat flux density is 2400kW/m 2, and the ablation duration is 60s.
The application of the carbon/carbon composite material surface grid structure reinforced ablation-resistant coating is characterized in that: the W grid reinforced Si-SiC laser cladding layer is applied to high-temperature aerobic protection of structural parts in an aircraft engine and thermal erosion environment.
Advantageous effects
According to the carbon/carbon composite material surface grid structure reinforced ablation-resistant coating, the preparation method and the application, a laser selective melting technology is adopted to manufacture a metal W grid on the carbon/carbon composite material surface in an additive manner, chemical combination is formed at the interface of the metal W grid and the metal W grid through in-situ reaction between W and C, and the interface combination strength is improved; the Si-SiC coating is prepared on the surfaces of the W grid structure and the carbon/carbon composite material matrix by utilizing a laser cladding method, the coating structure is compact, the barrier effect of external oxygen and the grid and matrix can be realized, and the high-temperature aerobic protection function is realized. Compared with the traditional Si-SiC coating, the W grid structure reinforced Si-SiC coating provided by the invention can effectively improve the stability of a coating sample under high Wen Yanliu flushing by means of the strong interface combination, extreme high temperature resistance and melt flow resistance characteristics of a high-melting grid structure under the ablation flushing of oxyacetylene flame, delay the exposure failure of a C/C composite material matrix and enhance the ablation resistance of the coating. Therefore, the invention overcomes the defects of low bonding strength and no air flow scouring resistance of the Si-SiC laser cladding layer on the surface of the C/C composite material, provides the feasibility of the W grid reinforced Si-SiC laser cladding layer applied to an aircraft engine, and has important reference significance and practical value for high-temperature aerobic protection of structural parts in a thermal erosion environment.
The invention provides a C/C composite material surface grid structure reinforced anti-ablation coating and a preparation method thereof. Taking spherical W powder as a raw material, and adopting a laser selective melting technology to manufacture a grid structure on the flat surface of the C/C composite material in an additive way; si, siC and C powder are used as raw materials, a laser cladding technology is adopted to prepare a Si-SiC coating on the surfaces of the W grid and the C/C composite material matrix, and finally the W grid structure reinforced Si-SiC coating is obtained. The reasons for the enhanced ablation resistance of the grid structure enhanced Si-SiC coating compared to the Si-SiC coating include two aspects: firstly, as the melting point (3410 ℃) of W is far higher than the melting point (1410 ℃) of Si in the coating, when the ablation temperature is between the melting points of W and Si, the gradually melted coating flows under the scouring of oxy-acetylene flame flow, and the unmelted W grid can block the flow of melt, so that the exposure of a matrix caused by the flow consumption of the coating is avoided, and the ablation resistance enhancing effect of the grid structure on the Si-SiC coating is effectively exerted; secondly, in the laser additive manufacturing process, molten W at the bottom layer of the grid can be contacted with the C/C composite material and react to generate WC, and the existence of chemical bonding at the interface can remarkably improve the bonding strength of the W grid and further enhance the flame flow scouring resistance of the Si-SiC coating. Meanwhile, si and SiC components in the coating can be oxidized in a high-temperature ablation process to generate a high-melting-point and compact SiO 2 glass film which is covered on the surface of the sample, so that the high-temperature airflow erosion resistance of the sample is improved. In the laser cladding preparation of the coating, the existence of C powder in the raw material can react with Si to generate more high-melting-point SiC, and the reduction of the proportion of the low-melting-point Si component can also enhance the ablation resistance of the sample.
Table 1 compares the mass ablation rates of Si-SiC coating samples and W-grid structure enhanced Si-SiC coating samples after being subjected to oxyacetylene flame ablation and assessment. The finding shows that the mass ablation rate of the Si-SiC coating sample is positive, which indicates that the quality of the coating gradually decreases in the ablation process, namely the coating is lost and consumed under the scouring of oxyacetylene flame flow; the negative mass ablation rate of the W grid structure reinforced Si-SiC coating sample is derived from the coating weight increment caused by oxidation reaction, in other words, the ablation mass loss of the coating is obviously smaller than that of the Si-SiC coating, and the coating has stronger high-temperature airflow scouring resistance. As can be seen from fig. 4, the Si-SiC coating sample is ablated to significantly thin the coating and expose the C/C composite matrix, and the W-grid structure reinforced Si-SiC coating sample has partially exposed the grid structure, but the matrix is still well protected, which proves that the introduction of the grid structure can enhance the ablation resistance of the coating, and is beneficial to the ablation protection of the thermal structural components of the aircraft.
