CN115650751A - Fiber toughened silicon carbide cladding and preparation method thereof - Google Patents
Fiber toughened silicon carbide cladding and preparation method thereof Download PDFInfo
- Publication number
- CN115650751A CN115650751A CN202211254791.1A CN202211254791A CN115650751A CN 115650751 A CN115650751 A CN 115650751A CN 202211254791 A CN202211254791 A CN 202211254791A CN 115650751 A CN115650751 A CN 115650751A
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- fiber
- cladding
- toughened
- lining pipe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 151
- 239000000835 fiber Substances 0.000 title claims abstract description 96
- 238000005253 cladding Methods 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000005245 sintering Methods 0.000 claims abstract description 43
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 238000005238 degreasing Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000000280 densification Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 239000004014 plasticizer Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000001764 infiltration Methods 0.000 claims description 10
- 230000008595 infiltration Effects 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 235000021313 oleic acid Nutrition 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229940083037 simethicone Drugs 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000005728 strengthening Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000000197 pyrolysis Methods 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 7
- 238000009941 weaving Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000009954 braiding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Landscapes
- Ceramic Products (AREA)
Abstract
The invention discloses a fiber toughened silicon carbide cladding and a preparation method thereof, wherein the preparation method comprises the following steps: s1, preparing slurry; s2, preparing and molding the slurry into a silicon carbide lining pipe green body; s3, degreasing and sintering the silicon carbide lining pipe green body to form a high-density silicon carbide lining pipe; and S4, arranging a fiber woven layer on the outer surface of the silicon carbide inner lining pipe, and carrying out densification treatment on the fiber woven layer. According to the invention, a silicon carbide fiber powder mixture is matched with an organic solvent and the like to prepare a slurry, and then the slurry is processed and formed into a cladding green body, and the silicon carbide lining pipe is prepared by combining degreasing and sintering treatment, and has the characteristics of high strength and high toughness; in the process of setting the fiber braided layer and subsequent densification, the method is beneficial to maintaining the straightness of the cladding tube, can meet the requirements of the straightness, the roundness and the design values of the inner and outer diameter parameters of the cladding, and reduces the processing amount of the subsequent cladding.
Description
Technical Field
The invention relates to a silicon carbide cladding, in particular to a fiber toughened silicon carbide cladding and a preparation method thereof.
Background
Regarding the structural design that the SiC composite cladding is mainly divided into three layers and two layers, compared with the two-layer structural design, the three-layer design can further ensure the air tightness of the cladding material, thereby improving the safety of the nuclear fuel element.
At present, the preparation process of the three-layer SiC composite cladding comprises the following steps: and after the lining is woven by fibers, the middle layer is densified by a CVI (chemical vapor infiltration) or PIP (PIP) process, and finally, the outermost layer is coated by a coating technology. However, due to the characteristic of the super-length-diameter ratio of the SiC composite cladding, parameters such as straightness, roundness, inner diameter and outer diameter of the SiC composite cladding are easily influenced by deformation of the lining in the preparation process. Meanwhile, the processing difficulty of SiC is increased due to the characteristics of high hardness and brittle texture of SiC, so that the preparation of the full-size SiC composite cladding is difficult to realize in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of a silicon carbide cladding with fiber strengthening and toughening.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the fiber toughened silicon carbide cladding comprises the following steps:
s1, preparing slurry; the slurry comprises the following raw materials in parts by weight: 45-89.7 parts of silicon carbide fiber powder mixture, 10-40 parts of organic solvent, 0.1-5 parts of dispersant, 0.1-5 parts of plasticizer and 0.1-5 parts of defoamer;
s2, preparing and molding the slurry into a silicon carbide lining pipe green body;
s3, degreasing and sintering the silicon carbide lining pipe green body to form a high-density silicon carbide lining pipe;
and S4, arranging a fiber woven layer on the outer surface of the silicon carbide lining pipe, and carrying out densification treatment on the fiber woven layer to form a silicon carbide cladding with fiber strengthening and toughening.
Preferably, in step S1, the silicon carbide fiber powder mixture includes a silicon carbide material; the silicon carbide material comprises silicon carbide fibers and silicon carbide powder, and the volume percentage of the silicon carbide fibers in the silicon carbide material is 10-50%;
the diameter of the silicon carbide fiber is 0.01-10 μm, and the length-diameter ratio of the silicon carbide fiber is 10-1000.
