CN117125991A - Method for integrally preparing boride superhigh temperature ceramic coating through mixing - Google Patents
Method for integrally preparing boride superhigh temperature ceramic coating through mixing Download PDFInfo
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- CN117125991A CN117125991A CN202311064945.5A CN202311064945A CN117125991A CN 117125991 A CN117125991 A CN 117125991A CN 202311064945 A CN202311064945 A CN 202311064945A CN 117125991 A CN117125991 A CN 117125991A
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000005524 ceramic coating Methods 0.000 title claims abstract description 46
- 238000002156 mixing Methods 0.000 title claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000000843 powder Substances 0.000 claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 66
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011148 porous material Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052796 boron Inorganic materials 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 22
- RFBRDHGMLHXGOB-UHFFFAOYSA-N [Si].[Zr].[Hf] Chemical compound [Si].[Zr].[Hf] RFBRDHGMLHXGOB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052786 argon Inorganic materials 0.000 claims abstract description 21
- 229910001029 Hf alloy Inorganic materials 0.000 claims abstract description 20
- 239000011215 ultra-high-temperature ceramic Substances 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000010439 graphite Substances 0.000 claims description 30
- 229910002804 graphite Inorganic materials 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- GJIKIPCNQLUSQC-UHFFFAOYSA-N bis($l^{2}-silanylidene)zirconium Chemical group [Si]=[Zr]=[Si] GJIKIPCNQLUSQC-UHFFFAOYSA-N 0.000 claims description 7
- 229910021353 zirconium disilicide Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- TWRSDLOICOIGRH-UHFFFAOYSA-N [Si].[Si].[Hf] Chemical compound [Si].[Si].[Hf] TWRSDLOICOIGRH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 99
- 239000011248 coating agent Substances 0.000 abstract description 93
- 239000000463 material Substances 0.000 abstract description 51
- 239000002121 nanofiber Substances 0.000 abstract description 25
- 238000002360 preparation method Methods 0.000 abstract description 25
- 238000007254 oxidation reaction Methods 0.000 abstract description 24
- 230000003647 oxidation Effects 0.000 abstract description 23
- 239000000758 substrate Substances 0.000 abstract description 11
- 239000011153 ceramic matrix composite Substances 0.000 abstract description 10
- 238000005728 strengthening Methods 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 27
- 239000011159 matrix material Substances 0.000 description 25
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 25
- 239000012071 phase Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 19
- 239000002131 composite material Substances 0.000 description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 14
- 229910052726 zirconium Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007791 liquid phase Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000011065 in-situ storage Methods 0.000 description 9
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- 238000005516 engineering process Methods 0.000 description 8
- 229910052580 B4C Inorganic materials 0.000 description 7
- 229910026551 ZrC Inorganic materials 0.000 description 7
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 6
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- 230000008595 infiltration Effects 0.000 description 5
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- 238000001000 micrograph Methods 0.000 description 5
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- 239000002002 slurry Substances 0.000 description 4
- 239000011216 ultra-high temperature ceramic matrix composite Substances 0.000 description 4
- 238000002679 ablation Methods 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011184 SiC–SiC matrix composite Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- LRTTZMZPZHBOPO-UHFFFAOYSA-N [B].[B].[Hf] Chemical compound [B].[B].[Hf] LRTTZMZPZHBOPO-UHFFFAOYSA-N 0.000 description 2
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- 239000012298 atmosphere Substances 0.000 description 2
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- 239000011204 carbon fibre-reinforced silicon carbide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
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- 239000000155 melt Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910006249 ZrSi Inorganic materials 0.000 description 1
- FWXAUDSWDBGCMN-DNQXCXABSA-N [(2r,3r)-3-diphenylphosphanylbutan-2-yl]-diphenylphosphane Chemical compound C=1C=CC=CC=1P([C@H](C)[C@@H](C)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 FWXAUDSWDBGCMN-DNQXCXABSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- 239000010426 asphalt Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 230000000903 blocking effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 239000002241 glass-ceramic Substances 0.000 description 1
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
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- 238000004372 laser cladding Methods 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
- 239000011812 mixed powder Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
- C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
- C04B35/58078—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides
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- C04B35/71—Ceramic products containing macroscopic reinforcing agents
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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
- C04B41/5062—Borides, Nitrides or Silicides
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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Abstract
The invention relates to the technical field of ceramic matrix composite coating preparation, in particular to a method for integrally preparing boride superhigh temperature ceramic coating. The silicon-zirconium-hafnium alloy powder is directly contacted with a carbon/carbon porous material, then is placed in an argon environment together with the boron-containing mixture powder, is heated to be above the melting point of the alloy powder, is kept warm for 20-60min for reaction, and the silicon-zirconium-hafnium alloy and the boron-containing mixture cannot be contacted in the reaction process. According to the method, the boride ultrahigh-temperature ceramic coating is prepared by fully utilizing the volatilization and reaction paths of boron elements, the interface bonding strength of the coating and a substrate is up to more than 150MPa, the introduction of the boride ceramic coating obviously improves the oxidation resistance of the whole material, and in addition, the SiC micro-nano fiber capable of strengthening and toughening is introduced into the substrate and the coating.