TABLE 1 mass ablation Rate for Si-SiC coating samples and W-grid Structure enhanced Si-SiC coating samples
Drawings
FIG. 1 is a schematic diagram of a preparation process of a C/C composite surface grid structure enhanced ablation resistant coating
FIG. 2 is a scanning electron microscope photograph of a W-grid structure of a C/C composite material surface
FIG. 3 is a scanning electron microscope photograph of a W-grid structure enhanced Si-SiC coating on the surface of a C/C composite material
FIG. 4 shows the surface morphology of (a-b) Si-SiC coating samples after being ablated by an oxyacetylene flame and (c-d) W-grid structure enhanced Si-SiC coating samples
Detailed Description
The invention will now be further described with reference to examples, figures:
embodiment one:
(1) The C/C composite material with the density of 1.70g/cm 3 is processed into a block with the size of 10 multiplied by 8 multiplied by 6mm 3, and the surface of the coating to be prepared of the block is ensured to be plane.
(2) Spherical W powder with the particle size of 100 meshes is used as a preparation raw material of the grid structure, and laser selective melting equipment is utilized to perform additive manufacturing of the grid structure along the flat surface of the C/C composite material. Wherein the grid spacing is 1mm, the melting parameter of the selected laser area is 350W, the laser scanning speed is 300mm/s, and the spot diameter is 80 mu m.
(3) The preparation raw materials of the Si-SiC cladding layer are weighed, wherein the preparation raw materials comprise 65wt.% of Si powder, 20wt.% of SiC powder and 15wt.% of C powder, the particle sizes of the powder are 100 meshes, and the powder is ball-milled and mixed for 3 hours so as to realize uniform mixing of the components.
(4) Dispersing the mixed powder obtained in the step (3) in an absolute ethyl alcohol solvent, magnetically stirring for 2 hours to obtain Si-SiC coating slurry, and brushing the Si-SiC coating slurry on the surfaces of the W grid and the C/C composite material matrix. Subsequently, the slurry-coated sample was subjected to a baking treatment at 80℃for 1 hour to remove the solvent.
(5) And (3) irradiating the surface of the sample obtained in the step (4) by using a fiber laser in an argon atmosphere, and completing laser cladding treatment of preset powder and obtaining the W grid structure reinforced Si-SiC coating. Wherein, the laser cladding parameter is power 400W, scanning speed 4mm/s, and spot diameter 4mm.
(6) In order to detect the high temperature resistance and the scouring resistance of the coating, oxyacetylene flame ablation tests are respectively carried out on the Si-SiC coating and the W grid structure reinforced Si-SiC coating, and the mass ablation rates of all the samples are calculated and compared. Wherein, the heat flux density of the oxyacetylene flame is 2400kW/m 2, and the ablation duration is 60s.
Embodiment two:
(1) The C/C composite material with the density of 1.75g/cm 3 is processed into a block with the size of 10 multiplied by 8 multiplied by 6mm 3, and the surface of the coating to be prepared of the block is ensured to be plane.
(2) Spherical W powder with the particle size of 200 meshes is used as a preparation raw material of the grid structure, and laser selective melting equipment is utilized to perform additive manufacturing of the grid structure along the flat surface of the C/C composite material. Wherein, the grid spacing is 0.8mm, the melting parameter of the selected laser area is 300W, the laser scanning speed is 250mm/s, and the spot diameter is 80 mu m.
(3) The preparation raw materials of the Si-SiC cladding layer are weighed, wherein the preparation raw materials comprise 65wt.% of Si powder, 20wt.% of SiC powder and 15wt.% of C powder, the particle sizes of the powder are 200 meshes, and the powder is ball-milled and mixed for 3 hours so as to realize uniform mixing of the components.
(4) Dispersing the mixed powder obtained in the step (3) in an absolute ethyl alcohol solvent, magnetically stirring for 2 hours to obtain Si-SiC coating slurry, and brushing the Si-SiC coating slurry on the surfaces of the W grid and the C/C composite material matrix. Subsequently, the slurry-coated sample was subjected to a baking treatment at 80℃for 1 hour to remove the solvent.