Preferably, in step S1, the silicon carbide fiber powder mixture further includes a sintering aid, and the mass percentage of the sintering aid in the silicon carbide fiber powder mixture is 1 to 10%.
Preferably, the sintering aid is Al 2 O 3 -Re 2 O 3 Wherein Re is Sc, Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb or Lu.
Preferably, in the sintering aid, al 2 O 3 And Re 2 O 3 The proportion of (A) is 1wt% -99 wt%:99wt% -1 wt%.
Preferably, in step S1, the organic solvent is at least one of absolute ethyl alcohol, acetone, xylene, and polyethylene glycol.
Preferably, the dispersant is at least one of oleic acid, stearic acid and castor oil.
Preferably, the plasticizer is at least one of carboxymethyl cellulose, phenolic resin and tetramethyl ammonium hydroxide.
Preferably, the defoaming agent is at least one of ethylene glycol, glycerol and simethicone.
Preferably, in step S1, the raw materials are made into slurry by at least one of roll ball milling, planetary ball milling, magnetic stirring, and mechanical stirring.
Preferably, in step S2, the slurry is formed into a silicon carbide lined pipe green body by a compression molding or extrusion molding process.
Preferably, in step S3, the degreasing process is as follows: heating to 400-800 ℃ at the heating rate of 1-10 ℃/min under vacuum, and keeping the temperature for 1-10 h.
Preferably, in step S3, the sintering process is as follows: heating to 800-1200 ℃ at a heating rate of 10-20 ℃/min; then the temperature is raised to 1700 ℃ to 2200 ℃ at the heating rate of 5 ℃/min to 10 ℃/min, and the temperature is preserved for 0.5 to 4 hours.
Preferably, in step S3, the atmosphere of the sintering process is vacuum, or at least one of argon, helium and nitrogen.
Preferably, in the step S2, the inner diameter of the silicon carbide lining pipe green body is 7 mm-7.8 mm, the outer diameter is 8.5 mm-9 mm, and the wall thickness is 0.35 mm-1.0 mm; the length of the silicon carbide lining pipe green body is 1000 mm-4000 mm.
Preferably, in step S3, the highly dense silicon carbide lining tube is formed to have an inner diameter of 7.1mm to 7.9mm, an outer diameter of 8.4mm to 9.1mm, a wall thickness of 0.25mm to 1.0mm, and a length of 1000mm to 4000mm.
Preferably, in step S4, the inner diameter of the silicon carbide composite cladding is 7.1mm to 7.9mm, the outer diameter is 9.5mm to 10.1mm, the wall thickness is 0.3mm to 1.5mm, and the length is 1000mm to 4000mm; the straightness is 1/2000-1/100.
Preferably, in step S4, the diameter of the silicon carbide fiber used for the fiber woven layer is 5 μm to 20 μm.
Preferably, in step S4, the densification process employs at least one of chemical vapor infiltration, precursor impregnation cracking and reactive infiltration.
Preferably, the preparation method of the fiber-toughened silicon carbide cladding further comprises the following steps:
and S5, arranging a coating on the outer surface of the silicon carbide composite cladding.
Preferably, the coating comprises at least one of a silicon carbide coating, a chromium metal coating, and a high entropy coating.
The invention also provides a fiber toughened silicon carbide cladding prepared by adopting any one of the preparation methods.
The invention has the beneficial effects that: preparing slurry from a silicon carbide fiber powder mixture and an organic solvent, processing and molding the slurry into a cladding green body, and performing degreasing and sintering treatment to obtain the silicon carbide lining pipe with high strength and toughness; in the process of setting the fiber braided layer and subsequent densification, the method is beneficial to maintaining the straightness of the cladding tube, can meet the requirements of the straightness, the roundness and the design values of the inner and outer diameter parameters of the cladding, and reduces the processing amount of the subsequent cladding.
In addition, the preparation method does not need high-temperature and high-pressure processes, so that the preparation process is simplified; the prepared fiber toughened silicon carbide cladding has high density, high heat transfer performance and high mechanical performance.
Detailed Description
The preparation method of the fiber toughened silicon carbide cladding comprises the following steps:
s1, preparing slurry.
The slurry comprises the following raw materials in parts by weight: 45 to 89.7 parts of silicon carbide fiber powder mixture, 10 to 40 parts of organic solvent, 0.1 to 5 parts of dispersant, 0.1 to 5 parts of plasticizer and 0.1 to 5 parts of defoaming agent.