Description
Technical Field
The invention relates to the technical field of ceramic matrix composite coating preparation, in particular to an antioxidation and strong-binding coating preparation technology with good applicability to large-scale and special-shaped components.
Background
The development of modern high and new technologies, particularly aerospace and defense sophisticated technologies, place more stringent demands on high temperature structural materials. In the aerospace field and advanced weapon systems, the traditional heat protection materials can not meet the novel heat protection requirements, and military countries in the world concentrate on developing novel high-temperature-resistant materials. The ceramic matrix composite is a novel composite developed in recent years, and is listed as the development focus of the structural material of the new generation of aerospace ultra-high sound velocity aircraft. Wherein the carbon fiber tough ceramic matrix composite (C/SiC) has the characteristics of high temperature resistance, high strength, low density, small thermal expansion, good thermal conductivity, higher high temperature strength, corrosion resistance and the like, and replaces CaO/SiO with lower high temperature creep resistance 2 ·Al 2 O 3 (CAS)、Li 2 O·A 2 O 3 ·SiO 2 Glass ceramics such as (LAS) and carbon-based materials with poor oxidation resistance become the first choice materials for the wing leading edge, nose cone and rocket engine nozzle of the ultra-high sound velocity aircraft.
However, the main problems faced in the development of such materials are: the C phase (carbon fiber and carbon matrix) in the composite material starts to oxidize in an aerobic environment at about 400 ℃, the process starts from the flow of oxygen in a gas medium to the boundary of the material, the reaction gas is adsorbed on the surface of the material and diffuses inwards through the pores of the material, the material defect is taken as an active center, and oxidation reaction is carried out under the catalysis of impurity particles, so that generated CO and CO 2 The gases eventually desorb from the surface of the material, and the SiC matrix undergoes reactive oxidation at temperatures above 1650 ℃, which makes it difficult for ceramic matrix composites to meet the use requirements in long-term ultra-high temperature oxidizing environments. Therefore, the improvement of the oxidation resistance of the high-temperature ceramic matrix composite material becomes a key of research and is also a bottleneck problem facing the current industry and academia.
The preparation of the high-temperature oxidation-resistant ceramic protective coating on the surface of the composite material is an effective and mature mode. The coating can effectively isolate the matrix material from a severe oxidation environment, and the use temperature of the composite material in the oxidation environment is greatly improved. In the design and preparation of high temperature oxidation resistant coatings, key points to be considered are: (1) The coating material/component itself should have low oxygen permeability and be capable of blocking the diffusion of oxygen into the substrate to form an oxygen diffusion barrier layer, which is ideally capable of forming a well-adhering oxide film in situ. (2) The coating material has certain self-healing capability, the coating is easy to form microcracks during preparation or service, and when the coating contains components capable of generating a flowing glass phase, the flowing glass phase can be generated at high temperature to generate healing effect. (3) The coating and the matrix material should have excellent interface bonding strength, and the higher bonding strength can enable the coating to effectively resist thermal shock and strong scouring action and avoid the coating from peeling off. (4) The coating components and the coating and the matrix should have chemical compatibility to prevent adverse reactions from occurring to generate unfavorable phases or phase change at high temperature. (5) The coating should be as uniform as possible, the number of defects on the coating should be as small as possible to avoid non-uniform oxidation of the coating, and the volatilization of coating components should be reduced as much as possible to reduce the degree of damage to the coating.
Against the above-mentioned key points, current research progress and consensus is that:
(1) The first category of development to design complex coating material systems is multilayer composite coating systems, such as those made from SiC/B 4 C/SiC layer composition C f 3 layers of the anti-oxidation protection system for SiC materials are prepared by a CVD process. The second type is mullite (3 Al) 2 O 3 /2SiO 2 ) Coating systems, e.g. by high-energy pulsing of CO 2 Preparation of 3Al on C/C-SiC composite material surface by laser 2 O 3 /2SiO 2 And (3) coating, wherein the obtained coating is uniform and compact. The third category is the very high temperature ceramic coating systems that have been rapidly developed in recent years, which have higher withstand temperatures.
