CN116836002B - Be used for SiCfTi-Si-C composite coating on SiC surface and preparation method thereof - Google Patents
Be used for SiCfTi-Si-C composite coating on SiC surface and preparation method thereof Download PDFInfo
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- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 128
- 238000000576 coating method Methods 0.000 title claims abstract description 84
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 239000011863 silicon-based powder Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910009871 Ti5Si3 Inorganic materials 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 235000002639 sodium chloride Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002296 pyrolytic carbon Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 238000004140 cleaning Methods 0.000 abstract description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 87
- 239000010410 layer Substances 0.000 description 26
- 239000000843 powder Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000005253 cladding Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000001652 electrophoretic deposition Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
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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
-
- 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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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a Ti-Si-C composite coating for SiC f/SiC surfaces and a preparation method thereof. The composite coating has a three-layer structure comprising a TiC layer, a Ti 3SiC2 layer and a Ti 5Si3Cx layer from the surface of a SiC substrate to the outside, and the preparation method of the composite coating comprises the following steps: 1) Preparing SiC f/SiC with a carbon-rich surface; 2) Embedding; 3) Heat treatment; 4) And (5) cleaning. The TiC layer is used for relieving the thermal mismatch stress of the Ti 3SiC2 layer and the SiC matrix, the Ti 5Si3Cx layer is used for further improving the water-oxygen resistance of the composite coating, the composite coating can effectively improve the water-oxygen resistance and hydrothermal corrosion resistance of the SiC f/SiC composite material, and the composite coating has stronger bonding strength.
Description
Technical Field
The invention relates to the technical field of functional coatings, in particular to a Ti-Si-C composite coating for SiC f/SiC surfaces and a preparation method thereof.
Background
The silicon carbide continuous fiber reinforced silicon carbide composite material (SiC f/SiC) has the characteristics of high strength, high toughness, radiation resistance, high temperature resistance, oxidation resistance and the like, and is expected to become a novel accident-resistant cladding material for improving the overall system safety type of third and fourth generation nuclear reactors. Currently, siC f/SiC used for nuclear cladding materials is composed of components such as SiC fibers, pyrolytic carbon (PyC) interfaces, siC (CVI-SiC) matrixes prepared by chemical vapor infiltration, and the like. In boiling water reactors, high temperature water vapor containing oxygen is in direct contact with the nuclear fuel rod cladding, and the nuclear cladding material is required to possess high temperature resistance to oxygen corrosion. CVI-SiC reacts with oxygen in this environment to form the glassy phase SiO 2, and then SiO 2 reacts with a mixture of water and water vapor to form the gaseous product Si (OH) 4. In addition, in pressurized water reactors, the nuclear cladding material needs to resist the attack of high temperature oxygen-containing liquid water at 350 ℃, siO 2 can be converted into [ SiO 3]2-, and finally hydrolyzed into [ H 2SiO4]2- ], and the pores left by the escape of the gaseous products and the pores contained in SiC f/SiC prepared by the CVI process become channels for the invasion of water oxygen into the material. It can be seen that the hydrothermal corrosion resistance of CVI-SiC matrix needs to be improved.
At present, one scheme for improving the hydrothermal liquid oxygen corrosion resistance of SiC f/SiC is to prepare a SiC coating on the surface of a composite material, and the coating is coated to effectively reduce a diffusion channel of water and oxygen. However, CVD-SiC coatings possess a chemical composition similar to that of the SiC substrate, and as the corrosion time increases, siC grains in the CVD-SiC coating react with water oxygen in the environment at grain boundaries. The strong intergranular corrosion causes delamination of the coating and eventual failure. Thus, a new coating material is needed to further enhance the long-term resistance of SiC f/SiC to water oxygen. MAX phase materials, represented by Ti 3SiC2, have a special layered structure, giving them high fracture toughness and high damage tolerance. Meanwhile, ti 3SiC2 has excellent properties of radiation resistance, high temperature resistance, oxidation resistance, corrosion resistance and the like, and is an ideal coating material candidate for nuclear cladding SiC f/SiC. However, the coefficient of thermal expansion of Ti 3SiC2 (CTE, CTE of Ti 3SiC2 is 9X 10 -6K-1) is significantly different from that of CVI-SiC matrix (4.5X 10 -6K-1). The Ti 3SiC2 prepared at high temperature can generate extremely high thermal mismatch stress with CVI-SiC in the process of cooling to room temperature, so that the bonding strength of the Ti 3SiC2 coating is reduced, and the coating is delaminated and peeled off. The Ti 3SiC2 coating prepared by the processes of electrophoretic deposition, dip coating and the like which are developed at present has the problem of weak bonding force with the SiC matrix.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a Ti-Si-C composite coating for the surface of SiC f/SiC and a preparation method thereof, so as to solve the problems of poor long-time water and oxygen resistance of the conventional SiC f/SiC and weak bonding force of the conventional Ti 3SiC2 coating and a SiC matrix.
