CN113185127B - Ca-Ti-Y-Al-Si-O microcrystalline glass solder and glass packaging method of nuclear cladding tube port - Google Patents
Ca-Ti-Y-Al-Si-O microcrystalline glass solder and glass packaging method of nuclear cladding tube port Download PDFInfo
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- 238000005253 cladding Methods 0.000 title claims abstract description 104
- 239000011521 glass Substances 0.000 title claims abstract description 77
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 29
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 29
- 229910018557 Si O Inorganic materials 0.000 title claims abstract description 28
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 26
- 238000000498 ball milling Methods 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 239000011812 mixed powder Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000835 fiber Substances 0.000 abstract description 6
- 238000007789 sealing Methods 0.000 abstract description 6
- 230000005855 radiation Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 231100000957 no side effect Toxicity 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 105
- 229910010271 silicon carbide Inorganic materials 0.000 description 103
- 238000005538 encapsulation Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000008393 encapsulating agent Substances 0.000 description 5
- 238000012536 packaging technology Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910001093 Zr alloy Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003758 nuclear fuel Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 235000008429 bread Nutrition 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000941 radioactive substance Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- 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
-
- 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
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21C—NUCLEAR REACTORS
- G21C3/00—Reactor fuel elements and their assemblies; Selection of substances for use as reactor fuel elements
- G21C3/02—Fuel elements
- G21C3/04—Constructional details
- G21C3/06—Casings; Jackets
- G21C3/07—Casings; Jackets characterised by their material, e.g. alloys
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
- C04B2237/10—Glass interlayers, e.g. frit or flux
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/36—Non-oxidic
- C04B2237/365—Silicon carbide
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/38—Fiber or whisker reinforced
-
- 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
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/84—Joining of a first substrate with a second substrate at least partially inside the first substrate, where the bonding area is at the inside of the first substrate, e.g. one tube inside another tube
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- 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
Abstract
The invention relates to Ca-Ti-Y-Al-Si-O microcrystalline glass solder and SiC f According to the glass packaging method of the SiC nuclear cladding tube port, raw materials with excellent irradiation resistance and no side effect on the nuclear reaction process are selected, a glass ceramic solder with excellent mechanical properties and good air tightness is prepared by adopting a melting-water cooling method, and the glass ceramic solder is low in high-temperature viscosity, and has a thermal expansion coefficient and SiC by virtue of the glass ceramic solder f The characteristic of good SiC matching and wettability realizes SiC under the condition of no pressure and at the applicable temperature (less than or equal to 1450 ℃) of the third generation of domestic SiC fibers f Packaging and connection of ports of SiC nuclear cladding tubes, the prepared connection joint has a glass phase and a crystal phase, the glass phase ensures excellent sealing effect at high temperature, and the crystal phase is favorable for improving high-temperature strength and promoting SiC f The application of/SiC in the nuclear reactor reduces the risks of accidents such as nuclear radiation, nuclear leakage and the like and improves the operation safety of the nuclear reactor.
Description
Technical Field
The invention belongs to a nuclear fuel cladding tube packaging technology, and relates to Ca-Ti-Y-Al-Si-O microcrystalline glass solder and SiC f Glass packaging method of/SiC nuclear cladding tube port, in particular to SiC f The preparation of the Ca-Ti-Y-Al-Si-O glass packaging agent and the glass tablet at the port of the SiC nuclear cladding tube and the packaging technology thereof are mainly used for the port packaging and connection of the nuclear cladding tube.