The silicon carbide fiber powder mixture comprises a silicon carbide material and a sintering aid. The silicon carbide material further comprises silicon carbide fiber and silicon carbide powder, the silicon carbide fiber and the silicon carbide powder are mixed to form the silicon carbide material, and the silicon carbide fiber accounts for 10-50% of the volume percentage.
In the silicon carbide fiber powder mixture, the silicon carbide fiber is used as a short fiber and plays a role in reinforcing, so that the straightness, roundness, inner and outer diameter parameters and the like of the cladding can meet the requirements, and the compactness of the cladding can be improved. Preferably, the silicon carbide fibers have a diameter of 0.01 to 10 μm and an aspect ratio of 10 to 1000.
In the silicon carbide material, the mass percentage of the sintering aid is 1-10%. The sintering aid is Al 2 O 3 -Re 2 O 3 ，Al 2 O 3 And Re 2 O 3 The proportion of (1 wt%) to (99 wt%): 99wt% -1 wt%. Wherein Re is Sc, Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb or Lu.
For other raw materials of the slurry, the organic solvent is at least one of absolute ethyl alcohol, acetone, xylene and polyethylene glycol; the dispersant is at least one of oleic acid, stearic acid and castor oil; the plasticizer is at least one of carboxymethyl cellulose, phenolic resin and tetramethyl ammonium hydroxide; the defoaming agent is at least one of glycol, glycerol and simethicone.
When the slurry is prepared, all the raw materials with required mass are weighed and then mixed by at least one of roller ball milling, planetary ball milling, magnetic stirring and mechanical stirring to prepare the slurry.
S2, preparing the slurry into a silicon carbide lining pipe green compact with a thin wall and an ultra length-diameter ratio by a compression molding or extrusion molding process.
The inner diameter of the silicon carbide lining pipe green body is 7 mm-7.8 mm, the outer diameter is 8.5 mm-9 mm, and the wall thickness is 0.35 mm-1.0 mm; the length of the silicon carbide lining tube green body is 1000 mm-4000 mm.
And S3, degreasing and sintering the green compact of the silicon carbide lining pipe to form the high-density silicon carbide lining pipe.
Wherein the degreasing treatment comprises the following steps: heating to 400-800 ℃ at the heating rate of 1-10 ℃/min under vacuum, and keeping the temperature for 1-10 h.
The sintering treatment is as follows: heating to 800-1200 ℃ at a heating rate of 10-20 ℃/min; then the temperature is raised to 1700 ℃ to 2200 ℃ at the heating rate of 5 ℃/min to 10 ℃/min, and the temperature is preserved for 0.5 to 4 hours. The atmosphere of the sintering treatment is vacuum or at least one of argon, helium and nitrogen.
After degreasing and sintering treatment, the inner diameter of the formed high-density silicon carbide lining pipe is 7.1-7.9 mm, the outer diameter is 8.4-9.1 mm, the wall thickness is 0.25-1.0 mm, and the length is 1000-4000 mm.
And S4, arranging a fiber woven layer on the outer surface of the silicon carbide lining pipe, and carrying out densification treatment on the fiber woven layer to form the silicon carbide cladding with fiber strengthened and toughened.
The fiber braided layer can be directly formed on the outer surface of the silicon carbide lining pipe through a braiding machine and the like, so that the toughness of the silicon carbide cladding is improved. The fiber braided layer is formed by braiding silicon carbide fibers. If the diameter of the fiber is too large, the fiber weaving effect is poor; the fiber diameter is too small, and the fiber is easy to break in the weaving process; therefore, in order to ensure that the formed fiber braided layer has better effect, the diameter of the silicon carbide fiber is 5-20 μm.
The densification treatment of the fiber braided layer can adopt at least one of chemical vapor infiltration, precursor impregnation cracking and reaction infiltration.
The silicon carbide composite cladding obtained after densification has the inner diameter of 7.1-7.9 mm, the outer diameter of 9.5-10.1 mm, the wall thickness of 0.3-1.5 mm and the length of 1000-4000 mm; the straightness is 1/2000-1/100.
And S5, arranging a coating on the outer surface of the silicon carbide composite cladding.
The coating comprises at least one of a silicon carbide coating, a metal chromium coating and a high-entropy coating, and the metal chromium coating can be preferred.
The density of the fiber toughened silicon carbide cladding prepared by the invention reaches 95-99%, and the cladding leakage rate is 10- 13 ～1×10- 1 0Pa·m 3 And/s, the tensile strength at room temperature is 350MPa to 550MPa, and the tensile strength at a high temperature of 1200 ℃ is 400MPa to 600MPa.
