CN116514523B - Ceramic shell for vacuum circuit breaker and preparation process thereof - Google Patents
Ceramic shell for vacuum circuit breaker and preparation process thereof Download PDFInfo
- Publication number
- CN116514523B CN116514523B CN202310302744.8A CN202310302744A CN116514523B CN 116514523 B CN116514523 B CN 116514523B CN 202310302744 A CN202310302744 A CN 202310302744A CN 116514523 B CN116514523 B CN 116514523B
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- ceramic shell
- ceramic
- titanate
- ball milling
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- 239000000919 ceramic Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011521 glass Substances 0.000 claims abstract description 50
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 35
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 33
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 16
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 16
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 lanthanum aluminate Chemical class 0.000 claims abstract description 16
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 15
- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 claims abstract description 14
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 13
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 13
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 12
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000011257 shell material Substances 0.000 claims description 79
- 238000000498 ball milling Methods 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 31
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 27
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002241 glass-ceramic Substances 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000008395 clarifying agent Substances 0.000 claims description 7
- 229910001610 cryolite Inorganic materials 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 238000009966 trimming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000006025 fining agent Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 13
- 238000010292 electrical insulation Methods 0.000 abstract description 13
- 238000007789 sealing Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000243 solution Substances 0.000 description 24
- 239000000306 component Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000008157 edible vegetable oil Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 206010051246 Photodermatosis Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008845 photoaging Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 244000188595 Brassica sinapistrum Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
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- C04B33/13—Compounding ingredients
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- C04B33/24—Manufacture of porcelain or white ware
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
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- C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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- C04B2235/6567—Treatment time
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
Abstract
The invention discloses a ceramic shell for a vacuum circuit breaker and a preparation process thereof, and relates to the field of ceramic materials and manufacturing thereof. The invention discloses a ceramic shell which is prepared from the following raw materials in parts by weight: 30-40 parts of kaolin, 10-15 parts of pretreated nano boehmite, 22-25 parts of microcrystalline glass, 7-9 parts of copper calcium titanate, 5-8 parts of lanthanum aluminate, 2-3 parts of calcium carbonate, 1-3 parts of sodium silicate, 2-4 parts of magnesium oxide and 1-2 parts of sodium hexametaphosphate; the invention also provides a preparation process of the ceramic shell. The ceramic shell for the vacuum circuit breaker has excellent mechanical strength, high and low temperature resistance, hydrophobicity and electrical insulation, and is good in air tightness, high in breakdown strength, excellent in pollution resistance, high in flashover voltage and high in metal sealing strength, and the service life of the vacuum circuit breaker is prolonged.
Description
Technical Field
The invention belongs to the field of ceramic materials and manufacturing thereof, and particularly relates to a ceramic shell for a vacuum circuit breaker and a preparation process thereof.
Background
A vacuum interrupter is a power switching device that is capable of conducting current at maximum capacity or providing a reliable break in the circuit that ensures that the energy source in the circuit is completely blocked at one end of the break. The vacuum interrupter is a core component of the vacuum circuit breaker, and needs to have high insulation strength and bear high voltage, so that the vacuum interrupter generates electric arc as in air when current is opened in high vacuum, and the shell of the vacuum interrupter mainly provides a fracture effect. The vacuum arc-extinguishing chamber has casing made of insulating material and two ends sealed with metal cover plates to form one sealed container.
In order to ensure a sufficiently high vacuum level of the vacuum interrupter during operation, the insulating housing must be airtight and completely sealed to prevent chronic leakage of the insulating housing during storage and use of the vacuum interrupter. The vacuum arc-extinguishing chamber has high vacuum degree and high-voltage insulation performance, is used as a control element of a vacuum circuit breaker and is easy to be acted by a transverse force, so that the insulating shell has high mechanical strength, high electric breakdown strength, flashover high voltage resistance, high electrical insulation property, high-temperature degassing resistance, good air tightness and good sealing performance with metal, but has no special requirements on heat conductivity and dielectric loss.
In the current market, insulating housings used for vacuum circuit breakers mainly include glass insulating housings and ceramic insulating housings. The glass insulating shell has higher electric breakdown strength, good insulativity, excellent ageing resistance, good oil stain resistance and arc resistance, low operation and maintenance cost, lower strength, high price, iron-nickel-cobalt alloy sealing, longer production period, only adopting an exhaust process for whole assembly, lower production efficiency, high self-breaking rate and low quality, and is not suitable for a high-voltage system, and the surface of the glass insulating shell is easy to condense water to cause electricity leakage; the ceramic insulating shell has the advantages of high mechanical strength, good chemical stability, good insulativity, good corrosion resistance and the like, but is brittle, low in reliability, general in breaking strength, easy to cause flashover, easy to generate defects such as air holes and impurities, general in high-voltage breakdown resistance and greatly shortens the service life of the ceramic insulating shell. In recent years, glass ceramics are also used as an insulating shell of a vacuum circuit breaker, but the crystallization behavior of a glass ceramics system is extremely sensitive to a sintering process, so that the process control difficulty of the insulating shell is high, and the product performance stability is poor, so that the glass ceramics system is not widely popularized.
