CN115073214A - Method for preparing graphite piece oxidation-resistant coating based on silicon resin dip coating liquid precursor conversion method - Google Patents
Method for preparing graphite piece oxidation-resistant coating based on silicon resin dip coating liquid precursor conversion method Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 102
- 239000010439 graphite Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000000576 coating method Methods 0.000 title claims abstract description 55
- 239000011248 coating agent Substances 0.000 title claims abstract description 53
- 239000011347 resin Substances 0.000 title claims abstract description 48
- 229920005989 resin Polymers 0.000 title claims abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 44
- 239000010703 silicon Substances 0.000 title claims abstract description 44
- 238000003618 dip coating Methods 0.000 title claims abstract description 28
- 230000003647 oxidation Effects 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 20
- 239000012705 liquid precursor Substances 0.000 title claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 5
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- 230000003064 anti-oxidating effect Effects 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 claims 1
- XJWOWXZSFTXJEX-UHFFFAOYSA-N phenylsilicon Chemical compound [Si]C1=CC=CC=C1 XJWOWXZSFTXJEX-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000007770 graphite material Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910003465 moissanite Inorganic materials 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- 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
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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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- 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
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
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- 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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- 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
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Abstract
A method for preparing an oxidation-resistant coating of a graphite piece based on a silicon resin dip coating liquid precursor conversion method belongs to the technical field of application, and specifically comprises the following steps: step one, dip-coating an organic silicon resin solution on a graphite piece; step two, heating and curing the dip-coated graphite piece, wherein the curing process is set to keep the temperature at 120 ℃ for 1h, keep the temperature at 150 ℃ for 1h, keep the temperature at 180 ℃ for 2h, keep the temperature at 210 ℃ for 2h, and keep the temperature at 250 ℃ for 4h to obtain a cured graphite piece; step three, sintering the solidified graphite piece at high temperature, heating the solidified graphite piece to 800 ℃ from room temperature at a heating rate of 10 ℃/min under the protection of argon gas in the sintering process, preserving heat for 1h, then heating the solidified graphite piece to 1100 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, then reducing the temperature to 400 ℃ at a cooling rate of 2 ℃/min, and closing the program to naturally cool the solidified graphite piece to obtain a sintered graphite piece; and step four, repeating the step one and the step two on the sintered graphite piece to obtain the graphite piece protected by the antioxidant coating.
Description
Technical Field
The invention belongs to the technical field of application, and particularly relates to a method for preparing an oxidation resistant coating of a conventional graphite piece based on a silicon resin dip coating liquid precursor conversion method.
Background
The graphite material has the advantages of high temperature resistance, stable chemical property, excellent thermal shock resistance and outstanding high-temperature mechanical property, and is widely applied to the high-temperature fields of nuclear reactors, aerospace, scale prevention, rust prevention and the like. The graphite material can be oxidized in an aerobic high-temperature (400 ℃) environment, the oxidation rate is accelerated when the temperature is higher, and the graphite material can disappear after being oxidized in 1500 ℃ air for two hours.
From the preparation process of graphite, the graphite manufacturing is a high-energy-consumption and high-pollution process, and the preparation of the antioxidant coating of graphite has a profound significance from the resource perspective, the production cost, the product quality and other aspects.
Preparing the anti-oxidation coating on the graphite material surface can not change graphite own structural composition, high temperature resistant anti-oxidation coating prevents oxygen to graphite material internal diffusion to avoid the oxidation of graphite material self, in order to promote the oxidation resistance of graphite appearance spare as high as possible, coating material self should have excellent high temperature resistant oxidation resistance, and will closely combine with base member graphite material, also need have certain matching in the aspect of the coefficient of thermal expansion.
The prior method for preparing the oxidation resistant coating on the graphite surface mainly comprises a vapor deposition method, an embedding method, a precursor conversion method and the like, and various preparation methods have advantages and disadvantages.
The vapor deposition method utilizes gaseous substances to perform activation reaction on the surface of a solid material to form a solid film, and the components of a deposition product can be changed by regulating the types and the proportions of reaction gases. The oxidation-resistant coating prepared by the method has controllable components and compact tissue structure, and the coating prepared by the method is poor in combination with a graphite matrix material and high in manufacturing cost at present.
