CN116836002A - Be used for SiC f Ti-Si-C composite coating on SiC surface and preparation method thereof - Google Patents
Be used for SiC f Ti-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 167
- 238000000576 coating method Methods 0.000 title claims abstract description 92
- 239000011248 coating agent Substances 0.000 title claims abstract description 85
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 235000002639 sodium chloride Nutrition 0.000 claims description 8
- 239000011812 mixed powder 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
- 239000000758 substrate 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
- 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
- 239000011780 sodium chloride Substances 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 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
- 229910003465 moissanite Inorganic materials 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 115
- 239000010410 layer Substances 0.000 description 26
- 239000000843 powder Substances 0.000 description 12
- 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
- 238000000498 ball milling Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 230000005855 radiation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 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
- 239000003054 catalyst Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 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
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory 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
- 238000005303 weighing 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses Be used for SiC f Ti-Si-C composite coating on SiC surface and preparation method thereof. The composite coating comprises TiC layer and Ti layer from the surface of SiC matrix to the outside 3 SiC 2 Layer and Ti 5 Si 3 C x The preparation method of the composite coating comprises the following steps of: 1) Preparation of SiC with carbon-rich surface f SiC; 2) Embedding; 3) Heat treatment; 4) And (5) cleaning. The TiC layer is used for relieving Ti of the composite coating prepared by the preparation method 3 SiC 2 Thermal mismatch stress of layer and SiC matrix, ti 5 Si 3 C x The layer is used for further improving the water-oxygen resistance of the composite coating, and the composite coating can effectively improve SiC f The SiC composite material has strong bonding strength and has the resistance to water oxygen and hydrothermal corrosion.
Description
Technical Field
The invention relates to the technical field of functional coatings, in particular to a functional coating for SiC f Ti-Si-C composite coating on SiC surface and preparation method thereof.
Background
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 of third and fourth generation nuclear reactors. Currently, siC for nuclear cladding materials f /SThe iC is composed of SiC fiber, pyrolytic carbon (PyC) interface, siC (CVI-SiC) matrix prepared by chemical vapor infiltration, and other components. 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 glassy SiO 2 Subsequently SiO 2 Will react 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 attack by high temperature oxygen-containing liquid water at 350 ℃, siO 2 Also can be converted into [ SiO ] in the hydrothermal environment 3 ] 2- Finally hydrolyzing to [ H ] 2 SiO 4 ] 2- SiC prepared by CVI process with voids left by the escape of the gaseous product f The pores contained in the SiC will be channels for intrusion of water and oxygen into the material. It can be seen that the hydrothermal corrosion resistance of CVI-SiC matrix needs to be improved.
At present promote SiC f One solution to the hydrothermal liquid oxygen corrosion resistance of SiC is to prepare a SiC coating on the surface of the composite material, and the coating effectively reduces the 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. Therefore, a new coating material is needed to further promote SiC f Resistance to water oxygen for a long time of SiC. With Ti 3 SiC 2 The MAX phase material is typically of a particular layered structure, giving it high fracture toughness and high damage tolerance. At the same time Ti 3 SiC 2 Has excellent properties of radiation resistance, high temperature resistance, oxidation resistance, corrosion resistance and the like, and is ideal for nuclear cladding SiC f Coating material candidates for SiC. However, ti is 3 SiC 2 Coefficient of thermal expansion (CTE, ti) 3 SiC 2 Is 9X 10 (CTE) -6 K -1 ) Coefficient of thermal expansion with CVI-SiC matrix (4.5X10) -6 K -1 ) There is a large difference. Ti prepared at high temperature 3 SiC 2 Cooling to room temperatureGenerates extremely high thermal mismatch stress with CVI-SiC in the process, resulting in Ti 3 SiC 2 The bonding strength of the coating is reduced and the coating delaminates. Ti prepared by the processes of electrophoretic deposition, dip coating and the like which are developed at present 3 SiC 2 The coating has the problem of weak bonding force with the SiC matrix.
Disclosure of Invention
In order to solve the above-mentioned disadvantages of the prior art, an object of the present invention is to provide a SiC-based ceramic material f Ti-Si-C composite coating on SiC surface and preparation method thereof, so as to solve the problem of the prior SiC f Poor resistance to water and oxygen for a long time of/SiC, existing Ti 3 SiC 2 The binding force between the coating and the SiC matrix is weak.