(5) And (3) irradiating the surface of the sample obtained in the step (4) by using a fiber laser in an argon atmosphere, and completing laser cladding treatment of preset powder and obtaining the W grid structure reinforced Si-SiC coating. Wherein, the laser cladding parameter is power 350W, scanning speed 3mm/s, and spot diameter 4mm.
(6) In order to detect the high temperature resistance and the scouring resistance of the coating, oxyacetylene flame ablation tests are respectively carried out on the Si-SiC coating and the W grid structure reinforced Si-SiC coating, and the mass ablation rates of all the samples are calculated and compared. Wherein, the heat flux density of the oxyacetylene flame is 2400kW/m 2, and the ablation duration is 60s.
Embodiment III:
(1) The C/C composite material with the density of 1.80g/cm 3 is processed into a block with the size of 10 multiplied by 8 multiplied by 6mm 3, and the surface of the coating to be prepared of the block is ensured to be plane.
(2) Spherical W powder with the particle size of 300 meshes is used as a preparation raw material of the grid structure, and laser selective melting equipment is utilized to perform additive manufacturing of the grid structure along the flat surface of the C/C composite material. Wherein, the grid spacing is 0.5mm, the melting parameter of the selected laser area is power 250W, the laser scanning speed is 200mm/s, and the spot diameter is 80 mu m.
(3) The preparation raw materials of the Si-SiC cladding layer are weighed, wherein the preparation raw materials comprise 65wt.% of Si powder, 20wt.% of SiC powder and 15wt.% of C powder, the particle sizes of the powder are 300 meshes, and the powder is ball-milled and mixed for 3 hours so as to realize uniform mixing of the components.
(4) Dispersing the mixed powder obtained in the step (3) in an absolute ethyl alcohol solvent, magnetically stirring for 2 hours to obtain Si-SiC coating slurry, and brushing the Si-SiC coating slurry on the surfaces of the W grid and the C/C composite material matrix. Subsequently, the slurry-coated sample was subjected to a baking treatment at 80℃for 1 hour to remove the solvent.
(5) And (3) irradiating the surface of the sample obtained in the step (4) by using a fiber laser in an argon atmosphere, and completing laser cladding treatment of preset powder and obtaining the W grid structure reinforced Si-SiC coating. Wherein, the laser cladding parameter is power 300W, scanning speed 2mm/s, and spot diameter 4mm.
(6) In order to detect the high temperature resistance and the scouring resistance of the coating, oxyacetylene flame ablation tests are respectively carried out on the Si-SiC coating and the W grid structure reinforced Si-SiC coating, and the mass ablation rates of all the samples are calculated and compared. Wherein, the heat flux density of the oxyacetylene flame is 2400kW/m 2, and the ablation duration is 60s.
The effect of the invention is further seen from the accompanying drawings:
FIG. 1 is a schematic illustration of a process for preparing a C/C composite surface grid structure enhanced ablation resistant coating. According to the invention, a W grid structure is manufactured on the surface of a flat C/C composite material matrix by laser additive, and Si-SiC coating is laser cladding on the grid and the matrix surface to obtain a grid structure reinforced coating so as to improve the anti-ablation and anti-flushing performance of the sample.
FIG. 2 is a scanning electron micrograph of a W-grid structure of the surface of the C/C composite material. From this, it was found that the lattice structure uniformly covered the surface of the C/C composite matrix with a lattice spacing of about 0.5mm.
FIG. 3 is a scanning electron microscope photograph of a W grid structure reinforced Si-SiC coating on the surface of a C/C composite material. The Si-SiC coating prepared on the surfaces of the grids and the matrix has a compact structure, has no obvious defects such as cracks, holes and the like, and has the density close to 100%.
FIG. 4 shows the surface morphology of (a-b) Si-SiC coating samples after being ablated by an oxyacetylene flame and (c-d) W lattice structure enhanced Si-SiC coating samples. From the graph (a) and the graph (c), the phenomenon that the local coating of the ablation center area is washed away occurs in both samples after the ablation of the oxyacetylene flame with the heat flux density of 2400kW/m 2 for 60 seconds, and the observation times of the scanning electron microscope pictures are enlarged to obtain the graph (b) and the graph (d) for further comparison and distinction. From the graph (b), the distribution of carbon fibers is locally visible in the ablation center area of the Si-SiC coating sample, which proves that the C/C composite material matrix is exposed at the moment, and the coating loses the protection function; in contrast, the ablated central area of figure (d) has exposed the grid structure, but the coating is still present in the grid gaps and the substrate is well protected. Therefore, si-SiC coatings incorporating the lattice structure exhibit excellent ablation resistance and erosion resistance.