The embedding method is to put the graphite material of the matrix into the raw material of the coating, treat the graphite material at high temperature under the protection of inert gas or under a certain vacuum degree, and form the coating on the surface of the graphite matrix by means of reaction diffusion, but the method requires that the matrix material has higher porosity.
The precursor conversion method is a process method for converting the silicon-containing organic precursor into the ceramic by heating, crosslinking and cracking processes, and has the advantages of simplicity, easy control, high product purity, good performance and the like, but the compactness of the conventional powdery silicon material is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing an antioxidant coating of a graphite piece based on a precursor conversion method of a silicon resin dip-coating liquid, wherein a dip-coating method is combined with the precursor conversion method, and a high-temperature antioxidant coating is prepared on the surface of a graphite material.
The invention adopts the following technical scheme: a method for preparing an oxidation-resistant coating of a graphite piece based on a silicon resin dip coating liquid precursor conversion method comprises the following steps:
step one, dip-coating a graphite piece by using an organic silicon resin solution under the action of ultrasonic cavitation, and volatilizing a solvent to obtain the dip-coated graphite piece;
step two, heating and curing the dip-coated graphite piece, wherein the curing process is set to keep the temperature at 120 ℃ for 1h, keep the temperature at 150 ℃ for 1h, keep the temperature at 180 ℃ for 2h, keep the temperature at 210 ℃ for 2h, and keep the temperature at 250 ℃ for 4h to obtain a cured graphite piece;
step three, sintering the solidified graphite piece at high temperature, heating the solidified graphite piece to 800 ℃ from room temperature at a heating rate of 10 ℃/min under the protection of argon gas in the sintering process, preserving heat for 1h, then heating the solidified graphite piece to 1100 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, then reducing the temperature to 400 ℃ at a cooling rate of 2 ℃/min, and closing the program to naturally cool the solidified graphite piece to obtain a sintered graphite piece;
and step four, repeating the step one and the step two on the sintered graphite piece to obtain the graphite piece protected by the antioxidant coating.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the high-temperature oxidation resistant coating of the graphite piece, the dip coating method and the precursor conversion method are combined, the organic silicon resin high-temperature oxidation resistant coating is prepared on the surface of the graphite sample piece, the oxidation resistance is strong, and the bonding strength of the coating and a graphite matrix is high.
(2) According to the preparation method of the high-temperature oxidation-resistant coating of the graphite piece, when the organic silicon resin reaches 60%, the organic silicon resin is dissolved in a solvent under the influence of factors such as solubility and the like, the dissolution process is easy to agglomerate, and when the mass fraction is more than 60%, the organic silicon resin cannot be completely dissolved. In addition, the prepared dip-coating liquid has high resin content and high viscosity, so that the obtained graphite piece has poor anti-oxidation coating uniformity and cannot fully fill cavities, and air still remains in the graphite piece, so that the organic silicon resin solution with the organic silicon resin content of 30-60% is selected.
(3) The preparation method of the high-temperature oxidation-resistant coating for the graphite piece, provided by the invention, is simple and feasible, effectively reduces the cost and promotes industrial production.
(4) The preparation method of the high-temperature oxidation-resistant coating for the graphite piece, provided by the invention, has the advantages of good thickness uniformity, simplicity and convenience in operation, strong process controllability and good thermal shock stability.