The invention is further illustrated by the following specific examples.
Example 1
The raw materials comprise: 64.5wt% of silicon carbide fiber powder mixture, 35wt% of organic solvent, 0.15wt% of dispersing agent, 0.2wt% of plasticizer and 0.15wt% of defoaming agent. Wherein, the dispersant is oleic acid, the plasticizer is carboxymethyl cellulose, the defoamer is glycol, and the organic solvent is absolute ethyl alcohol; silicon carbide fiber powder mixtureComprises silicon carbide material and sintering additive, the proportion of the sintering additive is 5 percent, and the sintering additive is Al 2 O 3 -Y 2 O 3 In which Al is 2 O 3 And Re 2 O 3 In a ratio of 45wt%:55wt%, the silicon carbide material comprises silicon carbide fiber and silicon carbide powder, the volume ratio of the silicon carbide fiber is 40%, the diameter of the silicon carbide fiber is 0.1 μm, and the length-diameter ratio of the fiber is 500. The raw materials are mixed by adopting roller ball milling, silicon nitride is used as a milling ball, absolute ethyl alcohol is used as a ball milling medium, and the slurry is prepared by ball milling.
The slurry is subjected to an extrusion molding preparation process, and the prepared and molded lining pipe green body has the inner diameter of 7.5mm, the outer diameter of 8.5mm, the wall thickness of 0.5mm and the length of 4000mm. Degreasing in a vacuum environment, wherein the degreasing process comprises the steps of heating to 600 ℃ at the heating rate of 2 ℃/min and preserving heat for 5 hours; after degreasing, continuously sintering at high temperature, wherein the sintering process is to heat up to 1200 ℃ at the heating rate of 10 ℃/min; then the temperature is raised to 1900 ℃ at the speed of 5 ℃/min, the temperature is kept for 2h, and the sintering atmosphere is argon. After sintering, the compact lining pipe is obtained, the inner diameter of the compact lining pipe is 7.9mm, the outer diameter of the compact lining pipe is 8.5mm, the wall thickness of the compact lining pipe is 0.3mm, and the length of the compact lining pipe is 4000mm. And after the outer surface of the lining pipe is subjected to fiber weaving by adopting long fibers with the diameter of 10 mu m, densification is carried out at 1300 ℃ by adopting a CVI (chemical vapor infiltration) process, and SiC coating deposition is carried out on the outer surface by continuously adopting a CVD (chemical vapor deposition) process to prepare the silicon carbide cladding pipe.
After the silicon carbide cladding tube is subjected to coarse grinding treatment on the inner surface and the outer surface, the inner diameter is 7.9mm, the outer diameter is 9.9mm, the wall thickness is 1mm, and the length is 4000mm. The density of the obtained silicon carbide cladding tube is 99%, and the straightness is 1/100; the leakage rate of the cladding is 10- 13 Pa·m 3 (ii)/s, having a tensile strength of 400MPa at room temperature and a tensile strength of 450MPa at a high temperature of 1200 ℃.
Example 2
The raw materials comprise: 89.7wt% of silicon carbide fiber powder mixture, 10wt% of organic solvent, 0.1wt% of dispersing agent, 0.1wt% of plasticizer and 0.1wt% of defoaming agent. In the silicon carbide fiber powder mixture, the volume ratio of the silicon carbide fiber is 10 percent, the diameter of the silicon carbide fiber is 0.01 mu m, and the length-diameter ratio of the fiber is 1000. Otherwise, according to example 1, a slurry was prepared.
The slurry is subjected to compression molding preparation technology, and the prepared and molded lining pipe green body has the inner diameter of 7.8mm, the outer diameter of 8.5mm, the wall thickness of 0.35mm and the length of 4000mm. Degreasing in a vacuum environment, wherein the degreasing process comprises the steps of heating to 700 ℃ at a heating rate of 2 ℃/min and preserving heat for 4 hours; after degreasing, continuously sintering at high temperature, wherein the sintering process is to heat up to 1200 ℃ at the heating rate of 10 ℃/min; then the temperature is raised to 1700 ℃ at the speed of 5 ℃/min, the temperature is kept for 2h, and the sintering atmosphere is argon. After sintering, a compact lining pipe is obtained, the inner diameter of which is 7.9mm, the outer diameter of which is 8.4mm, the wall thickness of which is 0.25mm and the length of which is 4000mm. And after the outer surface of the lining pipe is subjected to fiber weaving by adopting long fibers with the diameter of 20 mu m, densification is carried out at the temperature of 1200 ℃ by adopting a CVI (chemical vapor infiltration) process, and SiC coating deposition is carried out on the outer surface by continuously adopting a CVD (chemical vapor deposition) process to prepare the silicon carbide cladding pipe.