Background
In 2011, 3 months and 11 days, near coastal region of the Japan Xiantai, there is a large Rich 9.0 level earthquake, and the earthquake and the strong tsunami caused by the earthquake are used for creating the first nuclear power station of Fudao under the control of Tokyo electric company in Japan again, and nuclear accidents caused by nuclear leakage are caused. The direct cause of the Fudao nuclear accident is that the power supply system of the unit is powered off due to tsunami, the water circulation of the loop system is stopped, the cooling system is out of order, the steam in the pressure vessel can not be normally sent out for generating electricity, the zirconium alloy cladding used for wrapping the fuel assembly is exposed in the steam, and reacts with water molecules in the zirconium alloy cladding at high temperature to generate zirconium oxide; meanwhile, the zirconia continuously releases excessive hydrogen, and when the excessive hydrogen and radioactive substances are discharged to an external factory building along with steam through a valve on the pressure suppression pool, the excessive concentration is caused by accumulation in a region between the containment and the factory building, and the excessive hydrogen and the radioactive substances act with oxygen at high temperature to explode, so that serious nuclear accidents occur.
After the Fudao nuclear accident, developing a new generation of pressurized water reactor nuclear fuel cladding material capable of replacing a zirconium alloy cladding becomes a key problem to be solved urgently, and the new generation of cladding tube material is resistant to irradiation and high temperature, has good chemical stability and good environmental performance (does not react with water severely and produces little hydrogen), can still keep the reactor core intact when the nuclear accident happens, ensures that nuclear fuel fission products and radioactive gas do not leak, and can reduce the probability of nuclear leakage accident to the greatest extent.
SiC f The SiC has good high-temperature mechanical property and chemical stability, high specific strength and high specific modulus, and also has excellent irradiation resistance, low irradiation waste heat and low induced radioactivity, so that the SiC is an ideal candidate material for a new generation of nuclear cladding tube. The port package is SiC f Based on the safe service of the SiC nuclear cladding tube, the port packaging technology becomes a key technology of the safe service of the SiC nuclear cladding tube. Due to the current SiC f The SiC core cladding tube adopts domestic third-generation silicon carbide fiber, and the highest service temperature is 1450 ℃, so the packaging temperature is lower than 1450 ℃; the cladding tube is a thin-wall slender tube, and excessive stress cannot be applied in the processing process, so that the cladding tube is prevented from being damaged; the packaging solder needs to have good irradiation resistance; the sealing plug needs to keep good mechanical property and air tightness under the accident working condition (1200 ℃ and 25 MPa). These service requirements are largeThe application of various packaging techniques in the packaging of nuclear cladding tubes is greatly limited. Currently, it is difficult for the conventional packaging technology to simultaneously satisfy the above requirements.
CaO-Y has been used in the invention patent SiCf/SiC core cladding tube port CaO-Y2O3-Al2O3-SiO2 glass encapsulation method (application number CN 201911162409.2) 2 O 3 -Al 2 O 3 -SiO 2 Glass is finished with SiC f Encapsulation of SiC nuclear cladding ports. The CYAS glass has lower high-temperature viscosity and thermal expansion coefficient (3.9X10) -6 ) With SiC f Coefficient of thermal expansion of SiC (4.0X10) -6 ) Matching with SiC f The SiC composite material has good wetting effect, and the connecting joint has a compact and stable tissue structure, so that the dual requirements of the nuclear cladding tube port on mechanical property and air tightness can be ensured. However, the CYAS glass is packaged by a pure glass phase, and no crystal phase exists in the CYAS glass, so that the prior packaging technology needs to be improved in order to further improve the high-temperature mechanical property of the CYAS glass.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides Ca-Ti-Y-Al-Si-O microcrystalline glass solder and SiC f Glass encapsulation method of SiC nuclear cladding tube port.
Technical proposal
SiC (silicon carbide) f The Ca-Ti-Y-Al-Si-O microcrystalline glass solder at the port of the SiC nuclear cladding tube is characterized by comprising the following components in percentage by mass: 3 to 10wt.% CaO, 1 to 5wt.% TiO 2 10 to 35wt.% of Y 2 O 3 20 to 40wt.% of Al 2 O 3 And 30 to 50wt.% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The mass percentage sum of each component in the raw material composition is 100 percent.