Drawings
FIG. 1: photo before sintering of the solidified graphite piece;
FIG. 2: a picture of the sintered solidified graphite piece;
FIG. 3: (a) and (b) photos of the graphite piece protected by the anti-oxidation coating before ablation in an anti-oxidation experiment;
FIG. 4: the corresponding photographs of the graphite pieces shown in FIGS. 3(a) and (b) after ablation oxidation in a muffle furnace;
FIG. 5: the graphite piece protected by the anti-oxidation coating compresses and destroys the picture;
FIG. 6: SEM photograph after compression failure of graphite piece protected by oxidation resistant coating;
FIG. 7: SEM photographs of untreated graphite test pieces after compression failure.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the accompanying drawings and the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
A method for preparing an oxidation-resistant coating of a graphite piece based on a silicon resin dip coating liquid precursor conversion method comprises the following steps:
step one, 120g of methyltriethoxysilane, 20g of phenyltrimethoxysilane and 45g of methylphenyldimethoxysilane are placed in a three-neck flask, 25g of isopropanol is added to serve as a solvent, 0.8g of 10mol/L concentrated hydrochloric acid and 50g of deionized water serve as catalysts, the catalysts are added for 5 times (preventing bumping), the reaction temperature is controlled to be 75 ℃, and the reaction is carried out for 10 hours to prepare the methylphenylsilicone resin. Removing the upper-layer solvent by using a siphon principle to obtain lower-layer silicon resin, standing for 12 hours, sucking the residual solvent on the upper part by using a dropper, adding the silicon resin into a three-mouth flask, building a reduced pressure distillation device until no solvent is evaporated, keeping the temperature at 120 ℃ for 1.5 hours, taking out the silicon resin while hot, cooling and standing, crushing the silicon resin into powder, and dissolving the silicon resin in the solvent to obtain a silicon resin solution (namely a dip-coating solution), wherein the mass ratio of the silicon resin in the silicon resin solution is 30-60%; taking a graphite piece (about 15mm multiplied by 20mm) with a certain specification, polishing and chamfering with 800-mesh abrasive paper, reducing the influence of poor dip-coating effect caused by boundary resin tape casting, cleaning with ethanol by using an ultrasonic device, placing in a vacuum oven at 80 ℃ for drying for at least two hours, dip-coating an organic silicon resin solution on the surface of the graphite piece by using ultrasonic cavitation, and then placing in the oven at 80 ℃ for fully volatilizing a solvent to obtain a dip-coated graphite piece; the dip-coating process is carried out in ultrasonic equipment, and the graphite piece is immersed in the dip-coating liquid, so that the dip-coating liquid can be fully immersed in micropores of the graphite piece, the formation of an anti-oxidation coating is promoted, and the density of the coating is improved;
step two, placing the dip-coated graphite piece in a forced air drying oven for heating and curing, wherein the curing process is set to keep the temperature at 120 ℃ for 1h, keep the temperature at 150 ℃ for 1h, keep the temperature at 180 ℃ for 2h, keep the temperature at 210 ℃ for 2h, and keep the temperature at 250 ℃ for 4h to obtain a cured graphite piece;
and step three, sintering the solidified graphite piece at high temperature in a tubular furnace, heating to 800 ℃ from room temperature at a heating rate of 10 ℃/min under the protection of argon gas in the sintering process, preserving heat for 1h, heating to 1100 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, reducing the temperature to 400 ℃ at a cooling rate of 2 ℃/min, and closing the program to naturally cool to obtain the sintered graphite piece.
And step four, repeating the step one and the step two on the sintered graphite piece to obtain the graphite piece protected by the antioxidant coating.
Influenced by the volume of the tube furnace, the number of the sintered blocks of the graphite piece in example 1 is ten, eight graphite samples with relatively intact surface coatings are taken, the graphite samples are soaked in the ultrasonic cavitation and the organic silicon resin solution again, the dried graphite samples are placed in a blast oven for curing, the curing and temperature rising procedures are consistent with the steps, nano aluminum powder is added as an oxygen scavenger, then the nano aluminum powder is placed in nano cerium oxide, and the cerium oxide is used as a plugging filler to reduce the damage of an internal structure caused by external oxygen. Placing the massive graphite coated with the deoxidant and the plugging filler in a muffle furnace, adding two graphite pieces which are not subjected to dip coating treatment as a control group, measuring the oxidation resistance of the massive graphite pieces in an air atmosphere, heating to 800 ℃ at a speed of 10 ℃/min, preserving the temperature for 1h, closing the program, naturally cooling, weighing, and measuring the oxidation weight loss. The graphite sample after dip coating treatment loses weight of 4.772% after being oxidized, and the graphite sample without treatment loses weight of 6.961%, which shows that the oxidation resistance of the graphite can be reduced to a certain degree by treating the blocky graphite by adopting the organic silicon resin dip coating process. The selected block graphite is compact, the silicone resin dipped on the surface is less, and the method mainly plays a role in sealing and filling the surface pores. Most coatings reported in the prior art mostly adopt methods such as powder embedding or vapor deposition, wherein the embedding method requires that a matrix material has higher porosity, particularly the size of embedded powder seriously influences the uniformity of the coating and is difficult to control, the vapor deposition method has the big problems that the coating prepared by the method is poor in combination with the graphite matrix material, the preparation cost is high, a high-temperature environment is often needed, the anti-oxidation coating prepared by dip-coating the organic silicon resin solution is uniform, the heat resistance of the used organic silicon resin is good, can generate ceramic under high temperature, is different from directly using ceramic powder as an anti-oxidation coating, has good surface uniformity of the coating prepared by ceramic transformation of organic silicon resin, the operation is very simple and convenient, the conventional coating preparation generally needs to separately manufacture the bonding layer, the oxygen barrier layer and the packing layer, the process is complicated, and the special requirement is provided for the porosity of the graphite.