The main component of the ceramic insulating shell used in the commercial vacuum arc-extinguishing chamber is high-alumina ceramic of a CAS system containing 95% of alumina, the relative dielectric constant is smaller, the ceramic insulating shell is difficult to bear very high voltage and is easy to break down, so that the conventional method is to coat an insulating shell on the ceramic insulating shell so as to improve the dielectric insulation strength and high-voltage breakdown resistance of the insulating shell. The materials of the insulating shell are organic materials such as polyurethane and epoxy resin with good insulation, and ceramic materials with high dielectric properties such as barium strontium titanate and barium titanate, however, the bonding effect between the coating layer and the base layer is poor due to the different materials of the coating layer and the base layer, the service effect and the service life of the insulating shell are finally affected, and the requirements of the increasingly developed power industry cannot be met.
Disclosure of Invention
The invention aims to provide a ceramic shell for a vacuum circuit breaker and a preparation process thereof, wherein the ceramic shell has excellent mechanical strength, high and low temperature resistance, hydrophobicity and electrical insulation, and is good in air tightness, high in breakdown strength, excellent in pollution resistance, high in flashover voltage and high in metal sealing strength, and the service life of the vacuum circuit breaker is prolonged.
In order to achieve the purpose of the invention, the invention provides a ceramic shell for a vacuum circuit breaker, wherein the ceramic shell is a shell material of a vacuum arc-extinguishing chamber in the vacuum circuit breaker, and comprises the following raw materials in parts by weight: 30-40 parts of kaolin, 10-15 parts of pretreated nano boehmite, 22-25 parts of microcrystalline glass, 7-9 parts of copper calcium titanate, 5-8 parts of lanthanum aluminate, 2-3 parts of calcium carbonate, 1-3 parts of sodium silicate, 2-4 parts of magnesium oxide and 1-2 parts of sodium hexametaphosphate;
the microcrystalline glass is Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 Microcrystalline glass.
Further, the Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 The microcrystalline glass consists of the following raw materials in percentage by weight: 52.5-58.0% SiO 2 、18.5～22.5％Li 2 O、8.4～8.8％TiO 2 、2.4～3.0％CeO 2 、4.5～5.1％SrO、3.9～4.6％ZrO 2 1.5 to 1.9 percent of cryolite and 1.8 to 2.6 percent of clarifying agent.
Further, the clarifying agent is sodium fluosilicate.
Further, the Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 The preparation method of the microcrystalline glass comprises the following steps: the preparation method comprises the steps of weighing glass ceramics raw materials with required quality, uniformly mixing, preserving heat and melting for 3-5 h at 1350-1480 ℃, cooling to 950-1000 ℃ at the rate of 30-40 ℃/min, preserving heat for 1-1.5 h, cooling to 850-890 ℃ at the rate of 20 ℃/min, preserving heat for 0.5-1 h, cooling to 590-720 ℃ at the rate of 20-25 ℃/min, preserving heat for 1-1.5 h, carrying out ball milling after furnace cooling, and obtaining Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 Microcrystalline glass.
Further, the preparation method of the pretreated nano boehmite comprises the following steps: adding a titanate coupling agent into toluene, and uniformly stirring to obtain a titanate-toluene solution; then putting the nano boehmite into titanate-toluene solution, carrying out ultrasonic treatment for 40-60 min, carrying out suction filtration, washing with absolute ethyl alcohol to remove surface residual solution, and then placing the solution in a vacuum drying oven at 150-180 ℃ for 1-2 h.
Further, the ratio of the nano boehmite to the titanate-toluene solution is 300-360 g/L, and the concentration of the titanate-toluene solution is 3.2-3.6 mM.