The SiC f The preparation method of the Ca-Ti-Y-Al-Si-O microcrystalline glass solder at the port of the SiC nuclear cladding tube is characterized by comprising the following steps of: the mass fraction ratio is as follows: 3 to 10wt.% CaO, 1 to 5wt.% TiO 2 10 to 35wt.% of Y 2 O 3 20 to 40wt.% of Al 2 O 3 And 30 to 50wt.% SiO 2 Placing in a ball mill for ball milling and mixing uniformlyObtaining mixed powder, placing the mixed powder into an alumina crucible, placing the alumina crucible into a heat treatment furnace, preserving heat for 3-5 hours under the conditions of air atmosphere and heat treatment temperature 1580-1680 ℃, taking out and pouring the mixed powder into cold water to obtain transparent and colorless glass blocks; and crushing, ball milling and sieving the obtained glass blocks to obtain the microcrystalline glass solder.
The ball milling time is not less than 7 hours, and the rotating speed of the ball mill is 200-300 r/min.
The granularity of the mixed powder is 0.5-1.5 mu m.
Adopt the SiC f Ca-Ti-Y-Al-Si-O microcrystalline glass solder pair SiC at port of SiC nuclear cladding tube f Method for encapsulating a SiC nuclear cladding tube port, characterized by the steps of:
step 1: uniformly mixing 70-90 wt.% of absolute ethyl alcohol with the glass solder to obtain a glass powder packaging agent;
step 2: placing the glass powder packaging agent into a round tabletting mold, and applying pressure of 6-12 MPa to press to obtain a glass tabletting; the diameter of the circular tabletting mold is matched with the protruding diameter of the plug head of the cladding tube; the thickness of the round pressing piece is not less than 3mm;
step 3: uniformly coating the glass powder packaging agent on SiC f The coating depth of the inner wall of the SiC nuclear cladding tube and the protruding part of the cladding tube plug is larger than the protruding height of the cladding tube plug; placing a glass pressing sheet on the convex part of the plug head of the cladding tube, and assembling the glass pressing sheet on SiC f A SiC nuclear cladding tube;
step 4: siC to be assembled with plug f Placing the SiC nuclear cladding tube in a heat treatment furnace, heating up at 2-10 ℃/min under the argon atmosphere, preserving heat for 30-60 min at the heat treatment temperature of 1350-1430 ℃, cooling down to room temperature at 2-10 ℃/min after the heat preservation is finished, and finishing SiC f Encapsulation of SiC nuclear cladding tubes.
The SiC is f Placing the SiC nuclear cladding tube and the cladding tube plug head into absolute ethyl alcohol for ultrasonic cleaning, and cleaning the SiC after cleaning f Placing the SiC nuclear cladding tube and the cladding tube plug in an oven for drying and then for assembly;
advantageous effects
The invention proposesCa-Ti-Y-Al-Si-O microcrystalline glass solder and SiC f According to the glass packaging method of the SiC nuclear cladding tube port, raw materials with excellent irradiation resistance and no side effect on the nuclear reaction process are selected, a glass ceramic solder with excellent mechanical properties and good air tightness is prepared by adopting a melting-water cooling method, and the glass ceramic solder is low in high-temperature viscosity, and has a thermal expansion coefficient and SiC by virtue of the glass ceramic solder f The characteristic of good SiC matching and wettability realizes SiC under the condition of no pressure and at the applicable temperature (less than or equal to 1450 ℃) of the third generation of domestic SiC fibers f Packaging and connection of ports of SiC nuclear cladding tubes, the prepared connection joint has a glass phase and a crystal phase, the glass phase ensures excellent sealing effect at high temperature, and the crystal phase is favorable for improving high-temperature strength and promoting SiC f The application of/SiC in the nuclear reactor reduces the risks of accidents such as nuclear radiation, nuclear leakage and the like and improves the operation safety of the nuclear reactor.
The Ca-Ti-Y-Al-Si-O microcrystalline glass solder is prepared by a melting-water cooling method, and can finish SiC under the conditions of the applicable temperature of the third generation of SiC (less than or equal to 1450 ℃) and no pressure f Packaging/connection of SiC nuclear cladding tubes, which facilitates further propulsion of SiC f Use of/SiC in a nuclear reactor.