The technical scheme for solving the technical problems is as follows:
be used for SiC f The Ti-Si-C composite coating on the SiC surface is characterized in that the structure of the composite coating is sequentially provided with a TiC layer and Ti from the SiC substrate surface to the outside 3 SiC 2 Layer and Ti 5 Si 3 C x The total thickness of the composite coating is 5-40 mu m, the thickness of the TiC layer is 0-15 mu m, and the Ti is 3 SiC 2 The thickness of the layer is 2-20 mu m, the Ti is 5 Si 3 C x The thickness of the layer is 0-15 mu m.
Further, the total thickness of the composite coating is 10 μm, the thickness of the TiC layer is 1 μm, and the Ti is 3 SiC 2 The thickness of the layer is 4 μm, the Ti 5 Si 3 C x The layer thickness was 5 μm.
The above is used for SiC f The preparation method of the Ti-Si-C composite coating on the SiC surface comprises the following steps:
1) Preparing SiC matrix with carbon and silicon molar ratio of 1.05-1.50 by using CVI process, or preparing pyrolytic carbon with thickness of 20-120 nm on the surface of SiC matrix with carbon and silicon molar ratio of 0.8-1.2 by using CVD process to prepare SiC with carbon-rich surface f /SiC；
2) SiC with carbon-rich surface in step 1) f Completely embedding SiC into mixed powder containing titanium powder, silicon powder and reaction auxiliary agent;
3) SiC of step 2) f Carrying out heat treatment on the SiC and the mixed powder under the protection of flowing argon to generate TiC-Ti 3 SiC 2 -Ti 5 Si 3 C x Ti-Si-C composite coating with structure;
4) Cleaning the composite coating prepared in the step 3) by using deionized water at 70-90 ℃ to prepare SiC containing Ti-Si-C composite coating with pure components f /SiC。
Further, the molar ratio of the titanium powder to the silicon powder in the step 2) is 3:0.5 to 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 and under the normal pressure, the temperature is firstly raised to 500-600 ℃ for heat preservation for 0.5-1.5 h, dehydration and drying are carried out, then the temperature is raised to 1100-1300 ℃, the temperature is kept for 1-5 h, and then the furnace cooling is carried out.
The invention has the following beneficial effects:
1) The invention can realize the total thickness of the coating, tiC and Ti by controlling the mole ratio of carbon and silicon of the SiC matrix, the addition amount of silicon powder and the heat treatment temperature and time 3 SiC 2 、Ti 5 Si 3 C x Control of the thickness of each layer: 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, ti 3 SiC 2 The greater the layer thickness, the smaller the total thickness of the coating; the longer the heat preservation time is, ti 5 Si 3 C x The greater the layer thickness and the greater the overall thickness of the coating. 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 invention is designed with TiC-Ti 3 SiC 2 -Ti 5 Si 3 C x Ti-Si-C composite coating with structure effectively improves SiC f SiC as a nuclear cladding materialThe material has resistance to water oxygen and hydrothermal corrosion. Meanwhile, compared with the prior Ti prepared by using the processes of electrophoretic deposition, dip coating and the like 3 SiC 2 A coating layer, the composite coating layer and SiC f The bonding strength of/SiC is higher.
3) The preparation method realizes TiC-Ti by using the reaction auxiliary agent 3 SiC 2 -Ti 5 Si 3 C x The synchronous synthesis of the three-layer structure has high efficiency, short period and low cost.
Drawings
FIG. 1 is SiC without coating and with Ti-Si-C composite coating prepared f Macroscopic photograph of SiC;
FIG. 2 is a graph of SiC in example 1 f TiC-Ti with SiC surface preparation 3 SiC 2 -Ti 5 Si 3 C x Microstructure of Ti-Si-C composite coating of structure;
FIG. 3 shows the TiC-Ti-containing composition obtained in example 2 3 SiC 2 -Ti 5 Si 3 C x Microstructure of Ti-Si-C composite coating of structure;
FIG. 4 shows the single phase Ti with which example 3 is prepared 3 SiC 2 Microstructure of the coating.