The invention also provides a preparation process of the ceramic shell for the vacuum circuit breaker, which comprises the following steps:
(1) Weighing the raw materials of the ceramic shell according to parts by weight for standby;
(2) Adding kaolin, calcium carbonate, magnesium oxide and pretreated nano boehmite into a ball mill, and ball milling for 20-24 hours to obtain premix;
(3) Ball milling microcrystalline glass and sodium hexametaphosphate in a ball mill, adding the mixture into a premix, uniformly mixing, and then adding sodium silicate, copper calcium titanate and lanthanum aluminate for mixing to obtain a mixture;
(4) Mixing the mixture, the ball stone and water according to the mass ratio of 1:3:1.2, mixing, ball milling, sieving, removing iron, squeezing mud, ageing, vacuum pugging, shaping, trimming and drying to obtain a blank;
(5) And (3) placing the obtained blank into a sintering furnace, heating to 400-500 ℃ at the speed of 5-8 ℃/min, preserving heat for 2-3 h, heating to 1200-1280 ℃ at the speed of 10-15 ℃/min, preserving heat for 3-4 h, and naturally cooling to room temperature.
Further, the ball milling speed in the step (3) is 350-460 r/min, and the ball milling time is 16-18 h.
Further, the ball milling speed in the step (4) is 420-500 r/min, the ball milling time is 20-28 h, and the ball milling speed is sieved by a 400-mesh sieve.
The invention has the following beneficial effects:
1. the ceramic shell is a ceramic/microcrystalline glass system, and by designing a proper microcrystalline glass system and combining proper ceramic components, the ceramic shell and metal can be matched and sealed, so that the ceramic shell has a proper thermal expansion coefficient and high sealing strength, and the ceramic shell has the advantages of good air tightness, high bending strength, high breaking strength, good electrical insulation and high electric breakdown resistance.
2. The ceramic shell adopts kaolin, pretreated nano boehmite, calcium carbonate, sodium silicate, magnesium oxide, sodium hexametaphosphate and other components to match, so that the sintering temperature of the ceramic shell is reduced, the cost is saved, and meanwhile, the components are uniformly dispersed and tightly combined, so that the ceramic shell has good mechanical strength and electrical insulation property and higher electric breakdown resistance.
3. The pretreated nano boehmite can be adsorbed on the surface of the nano boehmite after being pretreated by the titanate coupling agent, so that the dispersibility and the binding force of the nano boehmite in each component are improved, the density, the strength and the toughness of the ceramic shell are further improved, and the ceramic body grains are uniformly distributed. The heat treatment process of the ceramic shell of the invention is to slowly heat up to 400-500 ℃ and then heat up to 1200-1280 ℃ at a certain speed, so that nano boehmite is firstly converted into gamma-alumina at a lower temperature, and gamma-Al with higher activity 2 O 3 The ceramic material can form liquid phase or solid solution with each component in the ceramic shell at the sintering temperature, and the components are tightly combined under the action of surface tension, so that the density of the ceramic shell is improved, and the ceramic piece has a proper heat conductivity coefficient and excellent insulativity; then sintering and converting into alpha-Al at high temperature 2 O 3 Further, the comprehensive properties of the invention, such as mechanical strength, high temperature stability, chemical stability, electrical insulation and the like, are improved.
4. The microcrystalline glass is prepared from SiO 2 、Li 2 O、TiO 2 、CeO 2 、SrO、ZrO 2 Li is prepared from cryolite and other raw materials in a certain proportion 2 O 3 -CeO 2 -SiO 2 -TiO 2 Microcrystalline glass, improved fluidity of ceramic shell during sintering process, and improved fluidity of ceramic shellThe glass phase in the ceramic shell is easy to form a liquid phase in the high-temperature sintering process, so that the removal of pores in the ceramic is facilitated, the binding force with other components is improved, the bending strength and the breaking strength of the ceramic shell are further improved, the hydrophobicity, weather resistance, flashover voltage, high and low temperature resistance, dirt resistance and electric breakdown resistance of the ceramic shell are improved, the thermal expansion coefficient of the ceramic shell is increased, and the ceramic shell and metal have higher sealing strength. The microcrystalline glass adopts silicon dioxide and lithium oxide in proper proportion to form metasilicic acid with higher expansion coefficient, lithium disilicate crystal and the like, so that the microcrystalline glass has higher thermal expansion coefficient, higher flexural strength, electrical insulation and the like; ceO (CeO) 2 SrO and TiO 2 The glass ceramics can be uniformly and densely stacked in crystalline phases, has higher electrical insulation property and mechanical strength, and can also improve the electric breakdown resistance and dielectric property of the glass ceramics.