(2) When the coating material contains B element and Si element, liquid phase B can be generated in an oxidizing atmosphere 2 O 3 、SiO 2 The layer fills cracks and holes in the coating, so that the coating has a self-healing function and a good oxidation resistance function.
(3) The traditional method for improving the interface bonding strength of the coating and avoiding the cracking of the coating by optimizing the preparation process of the coating and adopting nanofiber strength and the like mainly comprises the steps of reducing the thermal expansion mismatch between the coating and the substrate, reducing the thickness of the coating and enhancing the bonding force between the coating and the substrate. In recent years, a treatment mode of a nanofiber tough coating is developed, namely, silicon carbide nanofibers are grown on the surface of a matrix material in situ and used for toughening a composite coating (Y.H.Chu, H.J.Li, Q.G.Fu, et al oxidation protection of C/C composites with a multilayer coating of SiC and Si +SiC+SiC nanowires, carbon,50:1280-1288,2012; li Hejun, yanhui, before-payment steel, li Kezhi and Li Lou) and a preparation method of a bead string nanowire toughening and reinforcing ceramic coating, wherein the patent number is 201310106029.3. The applicant has also previously prepared coatings in this way, which have better toughness than coatings without the tough nanofibers, but which are essentially still distinct from "additional layers" outside the substrate, whose bond strength is still limited and which still have the risk of falling off.
(4) The coating material system which is the same as or similar to the base material is designed, so that good physical and chemical compatibility exists between the coating and the base, and adverse effects caused by thermal stress or phase change and the like are avoided.
(5) The uniformity of the coating is closely related to the preparation process of the coating, and the preparation processes of various coatings are generally divided into two main types at present: direct and indirect processes. The direct method is to directly coat the coating substance onto the substrate without chemical reaction, and includes physical vapor deposition, plasma spraying, liquid phase infiltration, hot pressing, etc. The indirect method refers to the method that the coating material is converted into the required material through chemical reaction, and the indirect method comprises a solid permeation method, a chemical vapor deposition method, a sol-gel method, a liquid phase reaction generation method, an in-situ growth method and the like. The process has advantages and disadvantages and application range.
Novel flight aiming at new technical requirementsThermal protection materials, coating materials of ceramic matrix composites begin to transform into Ultra-high temperature ceramic materials, ultra-high temperature ceramics (Ultra-high Temperature Ceramics, UHTCs) generally refer to transition metal boride, carbide and nitride materials, such as HfB, that can be used in an atmospheric environment above 2000 ℃ and have reasonably good high temperature oxidation resistance and thermal shock resistance 2 、ZrB 2 、TaB 2 HfC, zrC, taC, etc., and such materials have excellent physical properties such as high melting point, high thermal conductivity, high elastic modulus, etc., and can maintain high strength at ultra-high temperatures, while also having good thermal shock resistance and relatively moderate thermal expansion rate. The research of preparing high temperature resistant and antioxidant coating with superhigh temperature ceramic material has been widely conducted, and Zr-Si-C composite coating is prepared on monocrystalline and polycrystalline SiC substrate surface by chemical vapor reaction method at national northwest university of industry Yan Xiaowei. The inner layer of the composite coating is ZrC, and the middle layer is ZrSi 2 -ZrC complex phase, the outer layer being ZrC. The Italian aerospace research Center (CIRA) adopts a plasma spraying mode to spray the paint on C f ZrB is deposited on the surface of the SiC composite material 2 The coating improves the high temperature resistance and the ablation resistance of the matrix material. Ultramet in the United states published on the Web site an antioxidant coating system known as "Ultra2000" was developed which effectively protected C/C, C f The SiC and SiC/SiC composite materials are free from oxidation at the temperature of below 2500 ℃, and meanwhile, the coating has good anti-ablation performance, can be applied to high heat flux density environments such as rocket engines, space-earth round trip systems and the like, and is actually a HfC/SiC coating deposited by a CVD process.
The problems existing in the current research of the ultra-high temperature ceramic coating mainly comprise the following points:
(1) The interface binding force between the ultrahigh-temperature ceramic coating and the matrix material is weaker, even though the nanofiber is toughened or the multiphase material is compounded, an obvious interface exists between the coating and the matrix, and the layering phenomenon is still obvious under the working condition of extremely high temperature or thermal shock.
(2) The preparation difficulty of the coating of the large-sized and special-shaped components is high, and the problems of long preparation period, high cost, difficult guarantee of the uniformity of the coating and the like of the plasma spraying, chemical vapor deposition, hot pressing method and the like which are commonly adopted at present are solved. The liquid phase reaction generating method is to melt and infiltrate the coating material into the substrate or react with the substrate to generate the UHTC coating through high temperature heat treatment, and the method can quickly generate the ultra-high temperature ceramic coating, but carbide coatings (HfC and ZrC) are mainly prepared in the mode at present, and the preparation research of boride ceramic coatings is rare. The HfC/ZrC/SiC is more easily introduced into the porous carbon preform by PIP or RMI process than boride ceramic, forming carbide ultra-high temperature ceramic, but the thickness of the coating is difficult to control.