Claims (10)
1. A carbon/carbon composite surface grid structure enhanced anti-ablation coating comprises a Si-SiC coating; the method is characterized in that: the surface of the carbon/carbon composite material is provided with a metal W grid, and the Si-SiC coating is coated on the surface of the matrix of the carbon/carbon composite material through laser cladding; the high melting point of W and the in-situ reaction between W and C are utilized to enhance the erosion resistance and interface bonding strength of the whole coating, and the ablation resistance of the Si-SiC coating is enhanced by the W grid structure; the metal W grid is prepared by adopting laser cladding, molten W at the bottom layer of the grid can be contacted with the C/C composite material and react to generate WC in the laser additive manufacturing process, and the existence of chemical bonding at the interface can remarkably improve the bonding strength of the W grid and further enhance the flame flow scouring resistance of the Si-SiC coating.
2. The carbon/carbon composite surface mesh structure enhanced ablation resistant coating of claim 1, wherein: the metal W grid adopts a square grid structure.
3. The carbon/carbon composite surface mesh structure enhanced ablation resistant coating of claim 2, wherein: the grid spacing of the square grid structure is 0.4-1 mm.
4. A method for preparing the carbon/carbon composite material surface grid structure reinforced ablation-resistant coating according to any one of claims 1-3 by adopting a laser cladding method, which is characterized by comprising the following steps:
Step 1: processing the surface to be prepared of the coating of the C/C composite material into a flat surface so as to facilitate powder spreading by a machine in a subsequent laser selective melting link;
Step 2, manufacturing a W grid structure:
Taking spherical W powder as a raw material, and adopting laser selective melting equipment to perform additive manufacturing of a grid structure along the flat surface of the C/C composite material;
when the laser selective melting equipment is adopted, the laser selective melting parameter is 250-350W, the laser scanning speed is 200-350mm/s, and the spot diameter is 50-80 mu m;
Step 3, preparation of Si-SiC coating:
Dispersing raw material powder obtained by mixing Si powder, siC powder and C powder in an absolute ethyl alcohol solvent, magnetically stirring for 1-3 hours to prepare Si-SiC coating slurry, brushing the slurry on the surfaces of a W grid and a C/C composite material matrix, and then placing a sample after brushing the slurry in an environment of 60-100 ℃ for drying treatment for 0.5-1.5 hours to remove the solvent;
Under argon atmosphere, using a fiber laser to irradiate surface powder, completing laser cladding treatment and obtaining a W grid structure reinforced Si-SiC coating, wherein the laser cladding parameters are 300-400W, the scanning speed is 2-4mm/s, and the spot diameter is 4-5mm;
obtaining the carbon/carbon composite material surface grid structure reinforced anti-ablation coating.
5. The method according to claim 4, wherein: the particle size of the W powder is 100-300 meshes of spherical W powder.
6. The method according to claim 4, wherein: the ratio of Si powder, siC powder to C powder is 50-70wt.% of Si powder, 15-30wt.% of SiC powder and 5-15wt.% of C powder.
7. The method according to claim 4, wherein: and mixing the Si powder, the SiC powder and the C powder by ball milling for 1-3h.
8. The method according to claim 4, wherein: the particle sizes of the Si powder, the SiC powder and the C powder are all 100-300 meshes.
9. An ablation assessment method for a carbon/carbon composite material surface grid structure reinforced ablation-resistant coating according to any one of claims 1-3, which is characterized by comprising the following steps: and carrying out oxyacetylene flame ablation test on the Si-SiC coating and the W grid structure reinforced Si-SiC coating, wherein the oxyacetylene flame heat flux density is 2400kW/m 2, and the ablation duration is 60s.
10. Use of the carbon/carbon composite surface mesh structure reinforced ablation resistant coating of any one of claims 1-3, characterized in that: the W grid reinforced Si-SiC laser cladding layer is applied to high-temperature aerobic protection of structural parts in an aircraft engine and thermal erosion environment.
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