The invention selects low-activity elements with small nuclear irradiation decay rate, no side effect on the nuclear reaction process and excellent irradiation resistance, and prepares Ca-Ti-Y-Al-Si-O glass solder by a melting-water cooling method, and the prepared glass solder has small high-temperature viscosity, thermal expansion coefficient and SiC f The characteristics of good SiC matching and wettability can realize SiC under the condition of no pressure and at the applicable temperature (less than or equal to 1450 ℃) of the domestic third-generation SiC fiber f Encapsulation and connection of the SiC nuclear cladding ports.
The invention is characterized in that the original CaO-Y is 2 O 3 -Al 2 O 3 -SiO 2 A certain amount of TiO is added on the basis of glass 2 The prepared connecting joint has compact and stable internal structure, excellent mechanical property and air tightness. The connecting joint has both glass phase and crystal phase, the XRD pattern of the connecting joint has 'steamed bread peak' and yttrium silicate and mullite crystal peak which are special in amorphous form, and the glass phase can provide high-temperature sealing capability and also has obvious effectObvious infiltration filling effect, ensures SiC f Airtightness of the SiC nuclear cladding tube port; the crystal phase improves the high-temperature mechanical property, can further meet the dual requirements of the nuclear cladding tube port on the mechanical property and the air tightness, and is helpful for pushing SiC f The application of the SiC nuclear cladding tube reduces the risks of accidents such as nuclear radiation, nuclear leakage and the like and improves the operation safety of the nuclear reactor.
Drawings
FIG. 1 is a flow chart of the operation of the present invention
FIG. 2 is SiC f Drawing of SiC nuclear cladding tube
FIG. 3 is SiC f Drawing of SiC nuclear cladding tube port plug
FIG. 4 is a graph showing the thermal expansion coefficient of Ca-Ti-Y-Al-Si-O glass according to example 1 of the present invention.
FIG. 5 is a DSC chart of Ca-Ti-Y-Al-Si-O glass in example 1 of the present invention
FIG. 6 is a XRD pattern for Ca-Ti-Y-Al-Si-O glass according to example 1 of the present invention
FIGS. 7 and 8 are graphs showing the microscopic morphologies of CTYAS glasses according to examples 1, 2 and 3 of the present invention
Detailed Description
The invention will now be further described with reference to examples, figures:
example 1
CaO and TiO with granularity of 1 mu m are adopted 2 、Y 2 O 3 、Al 2 O 3 、SiO 2 The powder comprises the following components in percentage by mass: 5% CaO, 5% TiO 2 20% of Y 2 O 3 30% Al 2 O 3 40% SiO 2 The four powders are put into a ball milling tank to be ball milled for 12 hours at the rotating speed of 300r/min, the mixed powder after ball milling is put into an alumina crucible to be heat treated in air atmosphere, the heat treatment temperature is 1650 ℃, the heat preservation time is 2 hours, and the mixed powder is directly placed into cold water to be quenched after heat treatment, so that Ca-Ti-Y-Al-Si-O glass blocks are formed. Crushing and ball milling the glass blocks, and sieving the glass blocks by a 150-mesh screen to obtain Ca-Ti-Y-Al-Si-O glass powder. Adding alcohol into glass powder to form a packaging agent, wherein the mass fraction of the added alcohol is as follows90%. Coating an encapsulating agent on the inner wall of the cladding tube and the surface to be encapsulated of the cladding tube plug head, putting a glass pressing sheet with the thickness of 4mm on the cladding tube plug head, and mixing with SiC f The SiC nuclear cladding tube is assembled. Placing the assembled nuclear cladding tube and the plug in a tube furnace for heat treatment, wherein the heat treatment atmosphere is argon, the heat treatment temperature is 1400 ℃, the heat preservation time is 30min, and cooling to room temperature along with the furnace to finish SiC f Port encapsulation of SiC nuclear cladding tube.