After the silicon carbide cladding tube is subjected to coarse grinding treatment on the inner surface and the outer surface, the inner diameter is 7.9mm, the outer diameter is 10.0mm, the wall thickness is 1.05mm, and the length is 4000mm. The density of the obtained silicon carbide cladding tube is 99 percent, and the straightness is 1/2000; the leakage rate of the cladding is 10- 13 Pa·m 3 (ii)/s, wherein the tensile strength at room temperature is 350MPa and the tensile strength at a high temperature of 1200 ℃ is 400MPa.
Example 3
The raw materials comprise: 45wt% of silicon carbide fiber powder mixture, 45wt% of organic solvent, 5wt% of dispersing agent, 5wt% of plasticizer and 5wt% of defoaming agent. In the silicon carbide fiber powder mixture, the volume ratio of the silicon carbide fiber is 50%, the diameter of the silicon carbide fiber is 0.01 μm, and the length-diameter ratio of the fiber is 1000. Otherwise, according to example 1, a slurry was prepared.
The slurry is subjected to compression molding to prepare a molded lining pipe green body with the inner diameter of 7.1mm, the outer diameter of 8.4mm, the wall thickness of 0.65mm and the length of 4000mm. Degreasing in a vacuum environment, wherein the degreasing process comprises the steps of heating to 800 ℃ at the heating rate of 2 ℃/min and preserving heat for 10 hours; after degreasing, continuously sintering at high temperature, wherein the sintering process is to heat up to 1200 ℃ at the heating rate of 10 ℃/min; then the temperature is raised to 2200 ℃ at the speed of 5 ℃/min, the temperature is kept for 2h, and the sintering atmosphere is argon. After sintering, the compact lining pipe is obtained, the inner diameter of which is 7.5mm, the outer diameter of which is 8.2mm, the wall thickness of which is 0.35mm and the length of which is 4000mm. And after the outer surface of the lining pipe is subjected to fiber weaving by adopting long fibers with the diameter of 5 mu m, densification is carried out at the temperature of 1100 ℃ by adopting a CVI (chemical vapor infiltration) process, and SiC coating deposition is carried out on the outer surface by continuously adopting a CVD (chemical vapor deposition) process to prepare the silicon carbide cladding pipe.
After the silicon carbide cladding tube is subjected to coarse grinding treatment on the inner surface and the outer surface, the inner diameter is 7.5mm, the outer diameter is 9.5mm, the wall thickness is 1mm, and the length is 4000mm. The density of the obtained silicon carbide cladding tube is 99 percent, and the straightness is 1/500; the leakage rate of the cladding is 10- 13 Pa·m 3 (ii)/s, tensile strength at room temperature is 550MPa, and tensile strength at high temperature of 1200 ℃ is 600MPa.
Example 4
The raw materials comprise: 80wt% of silicon carbide fiber powder mixture, 15wt% of organic solvent, 1.5wt% of dispersant, 2wt% of plasticizer and 1.5wt% of defoaming agent. In the silicon carbide fiber powder mixture, the volume ratio of the silicon carbide fiber is 35%, the diameter of the silicon carbide fiber is 5 μm, and the length-diameter ratio of the fiber is 10. Otherwise, according to example 1, slurry was prepared.
The slurry is subjected to compression molding to prepare a molded lining pipe green body with the inner diameter of 7.5mm, the outer diameter of 8.5mm, the wall thickness of 0.5mm and the length of 4000mm. Degreasing in a vacuum environment, wherein the degreasing process comprises heating to 500 ℃ at a heating rate of 2 ℃/min and preserving heat for 3h; after degreasing, continuously sintering at high temperature, wherein the sintering process is to heat up to 1200 ℃ at the heating rate of 10 ℃/min; then the temperature is raised to 1800 ℃ at the speed of 5 ℃/min, the temperature is kept for 2h, and the sintering atmosphere is argon. After sintering, the compact lining pipe is obtained, the inner diameter of the compact lining pipe is 7.7mm, the outer diameter of the compact lining pipe is 8.4mm, the wall thickness of the compact lining pipe is 0.35mm, and the length of the compact lining pipe is 4000mm. After the outer surface of the inner liner tube is woven by fibers of long fibers with the diameter of 15 mu m, the densification is carried out at the temperature of 1100 ℃ by adopting a CVI (chemical vapor deposition) process, and the SiC coating deposition is carried out on the outer surface by continuously adopting a CVD (chemical vapor deposition) process to prepare the silicon carbide cladding tube.