5. On the basis of kaolin and pretreated nano boehmite, the ceramic is combined with microcrystalline glass, and a proper amount of copper calcium titanate, lanthanum aluminate, calcium carbonate, magnesium oxide and the like are added, so that crystal grains in the ceramic shell are fine and uniform, the density is high, the porosity is low, the mechanical strength, the high and low temperature resistance and the electrical insulation property of the ceramic shell are improved, and the ceramic has better waterproof property, pollution resistance, electric breakdown resistance and metal sealing matching property. The proper proportion of magnesium oxide and calcium carbonate is used as sintering auxiliary agents, so that the compactness of the ceramic shell is improved, meanwhile, crystal grains are thinned, the porosity is reduced, and the mechanical strength, the water resistance and the low temperature resistance of the ceramic shell are improved; the addition of sodium silicate improves the binding force among the components of the ceramic shell, improves the compactness of the ceramic shell, reduces the porosity of the ceramic shell, further improves the high-voltage breakdown resistance of the ceramic shell, and ensures that the ceramic shell and metal have higher sealing strength; the copper calcium titanate and the lanthanum aluminate are added in a certain proportion, so that the high dielectric property of the ceramic shell is maintained, the electrical insulation property and the high thermal stability of the ceramic shell are obviously improved, and the ceramic shell has better electric breakdown resistance and higher flashover voltage.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The nano-boehmite, also known as aluminum oxyhydroxide, in the present invention is selected from Hua Xiangke.
The copper calcium titanate and lanthanum aluminate in the invention are selected from Katian optical materials Co.
The titanate coupling agent is bis (dioctyl-oxy-pyrophosphato) ethylene titanate, and the model is KR-238S.
The ceramic housing for a vacuum interrupter according to the present invention will be described with reference to specific embodiments.
Example 1
The preparation process of the ceramic shell for the vacuum circuit breaker specifically comprises the following steps:
(1) Weighing according to parts by weight, adding 30 parts of kaolin, 2 parts of calcium carbonate, 2 parts of magnesium oxide and 20 parts of pretreated nano boehmite into a ball mill, and ball milling for 24 hours at the speed of 420r/min to obtain premix.
(2) And ball-milling 25 parts of glass ceramics and 1 part of sodium hexametaphosphate in a ball mill for 18 hours at the speed of 450r/min, adding the glass ceramics and the sodium hexametaphosphate into a premix, uniformly mixing, and adding 9 parts of copper calcium titanate, 8 parts of lanthanum aluminate and 3 parts of sodium silicate for mixing to obtain a mixture.
(3) Mixing the mixture, the ball stone and water according to the mass ratio of 1:3:1.2, ball milling is carried out after mixing, ball milling is carried out for 25 hours at the speed of 480r/min, sieving is carried out for 400 meshes, iron is removed, and then mud pressing, ageing for 72 hours, vacuum pugging, shaping, blank repairing and drying are sequentially carried out, thus obtaining the blank.
(4) And (3) placing the obtained blank into a sintering furnace, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 3 hours, heating to 1250 ℃ at a speed of 10 ℃/min, preserving heat for 4 hours, and naturally cooling to room temperature.
The microcrystalline glass is Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 The preparation method of the microcrystalline glass comprises the following steps: weighing 52.5 parts by weight of SiO 2 22.5 parts of Li 2 O, 8.8 parts of TiO 2 2.4 parts of CeO 2 5.1 parts of SrO, 4.6 parts of ZrO 2 Mixing 1.5 parts of cryolite and 2.6 parts of clarifying agent uniformly, then preserving heat and melting for 5 hours at 1450 ℃, then cooling to 950 ℃ at the rate of 40 ℃/min, preserving heat for 1.5 hours, then cooling to 890 ℃ at the rate of 20 ℃/min, preserving heat for 1 hour, then cooling to 720 ℃ at the rate of 25 ℃/min, preserving heat for 1.5 hours, cooling with a furnace, crushing, ball milling to obtain Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 Microcrystalline glass.
The preparation method of the pretreated nano boehmite comprises the following steps: adding 2.9g of titanate coupling agent into 1L of toluene, and uniformly stirring to obtain a titanate-toluene solution; then 300g of nano boehmite is put into titanate-toluene solution, ultrasonic treatment is carried out for 60min, suction filtration is carried out, absolute ethyl alcohol is used for cleaning to remove the surface residual solution, and then the solution is placed into a vacuum drying oven at 180 ℃ for 2h, thus obtaining the nano boehmite.
Example 2
The preparation process of the ceramic shell for the vacuum circuit breaker specifically comprises the following steps:
(1) Weighing according to parts by weight, adding 40 parts of kaolin, 3 parts of calcium carbonate, 4 parts of magnesium oxide and 16 parts of pretreated nano boehmite into a ball mill, and ball milling for 24 hours at the speed of 420r/min to obtain premix.
(2) And ball-milling 22 parts of glass ceramics and 2 parts of sodium hexametaphosphate in a ball mill for 18 hours at the speed of 450r/min, adding the glass ceramics and the sodium hexametaphosphate into a premix, uniformly mixing, and adding 7 parts of copper calcium titanate, 5 parts of lanthanum aluminate and 1 part of sodium silicate for mixing to obtain a mixture.
