CN114773084A - Method for preparing gadolinium oxysulfide ceramic hollow microspheres - Google Patents
Method for preparing gadolinium oxysulfide ceramic hollow microspheres Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 54
- 239000004005 microsphere Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 36
- MCVAAHQLXUXWLC-UHFFFAOYSA-N [O-2].[O-2].[S-2].[Gd+3].[Gd+3] Chemical compound [O-2].[O-2].[S-2].[Gd+3].[Gd+3] MCVAAHQLXUXWLC-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000004448 titration Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000005238 degreasing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical group CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920005646 polycarboxylate Polymers 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000005488 sandblasting Methods 0.000 claims description 3
- 238000005201 scrubbing Methods 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 8
- 239000011232 storage material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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Abstract
The invention discloses a method for preparing gadolinium oxysulfide ceramic hollow microspheres, which comprises the steps of adding an additive into a water solvent, uniformly mixing to prepare a premixed solution, wherein the additive comprises a dispersing agent, a monomer, a cross-linking agent, a green body reinforcing agent, a closed-pore forming agent and a sintering aid; gd is mixed with2O2Ball-milling S ceramic powder and premixed liquid to prepare Gd with the solid content of 75-85 percent2O2S, adding an initiator and a catalyst into the slurry, and uniformly mixing for later use; manufacturing a semi-circular arc-shaped super-hydrophobic rail coated with a super-hydrophobic film, placing the rail on an inclined rack, and attaching the lower part of the inclined surface of the rail by using a heating tape; selectingPositioning a titration needle cylinder 18-15 cm above the track by using a needle of a dispenser, and carrying out Gd2O2S ceramic slurry is injected into a titration needle cylinder, the inclined plane is controlled to be heated to 150-210 ℃, the size of liquid drops is controlled to be 0.18-1 mm through the air inlet pressure of compressed air and the size of a pinhole, the liquid drops drop on a metal rail coated with a super-hydrophobic film from the top end of the inclined plane, roll downwards and are heated and cured into Gd2O2S, preparing a microsphere blank; molding Gd2O2Drying and degreasing the S ball blank, and sintering to obtain Gd2O2S ceramic hollow microspheres.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic ceramic hollow microspheres, and particularly relates to a method for preparing gadolinium oxysulfide ceramic hollow microspheres.
Background
With the rapid development of quantum communication technology, the demands of military, government affairs and financial industry on quantum communication are very urgent, and the application demands of matched ultralow temperature technology with the temperature of below 2.5K and related equipment raw materials are increased. One of the most important devices for quantum computing is a novel cold storage material Gd2O2S, among the numerous magnetic cold storage materials, Gd2O2S has magnetic phase change in the temperature range of 2-7K, has a higher specific heat capacity peak value, and is a cold storage material with practical value.
At present Gd2O2The cold storage material S mainly adopts solid microspheres with the diameter of 0.16-0.45 mm, and the solid microspheres limit the capacity of storing liquid helium, so that the refrigeration efficiency is difficult to further improve. And a cold storage material Gd2O2S is made into hollow microspheres with similar specifications, which is helpful for storing liquid helium into Gd2O2Inside the S hollow ball, the liquid helium storage can be greatly improved, and the working efficiency of the refrigerator is further improved.
Disclosure of Invention
Aiming at Gd of the existing refrigerating machine2O2The invention provides a product status quo that S cold storage material can only provide solid microspheres, and provides a method for preparing Gd2O2The method of S ceramic hollow microsphere combines gel casting technology and super-hydrophobic surface technology and combines micron Gd2O2Preparing ceramic slurry with the solid content of 75-85% by using an S ceramic powder, adding a closed-cell pore-forming agent into the slurry, directly dripping the mixture on a super-hydrophobic surface with a certain inclination angle by using a titration syringe, and rolling and curing the mixture to Gd under a specific temperature condition2O2S ceramic ball blank, then drying, degreasing and high-temperature sintering are carried out, and Gd with better sphericity and size uniformity can be prepared after the high-temperature sintering2O2S closed cell hollow microspheres.
The invention is realized by the following technical scheme:
a method for preparing gadolinium oxysulfide ceramic hollow microspheres comprises the following steps:
step one, Gd2O2Preparation of S ceramic slurry
Preparation of premixed liquid
Selecting Gd with an average particle size of 1-2 mu m2O2S ceramic powder, preparing a premixed liquid of slurry with the solid content of 75-85% by using a gel casting process, wherein the premixed liquid comprises a water solvent and additives, the content of the water solvent accounts for 17.64-33.33% of the mass of the powder, and the additives added into the water solvent account for the mass of the powder in the following proportion: 0.50-2.12% of dispersing agent, 1.05-5.50% of monomer, 0.05-0.51% of cross-linking agent, 0.05-0.10% of blank reinforcing agent, 18.8-27.4% of closed-cell pore-forming agent and 0.9-2.0% of sintering aid, wherein a magnetic rotor or a mechanical stirring rod is used for stirring all the time in the process of preparing the premixed solution so as to uniformly mix all the additives in the aqueous solution;
the blank reinforcing agent is cotton fibers, the closed pore-forming agent is one or more of calcium sulfate, calcium hydroxide, calcium carbonate and aluminum sulfate, and the sintering aid is one or more of aluminum oxide, titanium oxide, zirconium oxide, boron oxide and bismuth oxide;
② ball milling
Gd is added2O2Carrying out planetary ball milling on the S ceramic powder and the prepared premixed liquid together to prepare Gd with the solid content of 75-85 percent2O2S sizing agent;
thirdly, adding curing agent
Gd after ball milling2O2Adding an initiator accounting for 0.06-0.30 per mill of the mass of the powder and a catalyst accounting for 0.12-0.34 per mill of the mass of the powder into the S slurry, and uniformly mixing for later use;
step two, manufacturing the semi-circular arc super-hydrophobic track
Manufacturing a semi-circular arc-shaped super-hydrophobic rail coated with a super-hydrophobic film, placing the rail on an inclined rack, enabling the inclination angle of the rail to be 25-35 degrees, and attaching the lower part of the inclined plane of the rail by using a heating belt;
step three, Gd2O2Titration forming of S microsphere blank
The selection specification is 24-28#The needle head of the dispenser is used for positioning a titration needle cylinder 18-15 cm above the track, and Gd is added2O2S ceramic slurry is injected into a titration needle cylinder, the inclined plane is controlled to be heated to 150-210 ℃, the size of ceramic slurry liquid drops is controlled through the air inlet pressure of compressed air and the size of a pinhole, the size of the liquid drops is 0.18-1 mm, the liquid drops drop on a metal track coated with a super-hydrophobic film from the top end of the inclined plane, roll downwards and are heated and cured into Gd2O2S, preparing a microsphere blank;
step four, Gd2O2Preparation of S microsphere blank
Molding Gd2O2Drying the S ball blank at 100-150 ℃ for 10-20 h, degreasing at 600-700 ℃ for 15-25 h, sintering at 1470-1590 ℃ in reducing atmosphere or inert atmosphere, and keeping the temperature at the highest temperature for 3-8 h to obtain Gd2O2S ceramic hollow microspheres.
Further, the dispersant is ammonium polyacrylate or ammonium polycarboxylate.
Further, the monomer is acrylamide or methacrylamide.
Further, the cross-linking agent is N-N' methylene-bis-acrylamide.
Furthermore, the planetary ball milling adopts a 20L ball milling tank, and the selected ballsThe milling tank is made of nylon or polyurethane, and zirconia balls are selected as a milling medium; the diameter of the selected grinding ball is 2-5 mm, and the material ball ratio ranges from 1:1 to 2: 1; the ball milling rotation speed is 100-200 r/min, the ball milling time is 8-20 h, and the ball milled slurry rotates at room temperature for 20s-1The viscosity value under the condition is 58-192 mPas.
Further, the initiator is ammonium persulfate.
Further, the catalyst is tetramethylethylenediamine.
Further, the semi-circular arc-shaped super-hydrophobic rail is manufactured by the following specific steps: the method comprises the steps of carrying out sand blasting treatment on the inner surface of a semicircular arc-shaped metal track, coating or depositing a layer of super-hydrophobic film on the inner surface of the track after alcohol scrubbing, wherein the thickness of the film is 10-25 mu m, the super-hydrophobic film is further added with a bonding agent with the mass fraction of 0-5% and used for firmly adhering a super-hydrophobic coating to the surface of a metal substrate, and a heating belt is attached to the semicircular arc bottom surface of the track or is wound on the whole semicircular arc track in a mode of being perpendicular to the axial direction.