(3) Boride superhigh temperature ceramic materials have been proved to have excellent oxidation resistance and ablation resistance. Therefore, the oxidation resistance of the boride superhigh temperature ceramic coating is necessarily better, and the main reason is that the introduced boron element can generate a large amount of boron-containing oxides in a low temperature region (below 1000 ℃ C.) and can heal the defects such as cracks; if the coating component contains silicide, borosilicate of borosilicate and silicon dioxide can be generated on the surface of the material in a medium temperature region (1000 ℃ to 1700 ℃), so that the oxidation resistance of the coating material is effectively improved. The boride superhigh temperature ceramic coating can be prepared by taking B-containing alloy powder as a raw material and utilizing technologies such as plasma spraying, laser cladding and the like, and B can also be introduced into a preform 4 C, pre-matrix and then carrying out reaction infiltration to generate boride matrix, but no liquid phase or gas phase reaction preparation of boride superhigh temperature ceramic coating is disclosed and reported at present and related patent description.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a boride superhigh temperature ceramic coating by adopting a mixed integrated reaction, which organically combines a liquid phase infiltration reaction and a vapor phase infiltration reaction to form a mixed integrated reaction, fully utilizes volatilization and reaction paths of boron elements to prepare the boride superhigh temperature ceramic coating, greatly improves the interfacial bonding capability between the coating and a matrix, greatly improves the oxidation resistance of the coating, and greatly reduces the preparation period and the cost.
The invention takes a carbon/carbon porous material with a certain pore as a preform, takes silicon-zirconium-hafnium alloy as a liquid reaction phase, and places the silicon-zirconium-hafnium alloy in a small graphite crucible and directly contacts with the preform; the mixture powder containing boron is placed around a small graphite crucible as a gaseous reaction phase, so that direct contact with the preform and the liquid reaction phase is avoided. The materials are integrally placed in a large graphite crucible, and then the temperature is raised to be higher than the melting point of the alloy to carry out mixed integral reaction.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a method for integrally preparing boride superhigh temperature ceramic coating, which comprises the following steps: the silicon-zirconium-hafnium alloy powder is directly contacted with a carbon/carbon porous material, then is placed in an argon environment together with boron-containing mixture powder, is heated to be above the melting point of the alloy powder, and is subjected to reaction after heat preservation for 20-60 min; the silicon zirconium hafnium alloy and the boron-containing mixture cannot be contacted during the reaction.
In the above technical solution, further, the silicon zirconium hafnium alloy powder is zirconium disilicide powder, hafnium disilicide powder or a mixture of the two; the boron-containing mixture powder is B 4 C powder, B 2 O 3 Powder or a mixture of both. The choice of the powder is related to the volatilizing ability of the powder in a high temperature state, and boron-containing powder which is easy to evaporate is preferably selected.
In the above technical solution, further, the porosity of the carbon/carbon porous material is 15-25%. The carbon/carbon porous material is a carbon fiber reinforced carbon-based composite material, the preparation method of the carbon/carbon porous material comprises a Chemical Vapor Infiltration (CVI) process, a resin/asphalt impregnation pyrolysis process, a liquid phase impregnation-pyrolysis process (PIP) process and the like, and the carbon/carbon porous material has no special requirements on the preparation process and only needs to regulate and control the porosity of the carbon/carbon composite material. The porosity is 15-25%, so that the alloy melt can infiltrate into the carbon/carbon material through the mutually communicated pores under the action of capillary force to generate solid-liquid reaction to generate zirconium carbide and silicon carbide ceramic phases; on the other hand, the silicon carbide micro-nano fiber can be grown in situ in the carbon/carbon material and on the surface of the carbon/carbon material, so that the inside matrix is strengthened, and the interface combination of the coating and the matrix is enhanced.
In the above technical scheme, further, the particle diameter of the silicon zirconium hafnium alloy powder is 100nm-500nm. The nano powder with smaller particle size has high oxidation activity, which can cause the problem of powder taking process in an anaerobic environment; the powder with larger particle size is not easy to infiltrate in liquid state, and the molten state and the infiltration effect of the powder determine the density of the final composite material, and are also the key of the homogenization preparation of the coating.