(3) Mixing the mixture, the ball stone and water according to the mass ratio of 1:3:1.2, ball milling is carried out after mixing, ball milling is carried out for 25 hours at the speed of 480r/min, sieving is carried out for 400 meshes, iron is removed, and then mud pressing, ageing for 72 hours, vacuum pugging, shaping, blank repairing and drying are sequentially carried out, thus obtaining the blank.
(4) And (3) placing the obtained blank into a sintering furnace, heating to 500 ℃ at the speed of 8 ℃/min, preserving heat for 3 hours, heating to 1280 ℃ at the speed of 15 ℃/min, preserving heat for 4 hours, and naturally cooling to room temperature.
The microcrystalline glass is Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 The preparation method of the microcrystalline glass comprises the following steps: weighing 58 parts by weight of SiO 2 18.5 parts of Li 2 O, 8.4 parts of TiO 2 3 parts of CeO 2 4.5 parts of SrO, 3.9 parts of ZrO 2 Mixing 1.9 parts of cryolite and 1.8 parts of clarifying agent uniformly, then preserving heat and melting for 5 hours at 1480 ℃, then cooling to 1000 ℃ at the rate of 30 ℃/min, preserving heat for 1.5 hours, then cooling to 850 ℃ at the rate of 20 ℃/min, preserving heat for 1 hour, then cooling to 650 ℃ at the rate of 20 ℃/min, preserving heat for 1.5 hours, cooling with a furnace, crushing, ball milling to obtain Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 Microcrystalline glass.
The preparation method of the pretreated nano boehmite comprises the following steps: 3.3g of titanate coupling agent is added into 1L of toluene and stirred uniformly to obtain a titanate-toluene solution; then 360g of nano boehmite is put into titanate-toluene solution, ultrasonic treatment is carried out for 60min, suction filtration is carried out, absolute ethyl alcohol is used for cleaning to remove the surface residual solution, and then the solution is placed into a vacuum drying oven at 180 ℃ for 2h, thus obtaining the nano boehmite.
Example 3
The preparation process of the ceramic shell for the vacuum circuit breaker specifically comprises the following steps:
(1) Weighing according to parts by weight, adding 35 parts of kaolin, 2 parts of calcium carbonate, 4 parts of magnesium oxide and 18 parts of pretreated nano boehmite into a ball mill, and ball milling for 24 hours at the speed of 420r/min to obtain premix.
(2) And (3) ball-milling 23 parts of glass ceramics and 1 part of sodium hexametaphosphate in a ball mill for 18 hours at the speed of 450r/min, adding the glass ceramics and the sodium hexametaphosphate into a premix, uniformly mixing, and adding 8 parts of copper calcium titanate, 7 parts of lanthanum aluminate and 2 parts of sodium silicate, and mixing to obtain a mixture.
(3) Mixing the mixture, the ball stone and water according to the mass ratio of 1:3:1.2, ball milling is carried out after mixing, ball milling is carried out for 25 hours at the speed of 480r/min, sieving is carried out for 400 meshes, iron is removed, and then mud pressing, ageing for 72 hours, vacuum pugging, shaping, blank repairing and drying are sequentially carried out, thus obtaining the blank.
(4) And (3) placing the obtained blank in a sintering furnace, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 3 hours, heating to 1280 ℃ at a speed of 10 ℃/min, preserving heat for 4 hours, and naturally cooling to room temperature.
The microcrystalline glass is Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 The preparation method of the microcrystalline glass comprises the following steps: weighing 55.8 parts by weight of SiO 2 20 parts of Li 2 O, 8.2 parts of TiO 2 2.8 parts of CeO 2 4.8 parts of SrO, 4.2 parts of ZrO 2 Mixing 1.8 parts of cryolite and 2.4 parts of clarifying agent uniformly, then preserving heat and melting for 5 hours at 1480 ℃, then cooling to 950 ℃ at the rate of 40 ℃/min, preserving heat for 1.5 hours, then cooling to 850 ℃ at the rate of 20 ℃/min, preserving heat for 1 hour, then cooling to 590 ℃ at the rate of 25 ℃/min, preserving heat for 1.5 hours, cooling with a furnace, crushing, ball milling to obtain Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 Microcrystalline glass.