After the silicon carbide cladding tube is subjected to coarse grinding treatment on the inner surface and the outer surface, the inner diameter is 7.7mm, the outer diameter is 9.9mm, the wall thickness is 1.1mm, and the length is 4000mm. The density of the obtained silicon carbide cladding tube is 99%, and the straightness is 1/1000; the leakage rate of the cladding is 10- 13 Pa·m 3 (ii)/s, having a tensile strength of 400MPa at room temperature and a tensile strength of 500MPa at a high temperature of 1200 ℃.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (17)
1. A preparation method of a fiber toughened silicon carbide cladding is characterized by comprising the following steps:
s1, preparing slurry; the slurry comprises the following raw materials in parts by weight: 45 to 89.7 parts of silicon carbide fiber powder mixture, 10 to 40 parts of organic solvent, 0.1 to 5 parts of dispersant, 0.1 to 5 parts of plasticizer and 0.1 to 5 parts of defoaming agent;
s2, preparing and molding the slurry into a silicon carbide lining pipe green body;
s3, degreasing and sintering the silicon carbide lining pipe green blank to form a high-density silicon carbide lining pipe;
and S4, arranging a fiber woven layer on the outer surface of the silicon carbide lining pipe, and carrying out densification treatment on the fiber woven layer to form a silicon carbide cladding with fiber strengthening and toughening.
2. The method for preparing the fiber-toughened silicon carbide cladding as claimed in claim 1, wherein in step S1, the silicon carbide fiber powder mixture comprises a silicon carbide material; the silicon carbide material comprises silicon carbide fiber and silicon carbide powder, and the volume percentage of the silicon carbide fiber in the silicon carbide material is 10-50%;
the diameter of the silicon carbide fiber is 0.01-10 [ mu ] m, and the length-diameter ratio of the silicon carbide fiber is 10-1000.
3. The method for preparing the fiber-toughened silicon carbide cladding as claimed in claim 2, wherein in step S1, the silicon carbide fiber powder mixture further comprises a sintering aid, and the sintering aid is 1 to 10% by mass of the silicon carbide fiber powder mixture.
4. The method of producing the fiber-toughened silicon carbide cladding as claimed in claim 3, wherein the sintering aid is Al 2 O 3 -Re 2 O 3 Wherein Re is Sc, Y, la, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb or Lu;
among the sintering aids, al 2 O 3 And Re 2 O 3 The proportion of (1 wt%) to (99 wt%): 99wt% -1 wt%.
5. The method for preparing the fiber-toughened silicon carbide cladding as claimed in claim 1, wherein in step S1, the organic solvent is at least one of absolute ethyl alcohol, acetone, xylene, and polyethylene glycol;
the dispersant is at least one of oleic acid, stearic acid and castor oil;
the plasticizer is at least one of carboxymethyl cellulose, phenolic resin and tetramethyl ammonium hydroxide;
the defoaming agent is at least one of ethylene glycol, glycerol and simethicone.
6. The method of claim 1, wherein in step S1 the feedstock is slurried by at least one of roll milling, planetary milling, magnetic stirring, and mechanical stirring.
7. The method for preparing the fiber-toughened silicon carbide cladding as claimed in claim 1, wherein in step S2, the slurry is formed into a green silicon carbide lined tube by a compression molding or extrusion molding process.
8. The method of preparing the fiber-toughened silicon carbide cladding as claimed in claim 1, wherein in step S3, the degreasing treatment is as follows: heating to 400-800 ℃ at the heating rate of 1-10 ℃/min under vacuum, and keeping the temperature for 1-10 h.
9. The method of preparing the fiber-toughened silicon carbide cladding as claimed in claim 1 wherein in step S3, the sintering process is as follows: heating to 800-1200 ℃ at a heating rate of 10-20 ℃/min; then the temperature is raised to 1700 ℃ to 2200 ℃ at the heating rate of 5 ℃/min to 10 ℃/min, and the temperature is preserved for 0.5 to 4 hours.
10. The method of claim 1, wherein the sintering atmosphere in step S3 is vacuum or at least one of argon, helium, and nitrogen.