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:
be used for SiC f The preparation method of the Ti-Si-C composite coating on the SiC surface comprises the following steps:
1) For SiC f SiC matrix with carbon and silicon molar ratio of 1.1 is prepared by using CVI process, and PyC with thickness of 60nm is deposited on the surface of the composite material by using CVD.
2) Titanium powder: weighing titanium powder and silicon powder according to a molar ratio of 3:2, and adding 6 times of titanium powder and silicon powder based on the total mass of the titanium powder and the silicon powderSodium chloride is used as a reaction auxiliary agent, and the powder is subjected to ball milling and mixing 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 carrying out carbon-rich treatment on the SiC obtained in the step 1) f The SiC composite material is placed in an alumina crucible, and 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 2h, cooling to room temperature along with the furnace, and conveying argon with the flow of 50sccm 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 deionized water at 80 ℃, and drying to obtain SiC f The TiC-Ti is prepared on the surface of the SiC composite material 3 SiC 2 -Ti 5 Si 3 C x Ti-Si-C composite coating with structure.
FIG. 1 photo shows SiC without a coating f SiC and TiC-Ti-containing particles prepared according to the method of example 1 3 SiC 2 -Ti 5 Si 3 C x SiC of Ti-Si-C composite coating with structure 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 result of FIG. 2 (b), it is known that the coating is TiC layer, ti layer, respectively from bottom to top 3 SiC 2 Layer of Ti 5 Si 3 C x A layer, wherein the TiC layer has a thickness of 1 μm, ti 3 SiC 2 Layer thickness of 4 μm, ti 5 Si 3 C x The thickness of the layer is 5 mu m, the bonding among the layers is perfect, and the phenomena of delamination, cracking and the like are not observed at the interface.
Example 2:
be used for SiC f The preparation method of the Ti-Si-C composite coating on the SiC surface comprises the following steps:
1) For SiC f Preparing SiC matrix with carbon and silicon molar ratio of 1.1 by using CVI process, and depositing PyC with thickness of 60nm 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 carrying out carbon-rich treatment on the SiC obtained in the step 1) f Placing the SiC composite material into an alumina crucible, and completely embedding the composite material 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 of 50sccm 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 deionized water at 80 ℃, and drying to obtain SiC f The surface of the SiC composite material is provided with single-phase Ti 3 SiC 2 Ti-Si-C composite coating with coating structure.
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 has a thickness of 11 μm, ti 3 SiC 2 The thickness of the layer is 3 μm, ti 5 Si 3 C x The thickness of the layer is 11 μm, wherein TiC and Ti 5 Si 3 C x The thickness is obviously increased, ti 3 SiC 2 The 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:
be used for SiC f The preparation method of the Ti-Si-C composite coating on the SiC surface comprises the following steps:
1) For SiC f Preparing SiC matrix with carbon and silicon molar ratio of 1.4 by using CVI process;
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 carrying out carbon-rich treatment on the SiC obtained in the step 1) f Placing the SiC composite material into an alumina crucible, and completely embedding the composite material 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 of 50sccm 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 deionized water at 80 ℃, and drying to obtain SiC f The TiC-Ti is prepared on the surface of the SiC composite material 3 SiC 2 -Ti 5 Si 3 C x Ti-Si-C composite coating with structure.
FIG. 4 shows the microstructure of the single-phase coating produced in example 3, with Ti alone remaining in the coating by varying the production process parameters 3 SiC 2 The layer thickness was 12 μm. 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 2.
TABLE 2 results of bond strength test of Ti-Si-C composite coatings
| Sample preparation | Coating bond Strength (MPa) | Coating stripping mode |
| Example 1 | 42.7 | Failure of interface |
| Example 2 | 14.4 | Failure of interface |
| Example 3 | 36.5 | Failure of interface |
The results show that the three implementations all have interface failure, the three coatings and the SiC matrix are proved to crack at the interface, the strength values of the three coatings and the SiC matrix are 42.7MPa, 14.4MPa and 36.5MPa respectively, and the experimental data prove that the three coatings have TiC-Ti involved in the invention 3 SiC 2 -Ti 5 Si 3 C x The Ti-Si-C composite coating with the structure has good bonding strength with the SiC matrix.
Test example 2:
the Ti-Si-C composite coating prepared by the three examples is used as a test sample, the hydrothermal corrosion resistance of the three examples and a control group is tested in static water with 360 ℃ and 18.6MPa and dissolved oxygen concentration of 246ppm, and the control group sample is SiC without preparing the Ti-Si-C composite coating f The results of the test of the SiC composite material are shown in Table 3.