Example 2
CaO and TiO with granularity of 1 mu m are adopted 2 、Y 2 O 3 、Al 2 O 3 、SiO 2 The powder comprises the following components in percentage by mass: 3% CaO, 2% TiO 2 30% of Y 2 O 3 25% Al 2 O 3 40% SiO 2 The four powders are put into a ball milling tank for ball milling for 15 hours at the rotating speed of 200r/min, the mixed powder after ball milling is put into an alumina crucible for heat treatment under the air atmosphere, the heat treatment temperature is 1630 ℃, the heat preservation time is 2 hours, and the mixed powder is directly placed into cold water for quenching after heat treatment to form Ca-Ti-Y-Al-Si-O glass blocks. Crushing and ball milling the glass blocks, and sieving the glass blocks by a 150-mesh screen to obtain Ca-Ti-Y-Al-Si-O glass powder. Adding alcohol into the glass powder to form a packaging agent, wherein the mass fraction of the added alcohol is 70%. Coating an encapsulating agent on the inner wall of the cladding tube and the surface to be encapsulated of the cladding tube plug head, putting a glass pressing sheet with the thickness of 3mm on the cladding tube plug head, and mixing with SiC f The SiC nuclear cladding tube is assembled. Placing the assembled cladding tube and plug in a tube furnace for heat treatment, wherein the heat treatment atmosphere is argon, the heat treatment temperature is 1420 ℃, the heat preservation time is 45min, and cooling to room temperature along with the furnace to finish SiC f Port encapsulation of SiC nuclear cladding tube.
Example 3
CaO and TiO with granularity of 1 mu m are adopted 2 、Y 2 O 3 、Al 2 O 3 、SiO 2 The powder comprises the following components in percentage by mass: 5% CaO, 3% TiO 2 27% of Y 2 O 3 20% of Al 2 O 3 45% SiO 2 Four powders were placed in a ball milling pot at a rate of 2Ball milling at 00r/min for 13h, placing the ball milled mixed powder into an alumina crucible, performing heat treatment under the air atmosphere, wherein the heat treatment temperature is 1600 ℃, the heat preservation time is 4 hours, and directly placing the mixture into cold water for quenching after the heat treatment to form Ca-Ti-Y-Al-Si-O glass blocks. Crushing and ball milling the glass blocks, and sieving the glass blocks by a 150-mesh screen to obtain Ca-Ti-Y-Al-Si-O glass powder. Adding alcohol into the glass powder to form a packaging agent, wherein the mass fraction of the added alcohol is 90%. Coating an encapsulating agent on the inner wall of the cladding tube and the surface to be encapsulated of the cladding tube plug head, putting a glass pressing sheet with the thickness of 5mm on the cladding tube plug head, and mixing with SiC f The SiC nuclear cladding tube is assembled. Placing the assembled cladding tube and plug in a tube furnace for heat treatment, wherein the heat treatment atmosphere is argon, the heat treatment temperature is 1400 ℃, the heat preservation time is 30min, and cooling to room temperature along with the furnace to finish SiC f Port encapsulation of SiC nuclear cladding tube.
Example 4
CaO and TiO with granularity of 1 mu m are adopted 2 、Y 2 O 3 、Al 2 O 3 、SiO 2 The powder comprises the following components in percentage by mass: 6% CaO, 4% TiO 2 25% of Y 2 O 3 20% of Al 2 O 3 45% SiO 2 The four powders are put into a ball milling tank to be ball milled for 13 hours at the rotating speed of 300r/min, the mixed powder after ball milling is put into an alumina crucible to be heat treated in air atmosphere, the heat treatment temperature is 1600 ℃, the heat preservation time is 4 hours, and the mixed powder is directly placed into cold water to be quenched after heat treatment, so that Ca-Ti-Y-Al-Si-O glass blocks are formed. Crushing and ball milling the glass blocks, and sieving the glass blocks by a 150-mesh screen to obtain Ca-Ti-Y-Al-Si-O glass powder. Adding alcohol into the glass powder to form a packaging agent, wherein the mass fraction of the added alcohol is 70%. Coating an encapsulating agent on the inner wall of the cladding tube and the surface to be encapsulated of the cladding tube plug head, putting a glass pressing sheet with the thickness of 5mm on the cladding tube plug head, and mixing with SiC f The SiC nuclear cladding tube is assembled. Placing the assembled cladding tube and plug in a tube furnace for heat treatment, wherein the heat treatment atmosphere is argon, the heat treatment temperature is 1420 ℃, the heat preservation time is 60min, and cooling to room temperature along with the furnace to finish SiC f Port encapsulation of SiC nuclear cladding tube.