In the above technical scheme, further, the mass ratio of the silicon-zirconium-hafnium alloy powder to the carbon/carbon porous material is 2-2.5:1. The silicon-zirconium-hafnium alloy powder is in direct contact with the carbon/carbon porous material, so that the alloy powder is immediately permeated into the pore structure of the carbon-carbon material through capillary action after being melted, and is subjected to solid-liquid reaction with a carbon matrix to generate zirconium carbide and silicon carbide ceramic phases; meanwhile, the mass ratio of the alloy powder to the carbon/carbon porous material is (2-2.5): 1, and the aim is to ensure that the pores in the carbon/carbon porous material are basically filled and densified by the ceramic phase, and meanwhile, no excessive alloy melt remains. The alloy melt is excessive and remains due to higher mass ratio, so that on one hand, carbon fibers can be corroded and damaged, on the other hand, the alloy melt can be adhered to a sample, and the sample taking difficulty is increased; the lower mass ratio may cause incomplete densification process of the material, resulting in excessive porosity of the final sample, affecting the service performance thereof.
In the above technical scheme, further, the mass ratio of the boron-containing mixture powder to the carbon/carbon porous material is 0.5-1:1. The mass ratio is determined to ensure that sufficient boride ceramic can be generated on the surface of the ultrahigh-temperature ceramic matrix composite material generated by liquid phase reaction through gas phase reaction besides the evaporation loss of the mixed powder. If the mass ratio is too low, the amount of boron evaporation is insufficient to produce a uniformly covered boride ceramic coating on the surface of the material.
In the technical scheme, further, argon is introduced after the argon is vacuumized, argon with the pressure of 20-50KPa is introduced after the vacuum degree is less than or equal to 10Pa, the purity of the argon is more than or equal to 99.99%, and the oxygen content is less than or equal to 10ppm. The furnace body is vacuumized to within 10Pa before heating, and the aim is to exhaust the air in the furnace body. Argon is filled after vacuum is pumped, so that the inert environment in the furnace body is kept, and simultaneously, the tiny oxygen in the argon is beneficial to the growth of micro-nano fibers. The argon pressure has obvious influence on the growth amount and morphology of the micro-nano fibers, and the micro-nano fibers are insufficient in growth and only can form nuclei instead of linearly grow when the pressure is too low, namely the argon content is too low. The excessive pressure can lead to the excessive content of the grown micro-nano fibers on one hand, and influences the density of the whole material, on the other hand, the excessive pressure of argon gas is introduced at room temperature, and the pressure in the furnace is possibly positive due to the volume expansion of the gas at high temperature, so that the damage of a furnace body sealing system is caused. After argon is filled, the temperature is raised to 1620 ℃ at a speed of 10 ℃/min, and the temperature is kept for 20-60min, wherein the optimal highest temperature is 1650 ℃ and the time of keeping the temperature is 40min. If the temperature is too low and the heat preservation time is too short, the immersion effect of the melt is not ideal, the gas phase reaction is not thorough, residual pores in the material can be caused, and the thickness of the surface coating is not uniform. If the temperature is too high and the heat preservation time is too long, the melt can cause obvious erosion damage to the carbon fiber in the preform, the mechanical property of the whole preparation material is obviously reduced, in addition, the heat preservation time is too long, the coating is easy to grow thicker, the thicker coating is easy to crack, and defects are introduced.
In the above technical solution, further, the method includes the following steps:
(1) Mechanically ball milling silicon-zirconium-hafnium alloy powder, and placing a carbon/carbon porous material on the alloy powder;
(2) Placing the boron-containing mixture powder around the powder in the step (1) without contacting with each other;
(3) And (3) vacuumizing in a closed environment, introducing argon, heating to a required temperature, and preserving the temperature for a period of time to react.
In the technical scheme, further, the silicon-zirconium-hafnium alloy powder in the step (1) is placed in a small graphite crucible, the small graphite crucible is placed in the middle of a large graphite crucible, and the boron-containing mixture powder in the step (2) is placed around the small graphite crucible in the large graphite crucible.
In the technical scheme, further, the upper end of the small graphite crucible is not covered, and the upper end of the large graphite crucible is covered. The top end of the small graphite crucible does not need a sealing cover, so that the evaporating gas can flow into the small graphite crucible, and boride ceramic is generated on the surface of the composite material through gas phase reaction. The top end of the crucible needs to be covered, so that the gas is prevented from evaporating to other areas of the high-temperature furnace body except the large graphite crucible, and a relatively airtight place is provided for the evaporation, flow and reaction of the gas phase.