The preparation method of the pretreated nano boehmite comprises the following steps: 3g of titanate coupling agent is added into 1L of toluene and stirred uniformly to obtain a titanate-toluene solution; then 340g of nano boehmite is put into titanate-toluene solution, ultrasonic treatment is carried out for 60min, suction filtration is carried out, absolute ethyl alcohol is used for cleaning to remove the surface residual solution, and then the solution is placed into a vacuum drying oven at 180 ℃ for 2h, thus obtaining the nano boehmite.
Example 4
The preparation process of the ceramic shell for the vacuum circuit breaker specifically comprises the following steps:
(1) The premix is prepared by adding 37.5 parts of kaolin, 2 parts of calcium carbonate, 2.5 parts of magnesium oxide and 19 parts of pretreated nano boehmite into a ball mill, and ball milling for 24 hours at the speed of 420 r/min.
(2) And (3) ball-milling 22.5 parts of microcrystalline glass and 1.5 parts of sodium hexametaphosphate in a ball mill for 18 hours at the speed of 450r/min, adding the mixture into a premix, uniformly mixing, and adding 7 parts of copper calcium titanate, 6 parts of lanthanum aluminate and 2 parts of sodium silicate for mixing to obtain a mixture.
(3) Mixing the mixture, the ball stone and water according to the mass ratio of 1:3:1.2, ball milling is carried out after mixing, ball milling is carried out for 25 hours at the speed of 480r/min, sieving is carried out for 400 meshes, iron is removed, and then mud pressing, ageing for 72 hours, vacuum pugging, shaping, blank repairing and drying are sequentially carried out, thus obtaining the blank.
(4) And (3) placing the obtained blank in a sintering furnace, heating to 500 ℃ at a speed of 5 ℃/min, preserving heat for 3 hours, heating to 1280 ℃ at a speed of 10 ℃/min, preserving heat for 4 hours, and naturally cooling to room temperature.
The compositions and preparation methods of the microcrystalline glass and the pretreated nano-boehmite are the same as those of the embodiment 3, and the embodiment 3 is specifically referred to.
Comparative example 1
The ceramic shell of this comparative example 1 was prepared in the same manner as in example 4, with specific reference to example 4. In contrast, the nanoboehmite of this comparative example 1 was untreated, i.e., 19 parts of nanoboehmite was added.
Comparative example 2
The ceramic shell of this comparative example 2 was prepared in the same manner as in example 4, with specific reference to example 4. In contrast, in this comparative example 2, 19 parts of pretreated alumina was added instead of pretreated nano-boehmite. The preparation method of the pretreated alumina comprises the following steps: 3.2g of titanate coupling agent is added into 1L of toluene and stirred uniformly to obtain a titanate-toluene solution; then 150g of alumina powder is put into titanate-toluene solution, ultrasonic is carried out for 30min, suction filtration is carried out, absolute ethyl alcohol is used for cleaning to remove the surface residual solution, and then the solution is placed into a vacuum drying oven at 120 ℃ for 2h, thus obtaining the product. Wherein, the alumina powder consists of the following components in percentage by mass: 1 alpha-Al 2 O 3 And gamma-Al 2 O 3 Composition is prepared.
Comparative example 3
The ceramic shell of this comparative example 3 was prepared in the same manner as in example 4, with specific reference to example 4. In contrast, in this comparative example 3, li was not added 2 O 3 -CeO 2 -SiO 2 -TiO 2 Microcrystalline glass, instead 22.5 parts of CAS crystallites were addedGlass. The preparation method of the CAS microcrystalline glass comprises the following steps: 60 parts by weight of SiO 2 10 parts by weight of Al 2 O 3 16 parts by weight of CaO, 1.5 parts by weight of B 2 O 3 6.0 parts by weight of ZnO and 2.5 parts by weight of TiO 2 1.5 parts by weight of Na 2 O, 2.0 parts by weight K 2 O and 0.5 part by weight Co 2 O 3 Uniformly mixing, smelting at 1350 ℃ to form glass liquid, carrying out water quenching on the glass liquid to form microcrystalline glass slag, grinding the microcrystalline glass slag, and sieving with 400 meshes to obtain the glass.
Comparative example 4
The ceramic shell of this comparative example 4 was prepared in the same manner as in example 4, with specific reference to example 4. In contrast, li in this comparative example 4 2 O 3 -CeO 2 -SiO 2 -TiO 2 The preparation method of the microcrystalline glass comprises the following steps: weighing 55.8 parts by weight of SiO 2 20 parts of Li 2 O, 8.2 parts of TiO 2 2.8 parts of CeO 2 4.8 parts of SrO, 4.2 parts of ZrO 2 Uniformly mixing 1.8 parts of cryolite and 2.4 parts of clarifying agent, then carrying out heat preservation and melting for 5 hours at 1480 ℃, then carrying out water quenching on glass liquid to form microcrystalline glass slag, then heating to 590 ℃, carrying out heat preservation for 3 hours, cooling along with a furnace, and carrying out ball milling to obtain the glass.