Example 5
CaO and TiO with granularity of 1 mu m are adopted 2 、Y 2 O 3 、Al 2 O 3 、SiO 2 The powder comprises the following components in percentage by mass: 4.8% CaO, 19.0% Y 2 O 3 28.6% Al 2 O 3 47.6% SiO 2 The four powders are put into a ball milling tank to be ball milled for 12 hours at the rotating speed of 300r/min, the mixed powder after ball milling is put into an alumina crucible to be heat treated in air atmosphere, the heat treatment temperature is 1600 ℃, the heat preservation time is 4 hours, and the mixed powder is directly placed into cold water to be quenched after heat treatment, so that Ca-Y-Al-Si-O glass blocks are formed. Crushing and ball milling the glass blocks, and sieving the glass blocks by a 150-mesh screen to obtain Ca-Y-Al-Si-O glass powder. Adding alcohol into the glass powder to form a packaging agent, wherein the mass fraction of the added alcohol is 90%. Coating an encapsulating agent on the inner wall of the cladding tube and the surface to be encapsulated of the cladding tube plug head, putting a glass pressing sheet with the thickness of 3mm on the cladding tube plug head, and mixing with SiC f The SiC nuclear cladding tube is assembled. Placing the assembled cladding tube and plug in a tube furnace for heat treatment, wherein the heat treatment atmosphere is argon, the heat treatment temperature is 1400 ℃, the heat preservation time is 30min, and cooling to room temperature along with the furnace to finish SiC f Port encapsulation of SiC nuclear cladding tube.
The embodiment of the invention can be used for preparing the SiC of the third-generation SiC fibers in China f Glass encapsulation/connection of the SiC nuclear cladding ports, it can again be seen from the examples that the following advantages are achieved:
1. the Ca-Ti-Y-Al-Si-O glass solder is prepared by a melting-water cooling method, and the solder and SiC f The SiC composite material has good wettability, and can realize SiC under the condition of no pressure and at the applicable temperature (less than or equal to 1450 ℃) of the domestic third-generation SiC fiber f Packaging and connection of SiC nuclear cladding tube, and the prepared connection joint has compact and stable internal structure, excellent mechanical property and air tightness, and the thermal expansion coefficient of the joint is equal to that of SiC f The SiC composite material can meet the double requirements of the cladding tube on mechanical property and air tightness.
2. The invention is characterized in that CaO-Y 2 O 3 -Al 2 O 3 -SiO 2 A certain amount of TiO is added on the basis of glass 2 The prepared connecting joint has both glass phase and crystal phase, the XRD pattern of the connecting joint has special steamed bread peaks and yttrium silicate and mullite crystal peaks, the glass phase can provide high-temperature sealing capability, has obvious infiltration filling effect, and ensures SiC f Airtightness of the SiC nuclear cladding tube port; the crystal phase improves the high-temperature mechanical property, can further meet the dual requirements of the nuclear cladding tube port on the mechanical property and the air tightness, and is helpful for pushing SiC f The application of the SiC nuclear cladding tube reduces the risks of accidents such as nuclear radiation, nuclear leakage and the like and improves the operation safety of the nuclear reactor. The composition of the changes of the present invention is not arbitrarily determinable.
3. According to the invention, the problem of insufficient brazing filler metal caused by sintering solidification and infiltration is solved by placing the glass pressing sheet on the plug head of the cladding tube, the probability of generating a welding line after heat treatment is reduced, a compact sealing layer can be formed above the plug head, and a compact connecting layer is formed between the cladding tube and the plug head, so that SiC is further effectively improved f Hermeticity of the SiC nuclear cladding tube.