The invention adopts a mixed integrated reaction method to prepare boride superhigh temperature ceramic coating, and utilizes the solid-liquid reaction of silicon-zirconium alloy and carbon matrix to rapidly densify (infiltration and reaction time is about 30 minutes) porous carbon material to generate carbon fiber toughened zirconium (hafnium) -silicon carbide superhigh temperature ceramic matrix composite material. At the same time, the boron vapor reacts with zirconium element on the surface of the material to generate zirconium boride which is used as a component of the ultra-high temperature ceramic coating. The liquid phase and gas phase reaction synchronously occur, so that the preparation period of the coating is greatly reduced, and the liquid phase and gas phase reaction substances mainly take the pore structure in the porous carbon material as a transport channel, so that the prepared coating and the matrix have no obvious interface before, have very high interface bonding strength and have excellent thermal shock resistance. In addition, the process retains the advantages of preparing the ceramic matrix composite material by liquid phase infiltration, and has good applicability to densification and coating preparation of large-scale and special-shaped components.
Compared with the prior art, the invention has the beneficial effects that:
the method organically combines the liquid phase permeation reaction and the gas phase permeation reaction to form the mixed integrated reaction, fully utilizes the volatilization and reaction path of boron element to prepare the boride superhigh temperature ceramic coating, greatly improves the interfacial bonding capability between the coating and a matrix and the oxidation resistance of the coating, and greatly reduces the preparation period and the cost. Specifically:
the interfacial bonding capability of the coating and the matrix is obviously improved, the coating has no obvious layer concept, namely, the coating and the matrix have no obvious interface before (see fig. 3 and fig. 4), so that the condition that the bonding strength of the coating and the matrix is limited (generally not more than 25 MPa) in the prior art is greatly improved, and the interfacial bonding strength in the invention is as high as more than 150MPa. In addition, the invention can prepare coatings with different thicknesses by regulating and controlling the parameters of the pore structure, the heat preservation time and the like of the preform (see fig. 5 and 6).
The boride-containing ultra-high temperature ceramic coating (shown in the accompanying drawings 1 and 2) prepared by the method can improve the oxidation resistance of the coating in a medium temperature area, thereby remarkably improving the oxidation resistance of the whole material (shown in the accompanying drawings 8).
The mixed integrated reaction is carried out in an argon protection atmosphere, siC micro-nanofibers can be generated in the carbon/carbon preform and the coating in the argon atmosphere, the introduced SiC micro-nanofibers can toughen the ultra-high temperature ceramic material (see fig. 7 (a)), and the introduction of the micro-nanofibers can improve the toughness of the ultra-high temperature ceramic material. According to the invention, the nano fiber grown in the argon atmosphere is grown in situ, so that the distribution non-uniformity caused by direct dispersion and introduction of the nano reinforced material is avoided, meanwhile, no metal catalyst is involved in the growth process (only silicon zirconium hafnium alloy powder), and the SiC micro-nano fiber has higher purity (atomic ratio C/Si=1-1.2). The growth process of the SiC micro-nano fiber and the matrix densification and coating preparation process are synchronously carried out, the process period is greatly shortened (about 150 minutes from the temperature rise to the end of the reaction), experimental equipment is simple, and only a high-temperature furnace, a graphite crucible and the like are needed, so that compared with the existing nanofiber toughening coating preparation technology, the method is simpler, more convenient and more efficient.
Drawings
Figure 1 is an XRD phase pattern of the coating prepared in example 1.
FIG. 2 is an XRD phase pattern of the coating prepared in example 2
FIG. 3 is a scanning electron microscope image of the cross-sectional microstructure of the ultra-high temperature ceramic matrix composite of the zirconium boride-containing ceramic coating prepared in example 1.
FIG. 4 is a high power back-scattering plot of the interface between the zirconium boride-containing ceramic coating prepared in example 1 and a substrate.
FIG. 5 is a scanning electron microscope image of the ultra-high temperature ceramic coating containing zirconium boride prepared in example 1.
FIG. 6 is a scanning electron microscope image of the ultra-high temperature ceramic coating containing zirconium boride prepared in example 3.
Fig. 7 (a) is a scanning electron microscope image of the pore channel of the in-situ grown SiC micro-nanofiber prepared in example 1. Fig. 7 (b) is a scanning electron microscope image of a pore channel without in-situ growth of SiC micro-nanofibers prepared in comparative example 1.
FIG. 8 is a graph comparing thermogravimetric curves of the ultra-high temperature ceramic matrix composite containing zirconium boride ceramic coating and the composite without zirconium boride ceramic coating prepared in example 1 and comparative example 1, respectively.
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited in any way.
Example 1
A method for preparing boride superhigh temperature ceramic coating by mixing integral reaction comprises the following steps:
(1) 100g of zirconium disilicide powder (the purity is more than or equal to 99.5 percent, the grain diameter is 1-3 mu m) and 30ml of absolute ethyl alcohol are weighed, the zirconium disilicide powder and the absolute ethyl alcohol are ball-milled with high energy to prepare nano slurry, the nano slurry is evaporated and dried on a rotary evaporator, and then the nano powder of the silicon-zirconium alloy is obtained after grinding, wherein the grain diameter of the powder is 100nm on average.