Comparative example 5
The ceramic shell of this comparative example 5 was prepared in the same manner as in example 4, with specific reference to example 4. In contrast, in this comparative example 5, li was not added 2 O 3 -CeO 2 -SiO 2 -TiO 2 The adding amount of the microcrystalline glass and the kaolin is 60 parts.
Comparative example 6
The ceramic shell of this comparative example 6 was prepared in the same manner as in example 4, with specific reference to example 4. Except that lanthanum aluminate was not added in this comparative example 6, the amount of kaolin added was 43.5 parts.
Comparative example 7
The ceramic shell of this comparative example 7 was prepared in the same manner as in example 4, with specific reference to example 4. In contrast, in comparative example 7, copper calcium titanate and lanthanum aluminate were not added, and kaolin was added in an amount of 50.5 parts.
Performance test:
1. the ceramic shells prepared in examples 1 to 4 and comparative examples 1 to 7 were respectively taken, and the performances such as weather resistance, low temperature resistance and electrical insulation performance of the appearance mechanical properties of the ceramic shells were detected according to the relevant standards of GB/T772 and GB/T1001.1, and the average data thereof were recorded.
(1) The test pieces were tested for mechanical strength, electrical properties, weather resistance and water resistance, and the specific test results are shown in table 1 below.
Wherein: static contact angle, tested according to DLT 376-2010; photo-aging: artificial photoaging is carried out by adopting GB/T16422.3 1997, a treated sample is placed into an ultraviolet weather-resistant test box, ultraviolet A340 fluorescent ultraviolet is used as a light source, the distance between the sample and the light source is kept to be 50mm, the sample and the light source are circularly exposed for 8 hours under the irradiation of the black standard temperature of 60+/-3 ℃, and then are exposed for 4 hours under the non-irradiation condensation of the black standard temperature of 50+/-3 ℃ until the exposure time reaches 5000 hours, wherein the irradiation intensity is 2000-2600 mu W/cm 2 S, the treated sample was then subjected to a measurement of hydrophobic properties using the DLT 376-2010 standard.
Table 1:
as can be seen from the results of Table 1, the ceramic shells of examples 1-4 all have superior mechanical strength. Proper microcrystalline glass is selected, so that the mechanical strength, hydrophobicity and flashover voltage of the ceramic shell are remarkably improved; nanometer boehmite is adopted and pretreated, so that the strength and toughness of the ceramic shell are obviously improved; the adoption of the proper proportion of the copper calcium titanate and the lanthanum aluminate obviously improves the flashover voltage of the ceramic shell.
(2) Test pieces were tested for electrical insulation, electrical shock strength, etc., and ag—cu—ti solder (expansion coefficient of 128×10 -7 Per c) the ceramic housing test pieces of the present invention were brazed to 316L stainless steel (900 c/10 min) and tested for sealing properties, and the specific test results are shown in table 2 below.
TABLE 2
From the results of Table 2, it can be seen that the ceramic envelope of the present invention has more excellent electrical insulation, impact strength and sealing properties.
2. The ceramic shells of example 4 and comparative examples 3 to 5 were taken for anti-fouling experiments and anti-icing experiments.
And (3) artificial simulation pollution experiment: the rapeseed edible oil is used as simulated organic pollutant, and the simulated inorganic pollutant solution is composed of kaolin, naCl and water. The step of manually spraying the filth is as follows: 2mL of edible oil is dissolved in 40mL of acetone for dilution, and then the diluted edible oil acetone solution is sprayed on the surface of the ceramic shell uniformly by a sprayer. Distilled water, kaolin and NaCl are mixed according to the mass ratio of 200:10: and 1, manually spraying the pollution liquid on the ceramic shell. Tap water is adopted in the experiment to simulate the natural rainwater. The specific results are shown in Table 3.
Manual simulation anti-icing experiment: after accurately weighing the ceramic shell, placing the ceramic shell into a refrigerator at the temperature of minus 15 ℃, and simultaneously fixing a water dripping device above the ceramic shell, wherein a plurality of small holes are formed in the bottom of the device, so that small water drops can continuously drip on the ceramic shell, and the experiment time is 12 hours. The relative ice coating based on the weight of the ceramic shell matrix is expressed as percentage of the weight gain (temperature-15 ℃, humidity 45.+ -. 3%). The specific results are shown in Table 3 below.