The technical scheme for solving the technical problems is as follows:
The Ti-Si-C composite coating for the SiC f/SiC surface is characterized in that the structure of the composite coating sequentially comprises a TiC layer, a Ti 3SiC2 layer and a Ti 5Si3Cx layer from the SiC substrate surface to the outside, the total thickness of the composite coating is 5-40 mu m, the thickness of the TiC layer is 0-15 mu m, the thickness of the Ti 3SiC2 layer is 2-20 mu m, and the thickness of the Ti 5Si3Cx layer is 0-15 mu m.
Further, the total thickness of the composite coating layer was 10 μm, the thickness of the TiC layer was 1 μm, the thickness of the Ti 3SiC2 layer was 4 μm, and the thickness of the Ti 5Si3Cx layer was 5 μm.
The preparation method of the Ti-Si-C composite coating for the SiC f/SiC surface comprises the following steps:
1) Preparing a SiC matrix with a carbon/silicon molar ratio of 1.05-1.50 by using a CVI process, or preparing pyrolytic carbon with a thickness of 20-120 nm on the surface of the SiC matrix with a carbon/silicon molar ratio of 0.8-1.2 by using a CVD process to prepare SiC f/SiC with a carbon-rich surface;
2) Completely embedding the SiC f/SiC with the carbon-rich surface in the step 1) into mixed powder containing titanium powder, silicon powder and a reaction auxiliary agent;
3) Carrying out heat treatment on the SiC f/SiC and the mixed powder in the step 2) under the protection of flowing argon to generate a Ti-Si-C composite coating with a TiC-Ti 3SiC2-Ti5Si3Cx structure;
4) And (3) cleaning the composite coating prepared in the step (3) by using deionized water at 70-90 ℃ to prepare the SiC f/SiC of the Ti-Si-C composite coating with pure components.
Further, the molar ratio of the titanium powder to the silicon powder in the step 2) is 3: 0.5-3: 3.
Further, the reaction auxiliary agent in the step 2) is halogenated salt.
Further, the halogenated salt includes sodium fluoride, potassium fluoride, sodium chloride, potassium chloride, sodium bromide, or potassium bromide.
Further, the adding mass of the reaction auxiliary agent in the step 2) is 4-8 times of the sum of the mass of the titanium powder and the mass of the silicon powder.
Further, the specific mode of the heat treatment in the step 3) is as follows: under the protection of argon with the flow of 10-100 sccm at normal pressure, heating to 500-600 ℃ for 0.5-1.5 h, dehydrating and drying, heating to 1100-1300 ℃, preserving heat for 1-5 h, and cooling along with a furnace.
The invention has the following beneficial effects:
1) The invention can control the total thickness of the coating and the thicknesses of each layer of TiC and Ti 3SiC2、Ti5Si3Cx by controlling the carbon and silicon mole ratio of the SiC matrix, the addition amount of silicon powder and the heat treatment temperature and time respectively: wherein, the higher the carbon content of the SiC matrix is, the larger the thickness of the TiC layer is and the larger the total thickness of the coating is; the higher the silicon powder content is, the larger the thickness of the Ti 3SiC2 layer is, and the smaller the total thickness of the coating is; the longer the hold time, the greater the Ti 5Si3Cx layer thickness and the greater the total coating thickness. The thickness of each layer and the total thickness of the coating are regulated and controlled, so that the optimization of the coating performance can be realized.
2) The Ti-Si-C composite coating with the TiC-Ti 3SiC2-Ti5Si3Cx structure effectively improves the resistance of SiC f/SiC serving as a nuclear cladding material to water oxygen and hydrothermal corrosion. Meanwhile, compared with the Ti 3SiC2 coating prepared by the previous process such as electrophoretic deposition, dip coating and the like, the composite coating has higher bonding strength with SiC f/SiC.
3) The preparation method provided by the invention realizes synchronous synthesis of the TiC-Ti 3SiC2-Ti5Si3Cx three-layer structure by using the reaction auxiliary agent, and has the advantages of high efficiency, short period and low cost.
Drawings
FIG. 1 is a macroscopic photograph of SiC f/SiC without coating and with Ti-Si-C composite coating prepared;
FIG. 2 is a microstructure of a Ti-Si-C composite coating with TiC-Ti 3SiC2-Ti5Si3Cx structure prepared on SiC f/SiC surface in example 1;
FIG. 3 is a microstructure of the Ti-Si-C composite coating having TiC-Ti 3SiC2-Ti5Si3Cx structure prepared in example 2;
FIG. 4 is a microstructure of the coating with single phase Ti 3SiC2 produced in example 3.
Detailed Description
The examples given below are only intended to illustrate the invention and are not intended to limit the scope thereof. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
a preparation method of a Ti-Si-C composite coating for SiC f/SiC surface comprises the following steps:
1) SiC f/SiC is used for preparing a SiC matrix with the molar ratio of carbon to silicon of 1.1 by using a CVI process, and then PyC with the thickness of 60 nm is deposited on the surface of the composite material by using CVD.
2) Titanium powder: the titanium powder and the silicon powder are weighed according to the molar ratio of 3:2, and based on the total mass of the titanium powder and the silicon powder, 6 times of sodium chloride is added as a reaction auxiliary agent, and the powder is ball-milled and mixed in absolute ethyl alcohol for 24 hours. And (3) after ball milling, drying the mixture, sieving the mixture by a 200-mesh sieve to obtain raw material powder required by preparing a coating, and placing the SiC f/SiC composite material subjected to carbon-rich treatment obtained in the step (1) into an alumina crucible, wherein the composite material is completely embedded by using the raw material powder.
3) Placing the alumina crucible into a tube furnace, heating to 500 ℃ and preserving heat for 1 h, removing crystal water possibly contained in mixed powder, heating to 1200 ℃ and preserving heat for 2 h, cooling to room temperature along with the furnace, and conveying argon with the flow rate of 50 sccm in the whole heat treatment process;
4) Washing off excessive powder adhered to the surface of the composite material subjected to the heat treatment in the step 3) by using 80 ℃ deionized water, and drying to obtain the Ti-Si-C composite coating with the TiC-Ti 3SiC2-Ti5Si3Cx structure on the surface of the SiC f/SiC composite material.
FIG. 1 is a photograph showing SiC f/SiC of an uncoated, ti-Si-C composite coating having a TiC-Ti 3SiC2-Ti5Si3Cx structure prepared by the method of example 1, siC f/SiC. The prepared coating has typical silvery white characteristics of metal, and the coating uniformly wraps the substrate. Fig. 2 shows the microstructure of the Ti-Si-C composite coating observed using scanning electron microscope back-scattered electron signals. As can be seen from fig. 2 (a), the coating layer can cover the uneven substrate surface with a thickness of 10 μm. From the analysis results of fig. 2 (b) 1, it is known that the coating layers are respectively a TiC layer, a Ti 3SiC2 layer and a Ti 5Si3Cx layer from bottom to top, wherein the TiC layer has a thickness of 1 μm, the Ti 3SiC2 layer has a thickness of 4 μm, the Ti 5Si3Cx layer has a thickness of 5 μm, the bonding between the layers is perfect, and no delamination, cracking and other phenomena are observed at the interface.
Example 2:
a preparation method of a Ti-Si-C composite coating for SiC f/SiC surface comprises the following steps:
1) Preparing a SiC matrix with a carbon-silicon molar ratio of 1.1 from SiC f/SiC by using a CVI process, and depositing PyC with a thickness of 60 nm on the surface of the composite material by using CVD;
2) Titanium powder: the titanium powder and the silicon powder are weighed according to the molar ratio of 3:1.33, and based on the total mass of the titanium powder and the silicon powder, 6 times of sodium chloride is added as a reaction auxiliary agent, and the powder is ball-milled and mixed in absolute ethyl alcohol for 24 hours. Drying the mixture after ball milling, sieving with a 200-mesh sieve to obtain raw material powder required by preparing a coating, and placing the carbon-rich SiC f/SiC composite material obtained in the step 1) into an alumina crucible, wherein the composite material is completely embedded by using the raw material powder;
3) Placing the alumina crucible into a tube furnace, heating to 500 ℃ and preserving heat for 1h, removing crystal water possibly contained in mixed powder, heating to 1200 ℃ and preserving heat for 5h, cooling to room temperature along with the furnace, and conveying argon with the flow rate of 50 sccm in the whole heat treatment process;
4) Washing off excessive powder adhered to the surface of the composite material subjected to the heat treatment in the step 3) by using 80 ℃ deionized water, and drying to obtain the Ti-Si-C composite coating with the single-phase Ti 3SiC2 coating structure on the surface of the SiC f/SiC composite material.
Fig. 3 shows the microstructure of the coating produced in example 2, the total thickness of the coating being raised to 25 μm by varying the production process parameters, wherein the TiC layer thickness is 11 μm, the Ti 3SiC2 layer thickness is 3 μm, and the Ti 5Si3Cx layer thickness is 11 μm, wherein the TiC and Ti 5Si3Cx thicknesses are significantly increased and the Ti 3SiC2 thickness is reduced. This illustrates that the preparation method according to the invention allows flexible control of the thickness of the coating produced.
Example 3:
a preparation method of a Ti-Si-C composite coating for SiC f/SiC surface comprises the following steps:
1) Preparing SiC matrix with carbon and silicon molar ratio of 1.4 by using CVI process on SiC f/SiC;
2) Titanium powder: the titanium powder and the silicon powder are weighed according to the molar ratio of 3:2, and based on the total mass of the titanium powder and the silicon powder, 6 times of sodium chloride is added as a reaction auxiliary agent, and the powder is ball-milled and mixed in absolute ethyl alcohol for 24 hours. Drying the mixture after ball milling, sieving with a 200-mesh sieve to obtain raw material powder required by preparing a coating, and placing the carbon-rich SiC f/SiC composite material obtained in the step 1) into an alumina crucible, wherein the composite material is completely embedded by using the raw material powder;
3) Placing the alumina crucible into a tube furnace, heating to 500 ℃ and preserving heat for 1h, removing crystal water possibly contained in mixed powder, heating to 1300 ℃ and preserving heat for 5h, cooling to room temperature along with the furnace, and conveying argon with the flow rate of 50 sccm in the whole heat treatment process;
4) Washing off excessive powder adhered to the surface of the composite material subjected to the heat treatment in the step 3) by using 80 ℃ deionized water, and drying to obtain the Ti-Si-C composite coating with the TiC-Ti 3SiC2-Ti5Si3Cx structure on the surface of the SiC f/SiC composite material.
FIG. 4 shows the microstructure of the single-phase coating produced in example 3, in which only the Ti 3SiC2 layer was retained by varying the production process parameters, with a thickness of 12. Mu.m. This illustrates that the preparation method according to the invention allows flexible control of the composition of the coating.
Test example 1:
The Ti-Si-C composite coatings prepared by the three embodiments are used as test samples, the coating strength of the three embodiments is tested according to national standard GB/T39685-2020 "method for testing bonding strength of ceramic coating", and the test results are shown in Table 1.