The conversion process of the precursor subjected to the ceramic pyrolysis is an organic-inorganic conversion process, the organic silicon resin coating can be subjected to side group fracture in the sintering process, the fractured side group can be discharged in a micromolecule form to generate a large number of pores, the silicon resin is dip-coated and cured again after sintering to be used as a sealing and filling layer, the oxidation area can be reduced, the oxidation resistance is improved, the uncrosslinked micromolecules can be pyrolyzed and escaped in a system at 300-390 ℃, and then inorganic conversion is carried out.
Si atoms on the main chain of the organic silicon resin are attacked by silicon hydroxyl at about 400 ℃ to generate linear or annular oligomers, the bond energy of Si-C bonds and C-C bonds is similar in the range of 500-650 ℃, micromolecular hydrocarbon is released, and then the cross-linking density of the polysiloxane is gradually improved. Pyrolysis continues to occur at about 700 ℃, bonds with high bond energy are also broken, and activated silicon atoms are oxidized to generate inorganic transformation, so that Si-O-C ceramic is generated.
And repeating the dip-coating curing step to prepare a part of graphite samples, and performing compression resistance test on the samples by using a universal electronic testing machine, wherein the compression strength of the graphite which is not subjected to the dip-coating curing treatment is 89Mpa, and the compression strength of the treated samples can reach 102 Mpa.
The surface of the graphite sample piece after compression failure is observed through SEM, and compared with an untreated graphite sample, the sample subjected to dip-coating sintering has a coating with uniform thickness.
Example 2
This example differs from example 1 in that: in the second step, the obtained solidified graphite piece is repeated for at least one time in the first step and the second step, and the pores on the surface of the graphite piece are filled.
Example 3
This example differs from example 1 in that: coating an oxygen scavenger on the surface of the graphite piece protected by the anti-oxidation coating to absorb oxygen in micropores on the surface. The oxygen scavenger is one or the combination of two of nano-scale metal magnesium powder and metal aluminum powder.
Example 4
The present example differs from example 1 in that: in resisting oxidationAnd the surface of the graphite piece protected by the chemical coating is coated with plugging filler to prevent external oxygen from damaging the internal structure. The plugging filler is nano SiC or TiO 2 Cerium oxide, zirconium oxide, SiO 2 One or more of the above.
Example 5
The present example differs from example 1 in that: after the surface of the graphite piece protected by the antioxidant coating is coated with the deoxidant, a layer of plugging filler is coated, so that the damage of an internal structure caused by external oxygen is reduced. The oxygen scavenger is one or the combination of two of nano-scale metal magnesium powder and metal aluminum powder; the plugging filler is nano SiC or TiO 2 Cerium oxide, zirconium oxide, SiO 2 Or a combination of one or more thereof.
Although the present description is described in terms of embodiments, not every embodiment includes only a single embodiment, and such description is for clarity only, and those skilled in the art should be able to integrate the description as a whole, and the embodiments can be appropriately combined to form other embodiments as will be understood by those skilled in the art.