Table 3:
| inorganic dirt accumulation phenomenon | Accumulation of organic pollutants | |
| Example 4 | The surface is dust-free | No pollution on surface |
| Comparative example 3 | Small amount of dust on surface | A small amount of surface pollution |
| Comparative example 4 | Small amount of dust on surface | A small amount of surface pollution |
| Comparative example 5 | Small amount of dust on surface | A small amount of surface pollution |
As can be seen from the results in Table 3, the ceramic shell of the invention has better dirt resistance and prolongs the service life of the vacuum circuit breaker.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (5)
1. The ceramic shell is a shell material of a vacuum arc-extinguishing chamber in the vacuum circuit breaker, and is characterized by comprising the following raw materials in parts by weight: 30-40 parts of kaolin, 10-15 parts of pretreated nano boehmite, 22-25 parts of microcrystalline glass, 7-9 parts of copper calcium titanate, 5-8 parts of lanthanum aluminate, 2-3 parts of calcium carbonate, 1-3 parts of sodium silicate, 2-4 parts of magnesium oxide and 1-2 parts of sodium hexametaphosphate;
the microcrystalline glass is Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 Microcrystalline glass;
the Li is 2 O 3 -CeO 2 -SiO 2 -TiO 2 The microcrystalline glass consists of the following raw materials in percentage by weight: 52.5-58.0% SiO 2 、18.5～22.5％Li 2 O、8.4～8.8％TiO 2 、2.4～3.0％CeO 2 、4.5～5.1％SrO、3.9～4.6％ZrO 2 1.5 to 1.9 percent of cryolite and 1.8 to 2.6 percent of clarifying agent;
the Li is 2 O 3 -CeO 2 -SiO 2 -TiO 2 The preparation method of the microcrystalline glass comprises the following steps: the preparation method comprises the steps of weighing glass ceramics raw materials with required quality, uniformly mixing, preserving heat and melting for 3-5 h at 1350-1480 ℃, cooling to 950-1000 ℃ at the speed of 30-40 ℃/min, preserving heat for 1-1.5 h, cooling to 850-890 ℃ at the speed of 20 ℃/min, preserving heat for 0.5-1 h, cooling to 590-720 ℃ at the speed of 20-25 ℃/min, preserving heat for 1-1.5 h, and ball milling after furnace cooling to obtain Li 2 O 3 -CeO 2 -SiO 2 -TiO 2 Microcrystalline glass;
the preparation method of the pretreated nano boehmite comprises the following steps: adding a titanate coupling agent into toluene, and uniformly stirring to obtain a titanate-toluene solution; then putting the nano boehmite into titanate-toluene solution, carrying out ultrasonic treatment for 40-60 min, carrying out suction filtration, washing with absolute ethyl alcohol to remove surface residual solution, and then placing the solution in a vacuum drying oven at 150-180 ℃ for 1-2 h to obtain the nano boehmite;
the ratio of the nano boehmite to the titanate-toluene solution is 300-360 g/L, and the concentration of the titanate-toluene solution is 3.2-3.6 mM.
2. The ceramic housing for a vacuum interrupter of claim 1, wherein the fining agent is sodium fluorosilicate.
3. Process for the preparation of a ceramic casing for a vacuum circuit breaker according to any one of claims 1 to 2, characterized in that it comprises in particular the following steps:
(1) Weighing the raw materials of the ceramic shell according to parts by weight for standby;
(2) Adding kaolin, calcium carbonate, magnesium oxide and pretreated nano boehmite into a ball mill, and ball milling for 20-24 hours to obtain premix;
(3) Ball milling microcrystalline glass and sodium hexametaphosphate in a ball mill, adding the mixture into a premix, uniformly mixing, and then adding sodium silicate, copper calcium titanate and lanthanum aluminate for mixing to obtain a mixture;
(4) Mixing the mixture, the ball stone and water according to the mass ratio of 1:3:1.2, mixing, ball milling, sieving, removing iron, squeezing mud, ageing, vacuum pugging, shaping, trimming and drying to obtain a blank;
(5) Placing the obtained blank into a sintering furnace, heating to 400-500 ℃ at the speed of 5-8 ℃/min, preserving heat for 2-3 h, heating to 1200-1280 ℃ at the speed of 10-15 ℃/min, preserving heat for 3-4 h, and naturally cooling to room temperature.
4. The process for preparing a ceramic shell for a vacuum circuit breaker according to claim 3, wherein the ball milling rate in the step (3) is 350-460 r/min and the ball milling time is 16-18 h.
5. The process for preparing a ceramic housing for a vacuum circuit breaker according to claim 3, wherein the ball milling rate in the step (4) is 420-500 r/min, the ball milling time is 20-28 h, and the screen is 400 mesh.
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