11. The method for preparing the fiber-toughened silicon carbide cladding as claimed in claim 1, wherein in step S2, the silicon carbide liner tube green body has an inner diameter of 7mm to 7.8mm, an outer diameter of 8.5mm to 9mm, and a wall thickness of 0.35mm to 1.0mm; the length of the silicon carbide lining pipe green body is 1000 mm-4000 mm.
12. The method for preparing the silicon carbide cladding with the fiber strengthened and toughened according to the claim 11, wherein in the step S3, the formed high-density silicon carbide lining pipe has an inner diameter of 7.1mm to 7.9mm, an outer diameter of 8.4mm to 9.1mm, a wall thickness of 0.25mm to 1.0mm and a length of 1000mm to 4000mm;
in the step S4, the inner diameter of the silicon carbide composite cladding is 7.1 mm-7.9 mm, the outer diameter is 9.5 mm-10.1 mm, the wall thickness is 0.3 mm-1.5 mm, and the length is 1000 mm-4000 mm; the straightness is 1/2000-1/100.
13. The method for producing the fiber-toughened silicon carbide cladding according to claim 1, wherein in step S4, the diameter of the silicon carbide fiber used in the fiber-woven layer is 5 μm to 20 μm.
14. The method of claim 1, wherein the densification process of step S4 employs at least one of chemical vapor infiltration, precursor dip pyrolysis, and reactive infiltration.
15. The method of making the fiber toughened silicon carbide cladding as claimed in any one of claims 1 to 14 further comprising the steps of:
and S5, arranging a coating on the outer surface of the silicon carbide composite cladding.
16. The method of making the fiber-toughened silicon carbide cladding as claimed in claim 15 wherein the coating comprises at least one of a silicon carbide coating, a metallic chromium coating, a high entropy coating.
17. A fiber-toughened silicon carbide cladding, characterized in that it has been obtained by the method of production according to any one of claims 1 to 16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211254791.1A CN115650751B (en) | 2022-10-13 | 2022-10-13 | Fiber-reinforced silicon carbide cladding and method for making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211254791.1A CN115650751B (en) | 2022-10-13 | 2022-10-13 | Fiber-reinforced silicon carbide cladding and method for making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115650751A true CN115650751A (en) | 2023-01-31 |
| CN115650751B CN115650751B (en) | 2023-10-31 |
Family
ID=84988395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211254791.1A Active CN115650751B (en) | 2022-10-13 | 2022-10-13 | Fiber-reinforced silicon carbide cladding and method for making same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115650751B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110170653A1 (en) * | 2008-09-18 | 2011-07-14 | Julien Cabrero | Nuclear fuel cladding with high heat conductivity and method for making same |
| CN103113110A (en) * | 2012-12-04 | 2013-05-22 | 海南大学 | Application method of composite silicon carbide ceramic fiber transition layer |
| CN103818056A (en) * | 2013-12-27 | 2014-05-28 | 西北工业大学 | Multilayer structure of SiC/SiC (silicon carbide) composite cladding tube and preparation method thereof |
| CN106904984A (en) * | 2017-02-27 | 2017-06-30 | 中国核动力研究设计院 | A kind of SiC short fiber composite materials and compound cladding tubes and preparation method thereof |
| CN109020589A (en) * | 2018-07-30 | 2018-12-18 | 西北工业大学 | A kind of crash-proof fuel kernel cladding tubes and preparation method |
| CN112062572A (en) * | 2020-08-19 | 2020-12-11 | 广东工业大学 | High-density silicon carbide ceramic and preparation method and application thereof |
| CN112209720A (en) * | 2020-10-10 | 2021-01-12 | 湖南金博碳素股份有限公司 | Carbon/silicon carbide bicontinuous phase composite material and preparation method thereof |
| CN112374902A (en) * | 2020-11-26 | 2021-02-19 | 中国核动力研究设计院 | Preparation method of high-densification SiCf/SiC clad composite pipe |
| CN112876257A (en) * | 2021-01-27 | 2021-06-01 | 中国核动力研究设计院 | SiCfTwo-layer composite cladding tube made of/SiC composite material and preparation method thereof |
| CN113563082A (en) * | 2021-08-06 | 2021-10-29 | 中国建筑材料科学研究总院有限公司 | Thin-wall silicon carbide ceramic heat exchange tube and preparation method and application thereof |
-
2022
- 2022-10-13 CN CN202211254791.1A patent/CN115650751B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110170653A1 (en) * | 2008-09-18 | 2011-07-14 | Julien Cabrero | Nuclear fuel cladding with high heat conductivity and method for making same |