(2) 45g of boron carbide powder (the purity is more than or equal to 99.9 percent and the particle size is 2-4 mu m) is weighed, the boron carbide powder is prepared into nano slurry after being evenly mixed by high-energy ball milling, the slurry is evaporated and dried on a rotary evaporator, and then the boron carbide powder is obtained by grinding.
(3) The mature liquid phase impregnation-cracking method is used for preparing the carbon/carbon porous pre-material (pore structure and evolution research in densification process of the C/C composite material, mechanical design and manufacturing engineering, 2022.51 (10), 4), the carbon/carbon porous material with the porosity of 15% is prepared, a small square block with the porosity of 32 multiplied by 42 multiplied by 20mm is cut out to serve as a pre-body, and the mass of the small square block is weighed to be 30g.
(4) 69g of the zirconium disilicide alloy nano-powder obtained in the step 1 is weighed and placed in a small graphite crucible, and then the carbon/carbon porous preform obtained in the step 3 is placed on the powder, wherein the mass ratio of the zirconium disilicide alloy to the preform is 2.3, and the upper end of the small graphite crucible is not covered.
(5) Placing the small graphite crucible in the step 4 in the middle of a large graphite crucible, then weighing 16.5g of the boron carbide powder obtained in the step 2, and laying the boron carbide powder around the small graphite crucible (the small graphite crucible is not in direct contact with the boron carbide powder), and sealing the upper end of the large graphite crucible.
(6) Placing the large graphite crucible in the step 5 into a vacuum high-temperature furnace, vacuumizing to below 10Pa, filling high-purity argon gas with the pressure of 50KPa (purity is more than or equal to 99.99 percent; oxygen content is less than or equal to 10 PPM) at the flow rate of 15cc/min, heating to 1650 ℃ at the heating rate of 10 ℃/min, preserving heat for 40min, cooling to 1200 ℃ at the rate of 5 ℃/min, and cooling to room temperature along with the furnace.
(7) And (3) after the step (6) is finished, obtaining the ultra-high temperature ceramic matrix composite material containing the zirconium boride ceramic coating (shown in figure 1). As can be seen from FIG. 1, a large amount of ZrB having good crystallinity is generated in the prepared coating 2 The ultrahigh-temperature ceramic phase is analyzed, the boron source is obtained by evaporating boron carbide powder in the step 5 of the embodiment, the gas-phase boron source flows into the small graphite crucible in the step 4, and the gas-phase boron source reacts with the carbon/carbon preform and zirconium element in the zirconium disilicide alloy melt to generate ZrB 2 In addition, the coating also comprises components such as SiC generated by solid-liquid reaction, and the coating of the zirconium boride-containing superhigh temperature ceramic is successfully prepared in the embodiment.
(8) The mass of the carbon/carbon porous material before the experiment and the mass of the whole material after the experiment were weighed, and the mass increase rate was found to be about 92%. As shown in FIG. 3, the coating has good uniformity and moderate thickness (the thickness of the coating is about 174 μm, see FIG. 5); as shown in figure 4, the coating and the matrix have no obvious boundary before, the interface bonding capability of the coating and the matrix is strong, and the bonding strength of the coating is higher than 150MPa through a micro-scratch experiment.
Example 2
The only difference between the embodiment and the embodiment 1 is that the powder weighed in the step 1 is hafnium disilicide powder, the hafnium disilicide alloy nanometer powder is synchronously adopted in the step 4, other implementation processes and specific parameters are consistent, the coating of the hafnium boride-containing ultra-high temperature ceramic is obtained after the step 7 is finished, and as shown in fig. 2, the coating prepared in the embodiment 2 contains hafnium boride, hafnium carbide and silicon carbide components.
Example 3
This example differs from example 1 in that in step 3, a carbon/carbon porous material having a porosity of 25% prepared by controlling the parameters of the polymer impregnation cracking process was selected as the preform; the other steps and test parameters were the same. The zirconium boride ceramic coating prepared in example 3 still has good uniformity and outstanding interfacial bonding capability, while the thickness of the coating is significantly increased (see fig. 6), which is closely related to the regulation of the porosity of the preform, that is, the thickness of the prepared coating can be controlled by regulating the porosity and pore distribution of the carbon/carbon porous material.