Claims (9)
1. A method for preparing an oxidation-resistant coating of a graphite piece based on a silicon resin dip coating liquid precursor conversion method is characterized by comprising the following steps:
step one, dip-coating a graphite piece by using an organic silicon resin solution under the action of ultrasonic cavitation, and volatilizing a solvent to obtain a dip-coated graphite piece;
step two, heating and curing the dip-coated graphite piece, wherein the curing process is set to keep the temperature at 120 ℃ for 1h, keep the temperature at 150 ℃ for 1h, keep the temperature at 180 ℃ for 2h, keep the temperature at 210 ℃ for 2h, and keep the temperature at 250 ℃ for 4h to obtain a cured graphite piece;
step three, sintering the solidified graphite piece at high temperature, heating the solidified graphite piece to 800 ℃ from room temperature at a heating rate of 10 ℃/min under the protection of argon gas in the sintering process, preserving heat for 1h, then heating the solidified graphite piece to 1100 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, then reducing the temperature to 400 ℃ at a cooling rate of 2 ℃/min, and closing the program to naturally cool the solidified graphite piece to obtain a sintered graphite piece;
and step four, repeating the step one and the step two on the sintered graphite piece to obtain the graphite piece protected by the antioxidant coating.
2. The method of claim 1, wherein: in the first step, the mass ratio of the organic silicon resin in the organic silicon resin solution is 30-60%; the organic silicon resin in the organic silicon resin solution is one or more of methyl silicon resin, phenyl silicon resin, methyl phenyl silicon resin, vinyl MQ silicon resin and hydrogen-containing silicon resin, and the solvent in the organic silicon resin solution is one or more of ethanol, isopropanol, dioxane, DMF, DMAC and acetone.
3. The method of claim 1, wherein: in the first step, the graphite piece is cleaned by ethanol by an ultrasonic device before dip-coating with the organic silicon resin, and then is dried in a drying oven, wherein the drying temperature is 80-120 ℃, and the drying time is more than or equal to 2 h.
4. The method of claim 1, wherein: in the first step, the temperature for volatilizing the solvent is 80 ℃, and the time is more than or equal to 2 h.
5. The method of claim 1, wherein: in the second step, the obtained solidified graphite piece is repeated for at least one time in the first step and the second step.
6. The method of claim 1, wherein: and coating an oxygen scavenger on the surface of the graphite piece protected by the anti-oxidation coating.
7. The method of claim 1, wherein: and coating plugging filler on the surface of the graphite piece protected by the antioxidant coating.
8. The method of claim 1, wherein: coating a layer of plugging filler after coating the deoxidant on the surface of the graphite piece protected by the anti-oxidation coating.
9. The method of claim 8, wherein: the oxygen scavenger is one or the combination of two of nano-scale metal magnesium powder and metal aluminum powder; the plugging filler is nano SiC or TiO 2 Cerium oxide, zirconium oxide, SiO 2 One or more of the above.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR975772A (en) * | 1947-12-26 | 1951-03-09 | Dow Corning | Graphite articles and their treatment process |
| CN102807394A (en) * | 2012-08-17 | 2012-12-05 | 航天材料及工艺研究所 | Method for preparing high temperature oxidation resisting coating on surface of carbon material |
| CN110820323A (en) * | 2019-10-31 | 2020-02-21 | 哈尔滨工业大学 | Preparation method of Si-C-O ceramic antioxidant coating on surface of carbon fiber |
| CN114315424A (en) * | 2022-01-14 | 2022-04-12 | 江西宁新新材料股份有限公司 | Preparation method of high-temperature-resistant coating and application of high-temperature-resistant coating in graphite product |
| CN114368981A (en) * | 2020-11-19 | 2022-04-19 | 北京纳斯特克纳米科技有限责任公司 | Graphite material, workpiece oxidation resistance treatment technology and application |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR975772A (en) * | 1947-12-26 | 1951-03-09 | Dow Corning | Graphite articles and their treatment process |
| CN102807394A (en) * | 2012-08-17 | 2012-12-05 | 航天材料及工艺研究所 | Method for preparing high temperature oxidation resisting coating on surface of carbon material |
| CN110820323A (en) * | 2019-10-31 | 2020-02-21 | 哈尔滨工业大学 | Preparation method of Si-C-O ceramic antioxidant coating on surface of carbon fiber |
| CN114368981A (en) * | 2020-11-19 | 2022-04-19 | 北京纳斯特克纳米科技有限责任公司 | Graphite material, workpiece oxidation resistance treatment technology and application |
| CN114315424A (en) * | 2022-01-14 | 2022-04-12 | 江西宁新新材料股份有限公司 | Preparation method of high-temperature-resistant coating and application of high-temperature-resistant coating in graphite product |
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