Claims (4)
1. SiC is adopted f Ca-Ti-Y-Al-Si-O microcrystalline glass solder pair SiC at port of SiC nuclear cladding tube f A method of packaging a SiC nuclear cladding tube port, characterized by:
the SiC is provided with f The Ca-Ti-Y-Al-Si-O microcrystalline glass solder at the port of the SiC nuclear cladding tube comprises the following components in percentage by mass: 3 to 10wt.% CaO, 1 to 5wt.% TiO 2 20 to 30wt.% of Y 2 O 3 20 to 30wt.% of Al 2 O 3 And 40 to 45wt.% SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The sum of the mass percentages of all the components in the raw material composition is 100 percent;
the preparation method of the glass ceramic solder comprises the following steps: the mass percentage ratio is as follows: 3 to 10wt.% CaO, 1 to 5wt.% TiO 2 20 to 30wt.% of Y 2 O 3 20 to 30wt.% of Al 2 O 3 And 40 to 45wt.% SiO 2 Ball milling and mixing in ball millMixing uniformly to obtain mixed powder, placing the mixed powder into an alumina crucible, placing the alumina crucible into a heat treatment furnace, preserving heat for 3-5 hours under the conditions of air atmosphere and heat treatment temperature 1580-1680 ℃, taking out, pouring into cold water, and obtaining transparent colorless glass blocks; crushing, ball milling and sieving the obtained glass blocks to obtain microcrystalline glass solder; the prepared microcrystalline glass solder has the advantages of low high-temperature viscosity, low thermal expansion coefficient and SiC f SiC matching and good wettability;
the packaging method comprises the following steps:
step 1: uniformly mixing 70-90 wt.% of absolute ethyl alcohol with microcrystalline glass solder to obtain a glass powder packaging agent;
step 2: placing the glass powder packaging agent into a round tabletting mold, and applying pressure of 6-12 MPa to press to obtain a glass tabletting; the diameter of the circular tabletting mold is matched with the protruding diameter of the plug head of the cladding tube; the thickness of the round pressing piece is not less than 3mm;
step 3: uniformly coating the glass powder packaging agent on SiC f The coating depth of the inner wall of the SiC nuclear cladding tube and the protruding part of the cladding tube plug is larger than the protruding height of the cladding tube plug; placing a glass pressing sheet on the convex part of the plug head of the cladding tube, and assembling the glass pressing sheet on SiC f A SiC nuclear cladding tube;
step 4: siC to be assembled with plug f Placing the SiC nuclear cladding tube in a heat treatment furnace, heating up at 2-10 ℃/min under the argon atmosphere, preserving heat for 30-60 min at the heat treatment temperature of 1400-1430 ℃, cooling down to room temperature at 2-10 ℃/min after the heat preservation is finished, and finishing SiC f And the packaging of the SiC nuclear cladding tube meets the double requirements of the nuclear cladding tube on mechanical properties and air tightness.
2. The method according to claim 1, characterized in that: the ball milling time is not less than 7 hours, and the rotating speed of the ball mill is 200-300 r/min.
3. The method according to claim 1, characterized in that: the granularity of the mixed powder is 0.5-1.5 mu m.
4. The method according to claim 1, characterized in that: the SiC is f Placing the SiC nuclear cladding tube and the cladding tube plug head into absolute ethyl alcohol for ultrasonic cleaning, and cleaning the SiC after cleaning f The SiC nuclear cladding tube and the cladding tube plug are put into an oven for drying and then used for assembly.
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CN109384475B (en) * | 2018-10-09 | 2021-10-01 | 长安大学 | Combined improvement of SiCfMethod for high-temperature water and oxygen corrosion resistance of/SiC composite material |
CN110903102B (en) * | 2019-11-25 | 2022-03-15 | 西北工业大学 | SiCfCaO-Y at port of/SiC nuclear cladding tube2O3-Al2O3-SiO2Glass packaging method |
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