| CN103113110A (en) * | 2012-12-04 | 2013-05-22 | 海南大学 | Application method of composite silicon carbide ceramic fiber transition layer |
| CN103818056A (en) * | 2013-12-27 | 2014-05-28 | 西北工业大学 | Multilayer structure of SiC/SiC (silicon carbide) composite cladding tube and preparation method thereof |
| CN106904984A (en) * | 2017-02-27 | 2017-06-30 | 中国核动力研究设计院 | A kind of SiC short fiber composite materials and compound cladding tubes and preparation method thereof |
| CN109020589A (en) * | 2018-07-30 | 2018-12-18 | 西北工业大学 | A kind of crash-proof fuel kernel cladding tubes and preparation method |
| CN112062572A (en) * | 2020-08-19 | 2020-12-11 | 广东工业大学 | High-density silicon carbide ceramic and preparation method and application thereof |
| CN112209720A (en) * | 2020-10-10 | 2021-01-12 | 湖南金博碳素股份有限公司 | Carbon/silicon carbide bicontinuous phase composite material and preparation method thereof |
| CN112374902A (en) * | 2020-11-26 | 2021-02-19 | 中国核动力研究设计院 | Preparation method of high-densification SiCf/SiC clad composite pipe |
| CN112876257A (en) * | 2021-01-27 | 2021-06-01 | 中国核动力研究设计院 | SiCfTwo-layer composite cladding tube made of/SiC composite material and preparation method thereof |
| CN113563082A (en) * | 2021-08-06 | 2021-10-29 | 中国建筑材料科学研究总院有限公司 | Thin-wall silicon carbide ceramic heat exchange tube and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115650751B (en) | 2023-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108558422B (en) | Preparation method of three-dimensional carbon fiber toughened ultrahigh-temperature ceramic matrix composite with high breaking power | |
| CN110317073B (en) | Preparation method of multi-stage fiber synergistic toughened antioxidant ceramic matrix composite material | |
| CN106904984B (en) | SiC short fiber composite material, composite cladding tube and preparation method thereof | |
| CN109437943B (en) | Cf/C-SiC-ZrB2Composite material and preparation method thereof | |
| CN108706978B (en) | Method for preparing silicon carbide ceramic matrix composite by combining spray granulation with 3DP and CVI | |
| CN107879758B (en) | C/C-SiC composite material with sandwich structure and preparation method thereof | |
| CN109265189B (en) | Method for rapidly preparing wave-absorbing ceramic matrix composite with electromagnetic impedance gradual change matrix | |
| CN113666765B (en) | Continuous fiber reinforced high-entropy ceramic matrix composite and preparation method thereof | |
| CN110282993B (en) | Preparation method of ceramic matrix composite containing interface phase | |
| CN110563479A (en) | Ultrahigh-temperature ceramic matrix composite and preparation method thereof | |
| CN107586117B (en) | Method for toughening alumina ceramic material by carbon fiber | |
| CN111302820B (en) | Preparation method of C/SiC composite material | |
| CN111285694A (en) | Preparation method of high-temperature wave-transparent silicon nitride radome | |
| CN113004051A (en) | SiCfInterface layer structure of/SiC composite material fuel cladding and preparation method | |
| CN115448744B (en) | Preparation method of carbon/carbon throat liner | |
| CN113896554B (en) | High-density fiber reinforced quartz ceramic composite material and preparation method thereof | |
| CN115650751B (en) | Fiber-reinforced silicon carbide cladding and method for making same | |
| CN113173791B (en) | SiBCN interface coating for SiC fiber reinforced composite material, and preparation method and application thereof | |
| CN113620713A (en) | WC/VCxHard material, method for the production thereof and use thereof | |
| CN115894082B (en) | (ZrHfTiTaNb) C-W metal high-entropy ceramic modified C/C composite material and preparation method thereof | |
| CN117024164A (en) | Ceramic modified carbon-carbon composite nose cone and preparation method thereof | |
| CN115124360B (en) | Carbon fiber toughened ceramic material and preparation method thereof | |
| CN114956836A (en) | Preparation method of SiBN/SiBCN composite interface layer on ceramic fiber surface | |
| CN110776322B (en) | Carbon-free composite ceramic submersed nozzle material and preparation method thereof | |
| CN107954722B (en) | Method for preparing Si3N4 gradient material through self-diffusion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |