CN111004032A - A kind of perovskite zircon type ceramic solidified body and its preparation method and application - Google Patents
A kind of perovskite zircon type ceramic solidified body and its preparation method and application Download PDFInfo
- Publication number
- CN111004032A CN111004032A CN201911203549.XA CN201911203549A CN111004032A CN 111004032 A CN111004032 A CN 111004032A CN 201911203549 A CN201911203549 A CN 201911203549A CN 111004032 A CN111004032 A CN 111004032A
- Authority
- CN
- China
- Prior art keywords
- solidified body
- perovskite
- type ceramic
- source
- ceramic solidified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052845 zircon Inorganic materials 0.000 title description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 title description 2
- 238000005245 sintering Methods 0.000 claims abstract description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005452 bending Methods 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000007711 solidification Methods 0.000 claims abstract description 3
- 230000008023 solidification Effects 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical group [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- DEIVNMVWRDMSMJ-UHFFFAOYSA-N hydrogen peroxide;oxotitanium Chemical compound OO.[Ti]=O DEIVNMVWRDMSMJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000002901 radioactive waste Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 7
- 238000002490 spark plasma sintering Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 239000002927 high level radioactive waste Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
- C04B35/488—Composites
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/301—Processing by fixation in stable solid media
- G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
-
- 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
- C04B2235/02—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
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- 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
- C04B2235/02—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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/443—Nitrates or nitrites
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/95—Products characterised by their size, e.g. microceramics
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention belongs to the technical field of high radioactive waste solidification treatment, and discloses a perovskite type ceramic solidified body and a preparation method and application thereof. The perovskite type ceramic solidified body is prepared by adding a calcium source, a titanium source and a zirconium source into a solvent and a ball milling medium for ball milling, wherein the mass ratio of the calcium source to the titanium source to the zirconium source is (40-46): (33-37): (17-24), drying to obtain mixed powder, carrying out dry pressing molding treatment on the mixed powder, heating the obtained blank to 1250-1400 ℃ in a protective atmosphere to carry out SPS sintering reaction, cooling to 800 ℃, cooling along with the furnace, and pressurizing to 20-50 MPa to obtain the product. The perovskite-type ceramic solidified body of the present invention has a particle diameter of 2 to 4 μm, a relative density of 95 to 99%, a hardness of 10 to 15HV, and a fracture toughness of 0.6 to 5MPa m1/2The bending strength is 100-150 MPa.
Description
Technical Field
The invention belongs to the technical field of high radioactive waste solidification treatment, and particularly relates to a perovskite type ceramic solidified body (CaZrTi)2O7) And a preparation method and application thereof.
Background
The safe disposal of nuclear waste is a central element of nuclear energy applications. At present, nuclear waste is mainly solidified by glass, and partial key nuclides have very low solubility in a glass solidified body and need to be solidified by using a ceramic or glass ceramic material, wherein the perovskite type ceramic solidified body has excellent stability, and the calcium position and the zirconium position of the perovskite type ceramic solidified body have higher solid solution capacity for actinide elements. Therefore, it is necessary to study a sintered perovskite-type ceramic solidified body.
The perovskite type ceramic solidified body is a compound which is difficult to synthesize, so that the traditional preparation method needs long synthesis time of about 72 hours and high sintering temperature to ensure the complete reaction. The traditional high-temperature solid phase method has the defects of slow temperature rise speed, slow temperature drop speed, long synthesis time and the like, and although the synthesis time is reduced by high-temperature self-propagation, the reaction temperature is too high (3000-. The chemical reagent used in the chemical method preparation process can generate secondary pollution in the treatment of high-level waste, and the treatment difficulty is increased. Therefore, a novel method for rapidly and efficiently preparing a perovskite type ceramic solidified body at a low temperature is urgently needed.
Deep geological repositories require cured substrates with greater density to take full advantage of the limited storage space. While the cured matrix requires good mechanical stability to withstand traffic impacts and geological storage pressures. The perovskite type ceramic solidified body prepared by the traditional preparation method at present has low density, more holes are displayed in the micro-morphology, and the grain size is larger and uneven, which greatly influences the mechanical property of the solidified body.
Disclosure of Invention
In order to solve the above-mentioned drawbacks and disadvantages of the prior art, a primary object of the present invention is to provide a perovskite-type ceramic solidified body. The perovskite type ceramic solidified body has higher density, more uniform grain diameter, reduced grain size by about one order of magnitude and excellent mechanical property.
Another object of the present invention is to provide a method for producing the above-mentioned perovskite-type ceramic solidified body.
Still another object of the present invention is to provide use of the above-mentioned perovskite-type ceramic solidified body.
The purpose of the invention is realized by the following technical scheme:
a perovskite type ceramic solidified body is prepared by adding a calcium source, a titanium source and a zirconium source into a solvent and a ball milling medium for ball milling, wherein the mass ratio of the calcium source to the titanium source to the zirconium source is (40-46): (33-37): (17-24), drying to obtain mixed powder, carrying out dry pressing molding treatment on the mixed powder, heating the obtained blank to 1250-1400 ℃ in a protective atmosphere to carry out SPS sintering reaction, cooling to 600-800 ℃, cooling along with the furnace, and pressurizing to 20-50 MPa to obtain the product.
Preferably, the solvent is absolute ethanol or acetone.
Preferably, the mass ratio of the calcium source to the titanium source to the zirconium source is (40-46): (33-37): (17-24).
Preferably, the proportion of the total mass of the calcium source, the titanium source and the zirconium source to the amount of the solvent is 1: (2-3).
Preferably, the calcium source is calcium titanate, calcium oxide, calcium hydroxide or calcium nitrate.
Preferably, the titanium source is nano titanium dioxide powder, titanium dioxide coarse powder or titanium sesquioxide.
Preferably, the zirconium source is zirconium oxide or zirconium nitrate.
Preferably, the perovskite-type ceramic solidified body has a particle size of 2 to 4 μm, a relative density of 95 to 99%, a hardness of 10 to 15HV, and a fracture toughness of 0.6 to 5MPa m1/2The bending strength is 100-150 MPa.
Preferably, the ball milling time is 2-24 h, the heating rate is 50-400 ℃/min, and the sintering time is 5-15 min.
Preferably, the protective atmosphere is vacuum, nitrogen or argon.
The perovskite type ceramic solidified body is applied to the field of solidifying high radioactive nuclear waste.
The invention adopts spark plasma sintering to prepare a perovskite type ceramic solidified body (CaZrTi)2O7) The uniaxial pressure is applied in the sintering process, so that the accumulation degree among particles can be increased, and the void volume is reduced, thereby increasing the density of a sample and realizing CaZrTi2O7The low-temperature rapid preparation not only meets the strict requirement of rapid disposal of nuclear waste, but also can promote the densification, the grain refinement, the improvement of the mechanical property, and effectively reduces the possibility of nuclide volatilization when the high-level nuclear waste is solidified.
Compared with the prior art, the invention has the following beneficial effects:
1. the perovskite type ceramic solidified body has higher compactness and purity, more uniform crystal grains, and the size of the crystal grains is reduced by about one order of magnitude, and has excellent mechanical properties.
2. The invention adopts spark plasma sintering to prepare the perovskite type ceramic solidified body, and can increase the degree of accumulation among particles and reduce the amount of gaps by applying uniaxial pressure in the sintering process, thereby increasing the density of a sample and realizing CaZrTi2O7The low-temperature rapid preparation not only meets the strict requirement of rapid disposal of nuclear waste, but also can promote the densification, the grain refinement, the improvement of the mechanical property, and effectively reduces the possibility of nuclide volatilization when the high-level nuclear waste is solidified.
3. The method shortens the preparation period of the perovskite zircon and improves the production efficiency.
Drawings
FIG. 1 shows a perovskite-type ceramic solidified body (CaZrTi) obtained in example 12O7) XRD pattern of (a).
FIG. 2 shows CaZrTi prepared in example 12O7SEM photograph of (a).
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The purity of the calcium titanate, the calcium oxide, the calcium hydroxide, the calcium nitrate, the nano titanium dioxide powder, the titanium dioxide coarse powder, the titanium oxide and the zirconium oxide in the embodiment of the invention is more than 99%.
Example 1
Mixing the components in a mass ratio of 40.1: 36.3: 23.6 adding absolute ethyl alcohol into the calcium titanate powder, the nano titanium dioxide powder and the zirconia powder, mixing for 24h on a roller ball mill, drying to obtain a mixed powder, dry-pressing and molding to obtain a block sample, heating the block to 1300 ℃ at a speed of 80 ℃/min in vacuum, preserving heat for 10min, performing SPS sintering, symmetrically cooling to 800 ℃, cooling with a furnace, pressurizing to 30MPa, and obtaining the perovskite type ceramic solidified body (CaZrTi)2O7)。
The obtained perovskite type ceramic solidified body contained a small amount of calcium titanate, and had a particle diameter of 3.72 μm, a pair density of 97.86%, a hardness of 10.78HV, and a fracture toughness of 1.72MPa m1/2The bending strength was 103.64 MPa.
FIG. 1 shows a perovskite-type ceramic solidified body (CaZrTi) obtained in this example2O7) XRD pattern of (a). As can be seen from FIG. 1, the sample obtained was CaZrTi2O7Pure phase, complete reaction and no impurity phase. FIG. 2 is an SEM photograph of a perovskite-type ceramic solidified body obtained in this example. As can be seen from FIG. 2, CaZrTi2O7The particle size is uniform and small, no obvious holes exist, the preparation method promotes the densification of the perovskite type ceramic solidified body, and simultaneously achieves the effect of refining grains.
Example 2
The difference from example 1 is that: the SPS sintering process comprises the following steps: the temperature is raised to 1200 ℃ at a rate of 50 ℃/min.
The grain diameter of the prepared purer perovskite type ceramic solidified body is 3.85 mu m, and the phaseThe pair density was 97.53%, the hardness was 10.48HV, and the fracture toughness was 1.65MPa m1/2The bending strength was 101.63 MPa.
Example 3
The difference from example 1 is that: sintering was carried out as in example 1, the sintering process being: the temperature is raised to 1350 ℃ at a speed of 100 ℃/min.
The prepared pure perovskite type ceramic solidified body is cracked, the grain diameter is 2.32 mu m, the pair density is 98.94 percent, the hardness is 11.56HV, and the fracture toughness is 1.06 MPa.m1/2The bending strength was 100.27 MPa.
Example 4
The difference from example 1 is that: the sintering process comprises the following steps: heating to 1300 deg.C at 120 deg.C/min, and pressurizing to 20 MPa.
The grain diameter of the prepared pure-phase perovskite type ceramic solidified body is 3.74 mu m, the pair density is 98.65 percent, the hardness is 11.06HV, and the fracture toughness is 1.85 MPa.m1/2The bending strength was 106.23 MPa.
Example 5
The difference from example 1 is that: taking calcium oxide powder, titanium dioxide coarse powder and zirconium oxide powder as raw materials, wherein the weight ratio of calcium oxide: titanium dioxide: the mass ratio of zirconia is 43.2: 34.5: 22.3, the sintering process comprises the following steps: the temperature is raised to 1300 ℃ at a speed of 120 ℃/min.
The pure-phase perovskite-type ceramic solidified body has a grain size of 2.64 mu m, a pair density of 99.04%, a hardness of 14.68HV, and a fracture toughness of 1.75MPa m1/2The bending strength was 114.66 MPa.
Example 6
The difference from example 1 is that: taking calcium hydroxide powder, nano titanium dioxide powder and zirconia powder as raw materials, wherein the weight ratio of calcium hydroxide: titanium dioxide: the mass ratio of zirconia is 45.4: 33.5: 21.1, the sintering process comprises the following steps: the temperature is raised to 1300 ℃ at the speed of 150 ℃/min, and the sintering environment is argon.
The grain diameter of the prepared pure-phase perovskite type ceramic solidified body is 2.85 mu m, the pair density is 98.87 percent, the hardness is 12.65HV, and the fracture toughness is 1.49 MPa.m1/2The bending strength was 113.25 MPa.
Example 7
The difference from example 1 is that: calcium nitrate powder, titanium dioxide coarse powder and zirconium oxide powder are used as raw materials, and the weight ratio of calcium hydroxide: titanium dioxide: the mass ratio of zirconia is 42.7: 35.2: 22.1, the sintering process comprises the following steps: the temperature is raised to 1300 ℃ at 200 ℃/min, and the sintering environment is nitrogen.
The pure-phase perovskite-type ceramic solidified body prepared has the grain diameter of 2.95 mu m, the pair density of 98.36 percent, the hardness of 11.76HV and the fracture toughness of 1.46 MPa-m1/2The bending strength was 115.03 MPa.
Example 8
The difference from example 1 is that: calcium nitrate powder, titanium oxide and zirconium oxide powder are used as raw materials, and calcium hydroxide: titanium dioxide: the mass ratio of zirconia is 45.6: 37.1: 17.3, sintering according to the method of the embodiment 1, wherein the sintering process comprises the following steps: the temperature is raised to 1300 ℃ at 200 ℃/min, and the sintering environment is nitrogen.
The grain diameter of the prepared pure-phase perovskite type ceramic solidified body is 2.49 mu m, the pair density is 98.84 percent, the hardness is 13.61HV, and the fracture toughness is 1.67 MPa.m1/2The bending strength was 112.66 MPa.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The perovskite type ceramic solidified body is characterized in that a calcium source, a titanium source and a zirconium source are added into a solvent and a ball milling medium for ball milling, and the mass ratio of the calcium source to the titanium source to the zirconium source is (40-46): (33-37): (17-24); drying to obtain mixed powder, carrying out dry pressing molding treatment on the mixed powder, heating the obtained blank to 1250-1400 ℃ in a protective atmosphere to carry out SPS sintering reaction, cooling to 600-800 ℃, cooling along with the furnace, and pressurizing to 20-50 MPa to obtain the material.
2. The perovskite-type ceramic solidified body according to claim 1, wherein the solvent is absolute ethanol or acetone.
3. The perovskite-type ceramic solidified body according to claim 1, wherein a mass ratio of the total mass of the calcium source, the titanium source, and the zirconium source to the solvent is 1: (2-3).
4. The perovskite-type ceramic solidified body according to claim 1, wherein the calcium source is calcium titanate, calcium oxide, calcium hydroxide, or calcium nitrate.
5. The perovskite-type ceramic solidified body according to claim 1, wherein the titanium source is nano titanium dioxide powder, titanium dioxide coarse powder, or titanium trioxide.
6. The perovskite-type ceramic solidified body according to claim 1, wherein the zirconium source is zirconium oxide or zirconium nitrate.
7. The perovskite-type ceramic solidified body according to claim 1, wherein the perovskite-type ceramic solidified body has a particle diameter of 2 to 4 μm, a relative density of 95 to 99%, a hardness of 10 to 15HV, and a fracture toughness of 0.6 to 5 MPa-m1 /2The bending strength is 100-150 MPa.
8. The perovskite-type ceramic solidified body according to claim 1, wherein the ball milling time is 2 to 24 hours, the temperature increase rate is 50 to 400 ℃/min, and the sintering time is 5 to 15 minutes.
9. The perovskite-type ceramic solidified body according to claim 1, wherein the protective atmosphere is vacuum, nitrogen or argon.
10. Use of a perovskite-type ceramic solidified body as defined in any one of claims 1 to 9 in the field of solidification of high-level nuclear waste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911203549.XA CN111004032A (en) | 2019-11-29 | 2019-11-29 | A kind of perovskite zircon type ceramic solidified body and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911203549.XA CN111004032A (en) | 2019-11-29 | 2019-11-29 | A kind of perovskite zircon type ceramic solidified body and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111004032A true CN111004032A (en) | 2020-04-14 |
Family
ID=70112518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911203549.XA Pending CN111004032A (en) | 2019-11-29 | 2019-11-29 | A kind of perovskite zircon type ceramic solidified body and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111004032A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118515479A (en) * | 2024-05-10 | 2024-08-20 | 西南科技大学 | A Gd-Nb co-doped perovskite and its preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2166424A (en) * | 1984-11-01 | 1986-05-08 | Atomic Energy Authority Uk | Synthetic rock materials |
| WO2001035422A2 (en) * | 1999-11-12 | 2001-05-17 | British Nuclear Fuels Plc | Encapsulation of waste |
| CN1767077A (en) * | 2005-08-06 | 2006-05-03 | 西南科技大学 | A kind of preparation method of base material for high radioactive waste solidification treatment |
| CN104496398A (en) * | 2014-12-04 | 2015-04-08 | 西南科技大学 | A kind of preparation method of perovskite zircon type artificial rock |
| CN108022665A (en) * | 2017-08-04 | 2018-05-11 | 西南科技大学 | A kind of self- propagating curing of radioactive pollution sand |
| CN110447077A (en) * | 2017-01-16 | 2019-11-12 | 俄罗斯联邦诺萨顿国家原子能公司 | The method for handling radioactive solution |
-
2019
- 2019-11-29 CN CN201911203549.XA patent/CN111004032A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2166424A (en) * | 1984-11-01 | 1986-05-08 | Atomic Energy Authority Uk | Synthetic rock materials |
| WO2001035422A2 (en) * | 1999-11-12 | 2001-05-17 | British Nuclear Fuels Plc | Encapsulation of waste |
| CN1767077A (en) * | 2005-08-06 | 2006-05-03 | 西南科技大学 | A kind of preparation method of base material for high radioactive waste solidification treatment |
| CN104496398A (en) * | 2014-12-04 | 2015-04-08 | 西南科技大学 | A kind of preparation method of perovskite zircon type artificial rock |
| CN110447077A (en) * | 2017-01-16 | 2019-11-12 | 俄罗斯联邦诺萨顿国家原子能公司 | The method for handling radioactive solution |
| CN108022665A (en) * | 2017-08-04 | 2018-05-11 | 西南科技大学 | A kind of self- propagating curing of radioactive pollution sand |
Non-Patent Citations (3)
| Title |
|---|
| SHI-KUAN SUN 等: "Reactive spark plasma synthesis of CaZrTi2O7 zirconolite ceramics for plutonium disposition", 《JOURNAL OF NUCLEAR MATERIALS》 * |
| 刘聪 等: "ZrO2对热压AlN陶瓷的显微结构与力学性能的影响", 《人工晶体学报》 * |
| 徐凯: "核废料玻璃固化国际研究进展", 《中国材料进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118515479A (en) * | 2024-05-10 | 2024-08-20 | 西南科技大学 | A Gd-Nb co-doped perovskite and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110002879B (en) | A dense and superhard high-entropy boride ceramic and its preparation method and application | |
| CN109879669B (en) | A kind of high-entropy ceramic composite material with high strength and its preparation method and application | |
| CN109987941B (en) | A kind of high-entropy ceramic composite material with oxidation resistance and its preparation method and application | |
| CN109400123B (en) | Fine-crystal alumina ceramic and preparation method and application thereof | |
| Vakifahmetoglu et al. | Reactive hydrothermal liquid‐phase densification (rHLPD) of ceramics–A study of the BaTiO3 [TiO2] composite system | |
| US9862648B2 (en) | Transparent metal fluoride ceramic | |
| CN105272229A (en) | Ceramic containing pyrochlore phase zirconic acid gadolinium powder and preparation method of ceramic | |
| Huang et al. | An effective strategy for preparing transparent ceramics using nanorod powders based on pressure-assisted particle fracture and rearrangement | |
| CN107285771A (en) | A kind of preparation method of the carbon ceramic material of two boron of ternary RE two | |
| Liu et al. | Transmittance enhancement of La0. 4Gd1. 6Zr2O7 transparent ceramic by aqueous AM gel-casting with pretreated powder | |
| CN111004032A (en) | A kind of perovskite zircon type ceramic solidified body and its preparation method and application | |
| Bettes et al. | Synthesis and processing of transparent polycrystalline doped yttrium aluminum garnet: a review | |
| US3917780A (en) | Preparation of lead lanthanum zirconate titanate bodies | |
| CN112830792A (en) | A high-hardness hafnium-based ternary solid solution boride ceramic and its preparation method and application | |
| CN100519469C (en) | Method for preparing massive compact high-pure single-phase Y2SiO5 ceramic block material at low temperature | |
| An et al. | Fabrication of transparent La2Zr2O7 by reactive spark plasma sintering | |
| CN101723670A (en) | Ti(CxN1-x)/Al2O3 composite material and preparation method thereof | |
| Feng et al. | Synthesis, densification, microstructure, and mechanical properties of samarium hexaboride ceramic | |
| JP2008137838A (en) | Alumina powder and method for producing the same | |
| CN104178651A (en) | Method of preparing zirconium oxide-tungsten metal ceramic | |
| CN115557793B (en) | A high-entropy ceramic with fine grain, high hardness and high toughness, its preparation method and application | |
| Shi et al. | Preparation of highly transparent silica glass by SPS sintering of SBA-15 | |
| Rezazadeh et al. | In-situ reactive synthesis of full dense Si2N2O by incorporating of Amourphous nanosized Si3N4; effect of MgO and Y2O3 | |
| CN103936007A (en) | Method for preparing titanium carbide nano-powder material | |
| Aydin et al. | Characterization and production of slip casts mullite–zirconia composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200414 |
|
| WD01 | Invention patent application deemed withdrawn after publication |