TABLE 1 Mass variation of samples from examples and control after 72h hydrothermal corrosion
| Sample preparation | Quality change (negative value indicates weightlessness) |
| Control group | -7.2％ |
| Example 1 | -0.8％ |
| Example 2 | -3.2％ |
| Example 3 | +0.1％ |
The results show that the weight loss rate of the control group is 7.2%, the weight loss of the example 1 is 0.8%, the weight loss of the example 2 is 3.2%, and the weight gain of the example 3 is 0.1% after 72h corrosion test. Test results prove that the invention relates to a catalyst with TiC-Ti 3 SiC 2 -Ti 5 Si 3 C x The Ti-Si-C composite coating with the structure can protect the substrate from corrosion in a certain time, thereby effectively improving SiC f Resistance to hydrothermal corrosion of SiC composites.
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 (9)
1. Be used for SiC f The Ti-Si-C composite coating on the SiC surface is characterized in that the structure of the composite coating is sequentially provided with a TiC layer and Ti from the SiC substrate surface to the outside 3 SiC 2 Layer and Ti 5 Si 3 C x The total thickness of the composite coating is 5-40 mu m, the thickness of the TiC layer is 0-15 mu m, and the Ti is 3 SiC 2 The thickness of the layer is 2-20 mu m, the Ti is 5 Si 3 C x The thickness of the layer is 0-15 mu m.
2. The method for SiC according to claim 1 f A Ti-Si-C composite coating on the surface of SiC, which is characterized in that the total thickness of the composite coating is 10 mu m, the thickness of a TiC layer is 1 mu m, and the Ti is 3 SiC 2 The thickness of the layer is 4 μm, the Ti 5 Si 3 C x The layer thickness was 5 μm.
3. The method for SiC of claim 1 or 2 f The preparation method of the Ti-Si-C composite coating on the SiC surface is characterized by comprising the following steps:
1) SiC with carbon-rich surface is prepared from SiC matrix with mole ratio of 1.05-1.50 of carbon to silicon or SiC matrix with mole ratio of 0.8-1.2 of carbon and silicon with pyrolytic carbon with thickness of 20-120 nm f /SiC；
2) SiC with carbon-rich surface as described in step 1) f Completely embedding SiC into mixed powder containing titanium powder, silicon powder and reaction auxiliary agent;
3) The SiC of the step 2) f Carrying out heat treatment on the SiC and the mixed powder under the protection of flowing inert gas to generate TiC-Ti 3 SiC 2 -Ti 5 Si 3 C x Ti-Si-C composite coating with structure.
4. A method for SiC according to claim 3 f The preparation method of the Ti-Si-C composite coating on the SiC surface is characterized by comprising the following steps of 2) the molar ratio of the titanium powder to the silicon powder is 3:0.5 to 3:3.
5. a method for SiC according to claim 3 f The preparation method of the Ti-Si-C composite coating on the SiC surface is characterized in that the reaction auxiliary agent in the step 2) is halogenated salt.
6. The method for SiC according to claim 5 f The preparation method of the Ti-Si-C composite coating on the SiC surface is characterized in that the halogenated salt is sodium fluoride, potassium fluoride, sodium chloride, potassium chloride, sodium bromide or potassium bromide.
7. The method according to claim 3, 5 or 6 for SiC f The preparation method of the Ti-Si-C composite coating on the SiC surface is characterized in that 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.
8. A method for SiC according to claim 3 f The preparation method of the Ti-Si-C composite coating on the SiC surface is characterized by comprising the following specific steps of: under the protection of argon with the flow of 10-100 sccm and under the normal pressure, the temperature is firstly raised to 500-600 ℃ for heat preservation for 0.5-1.5 h, dehydration and drying are carried out, then the temperature is raised to 1100-1300 ℃, the temperature is kept for 1-5 h, and then the furnace cooling is carried out.
9. A method for SiC according to claim 3 f The preparation method of the Ti-Si-C composite coating on the SiC surface is characterized in that deionized water at 70-90 ℃ is used for cleaning the composite coating in the step 3), and the SiC containing the Ti-Si-C composite coating with pure components is prepared f /SiC。
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