Comparative example 1
The comparative example and example 1 differ in that argon is not introduced in step 6, and the other steps and test parameters are the same. Fig. 7 (a) is a pore channel scanning electron micrograph of in-situ grown SiC micro-nanofibers prepared in example 1, and fig. 7 (b) is a pore channel scanning electron micrograph of non-in-situ grown SiC micro-nanofibers prepared in comparative example 1. As can be seen from the figure, in example 1, under argon atmosphere, a plurality of crisscrossed SiC micro-nanofibers were grown in the pore channels of the carbon/carbon porous preform, which fibers would be advantageous for the improvement of the fracture toughness of the internal matrix, whereas in comparative example 1, in which no argon atmosphere was found, no growth of SiC micro-nanofibers was observed, indicating that argon atmosphere is a main influencing factor for the growth of micro-nanofibers.
Comparative example 2
This comparative example differs from example 1 in that steps 2 and 5 are omitted, i.e., the boron-containing mixture powder is not placed in this comparative example. This comparative example is to demonstrate that the boron-containing mixture powder of the present invention is critical to the production of boride ceramic coatings, and in addition to demonstrate that boride ceramic coatings have significant beneficial effects on enhancing the oxidation resistance of materials. FIG. 8 is a graph showing the thermal weight loss curves of the superhigh temperature ceramic matrix composite containing the zirconium boride ceramic coating and the material without the zirconium boride ceramic coating obtained in example 1 and the comparative example, wherein the thermal weight loss rate of the composite material in a high temperature environment can reflect the high temperature oxidation resistance of the material to a certain extent. The weight loss on heat in comparative example 1 was 62.32%, while the weight loss on heat in example 1 was only 93.27%. The thermal weight loss rate in example 1 of the inventive method is much lower than that of comparative example 2, which indicates that the boride-containing ceramic coating prepared in example 1 has an important effect on the improvement of the oxidation resistance of the material.
Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art without departing from the scope of the technology, or the technology can be modified to be equivalent. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A method for integrally preparing boride superhigh temperature ceramic coating, which is characterized by comprising the following steps: the silicon-zirconium-hafnium alloy powder is directly contacted with a carbon/carbon porous material, then is placed in an argon environment together with boron-containing mixture powder, is heated to be above the melting point of the alloy powder, and is subjected to reaction after heat preservation for 20-60 min; the silicon zirconium hafnium alloy and the boron-containing mixture cannot be contacted during the reaction.
2. The method for preparing boride superhigh temperature ceramic coating according to claim 1, wherein the silicon zirconium hafnium alloy powder is zirconium disilicide powder, hafnium disilicide powder or a mixture of both; the boron-containing mixture powder is B 4 C powder, B 2 O 3 Powder or a mixture of both.
3. The method for integrally mixing a boride ultra-high temperature ceramic coating according to claim 1, wherein the porosity of the carbon/carbon porous material is 15-25%.
4. The method for preparing boride superhigh temperature ceramic coating according to claim 1, wherein the particle diameter of the silicon zirconium hafnium alloy powder is 100nm-500nm.
5. The method for integrally preparing the boride superhigh temperature ceramic coating according to claim 1, wherein the mass ratio of the silicon-zirconium-hafnium alloy powder to the carbon/carbon porous material is 2-2.5:1.
6. The method for integrally preparing a boride superhigh temperature ceramic coating according to claim 1, wherein the mass ratio of the boron-containing mixture powder to the carbon/carbon porous material is 0.5-1:1.
7. The method for integrally preparing boride superhigh temperature ceramic coating according to claim 1, wherein argon is introduced after vacuumizing, argon with the pressure of 20-50Kpa is introduced after vacuumizing to the vacuum degree of less than or equal to 10Pa, the purity of the argon is more than or equal to 99.99%, and the oxygen content is less than or equal to 10ppm.
8. A method of preparing a boride ultra-high temperature ceramic coating in a hybrid monolith according to claim 1, comprising the steps of:
(1) Mechanically ball milling silicon-zirconium-hafnium alloy powder, and placing a carbon/carbon porous material on the alloy powder;
(2) Placing the boron-containing mixture powder around the powder in the step (1) without contacting with each other;
(3) And (3) vacuumizing in a closed environment, introducing argon, heating to a required temperature, and preserving the temperature for a period of time to react.
9. The method for integrally preparing a boride superhigh temperature ceramic coating according to claim 8, wherein in step (1), the silicon-zirconium-hafnium alloy powder is placed in a small graphite crucible, the small graphite crucible is placed in the middle of a large graphite crucible, and the boron-containing mixture powder in step (2) is placed around the small graphite crucible in the large graphite crucible.
10. The method for integrally preparing a boride superhigh temperature ceramic coating according to claim 9, wherein the upper end of the small graphite crucible is not covered, and the upper end of the large graphite crucible is covered.
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