TABLE 1 Ti-Si-C composite coating bond Strength test results
The results show that the three implementations all have interface failure, and the three coatings and the SiC matrix are proved to crack at the interface, the strength values of the three coatings are 42.7 MPa, 14.4 MPa and 36.5 MPa respectively, and the experimental data prove that the Ti-Si-C composite coating with the TiC-Ti 3SiC2-Ti5Si3Cx structure has good bonding strength with the SiC matrix.
Test example 2:
The three examples and the control group were tested for their resistance to hydrothermal corrosion in 360 ℃ static water having a dissolved oxygen concentration of 246, ppm using the Ti-Si-C composite coating prepared in the above three examples as test samples, the control group sample being SiC f/SiC composite material from which no Ti-Si-C composite coating was prepared, and the test results are shown in table 2.
TABLE 2 Mass variation of samples from examples and control after 72h hydrothermal corrosion
The results show that the control group has a weight loss of 7.2%, example 1 has a weight loss of 0.8%, example 2 has a weight loss of 3.2% and example 3 has a weight gain of 0.1% after 72 h corrosion test. Test results prove that the Ti-Si-C composite coating with the TiC-Ti 3SiC2-Ti5Si3Cx structure can protect a substrate from corrosion within a certain time, and effectively improves the resistance of the SiC f/SiC composite material to hydrothermal corrosion.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (6)
1. The Ti-Si-C composite coating for the SiC f/SiC surface is characterized in that the structure of the composite coating sequentially comprises a TiC layer, a Ti 3SiC2 layer and a Ti 5Si3Cx layer from the SiC substrate surface to the outside, the total thickness of the composite coating is 10-40 mu m, the thickness of the TiC layer is 1-15 mu m, the thickness of the Ti 3SiC2 layer is 2-20 mu m, and the thickness of the Ti 5Si3Cx layer is 5-15 mu m;
The Ti-Si-C composite coating for the SiC f/SiC surface is prepared by the following method:
1) Taking a SiC matrix with a carbon/silicon molar ratio of 1.05-1.50 or a SiC matrix with a carbon/silicon molar ratio of 0.8-1.2, which has pyrolytic carbon with a thickness of 20-120 nm, as SiC f/SiC with a carbon-rich surface;
2) Completely embedding the SiC f/SiC with the carbon-rich surface in the step 1) into mixed powder containing titanium powder, silicon powder and a reaction auxiliary agent;
3) Carrying out heat treatment on the SiC f/SiC and the mixed powder in the step 2) under the protection of flowing inert gas to generate a Ti-Si-C composite coating with a TiC-Ti 3SiC2-Ti5Si3Cx structure;
Wherein, the mole ratio of the titanium powder to the silicon powder in the step 2) is 3: (0.5-3);
The specific heat treatment process of the step 3) comprises the following steps: under the protection of argon with the flow of 10-100 sccm at normal pressure, heating to 500-600 ℃ for 0.5-1.5 h, dehydrating and drying, heating to 1100-1300 ℃, preserving heat for 1-5 h, and cooling along with a furnace.
2. The Ti-Si-C composite coating for SiC f/SiC surfaces of claim 1, wherein the total thickness of the composite coating is 10 μιη, the TiC layer thickness is 1 μιη, the Ti 3SiC2 layer thickness is 4 μιη, and the Ti 5Si3Cx layer thickness is 5 μιη.
3. The Ti-Si-C composite coating for SiC f/SiC surfaces of claim 1, wherein the reaction aid of step 2) is a halogenated salt.
4. A Ti-Si-C composite coating for SiC f/SiC surfaces according to claim 3, wherein the halogenated salt is sodium fluoride, potassium fluoride, sodium chloride, potassium chloride, sodium bromide or potassium bromide.
5. The Ti-Si-C composite coating for SiC f/SiC surfaces according to claim 1 or 3 or 4, characterized in that step 2) the reaction auxiliary agent is added by a mass 4 to 8 times the sum of the mass of the titanium powder and the silicon powder.
6. The Ti-Si-C composite coating for SiC f/SiC surfaces of claim 1, wherein the composite coating in step 3) is cleaned with deionized water at 70-90 ℃ to obtain SiC f/SiC containing the Ti-Si-C composite coating with pure components.
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