Furthermore, the radius of the semicircular arc-shaped metal track is 50-100 mm, the thickness is 1-3 mm, the length is 10-20 m, the cross section of the semicircular arc-shaped metal track is semicircular, the opening of the semicircular arc-shaped metal track is upward, and the metal track is made of copper, aluminum or stainless steel.
Furthermore, the adhesive is protein glue, resin glue or chlorinated rubber.
The invention has the beneficial effects that:
gd prepared by the invention2O2The S ceramic hollow microsphere has the advantages of high sphericity, good size uniformity, less working procedures, low equipment investment, high production efficiency and the like, and specifically comprises the following steps:
（1）Gd2O2the S ceramic hollow microsphere has higher sphericity
Because the ceramic liquid drop is always on the super-hydrophobic surface, when the hydrophobic angle is more than 160 degrees, the ceramic liquid drop is always kept to be a more ideal sphere, and simultaneously, because the solid content of the slurry is higher and the moisture content is lower, the shrinkage deformation of the sphere blank is extremely small in the evaporation curing process, the rolling process is also beneficial to the sphericization, and the whole process can always keep higher sphericity. The improvement of sphericity is favorableIncrease Gd2O2The storage capacity, the mechanical strength and the abrasion resistance (reducing energy consumption and material loss) of the S hollow microspheres during movement in a cylinder;
（2）Gd2O2the S ceramic hollow microsphere has better specification uniformity
Due to Gd2O2S ceramic liquid drops can be set to be in an intermittent dropping or continuous spraying mode during titration, the inclined plane is in an inclined state, meanwhile, as the track is designed to be in a semi-circular arc shape, after the liquid drops contact the track, the liquid drops slide down to the same downhill direction under the action of the super-hydrophobic membrane, and the situation that the liquid drops are fused and enlarged is avoided, the uniformity of the spherical size of the S ceramic liquid drops can be ensured, and the spherical size can be adjusted through the size of a titration pinhole, if 26 is used, the S ceramic liquid drops slide down to the same downhill direction#A dispensing needle cylinder, wherein the size range of the hollow ball blank is 0.22-0.48 mm after the liquid drops are solidified and fall to the collecting tank;
(3) less working procedures, low process cost and high production efficiency
The forming process can be finished in one step, the hollow ball blank curing process can be seamlessly connected with the subsequent collecting process, the process quantity, the process cost and the equipment investment are greatly reduced, and the automation degree and the efficiency can be greatly improved due to the simple process;
（4）Gd2O2the S ceramic microspheres can form a closed cell structure
Because of the forming mode and the addition of the closed pore-forming agent, closed pores with communicated or not communicated interior of the microspheres can be formed after high-temperature sintering, thereby successfully preparing the Gd with a closed pore tissue structure2O2S ceramic hollow microspheres.
Detailed Description
Preparation of Gd2O2The method for preparing the S ceramic hollow microsphere comprises the following steps:
step one, Gd2O2Preparation of S ceramic slurry
Preparation of premixed liquid
Selecting Gd with an average particle size of 1-2 mu m2O2S ceramic powder, preparing a premixed solution of slurry with the solid content of 75-85% by using a gel casting process, and dissolving the premixed solution in waterThe content of the additive accounts for 17.64-33.33% of the mass of the powder, and the additives added into the aqueous solution account for the mass of the powder in the following proportion: 0.50-2.12% of dispersing agent, 1.05-5.50% of monomer, 0.05-0.51% of cross-linking agent, 0.05-0.10% of blank reinforcing agent, 18.8-27.4% of closed-cell pore-forming agent and 0.9-2.0% of sintering aid, wherein a magnetic rotor or a mechanical stirring rod is used for stirring all the time in the process of preparing the premixed solution so as to uniformly mix all the additives in the aqueous solution;
the blank reinforcing agent is cotton fiber, the closed pore-forming agent is one or more of calcium sulfate, calcium hydroxide, calcium carbonate and aluminum sulfate, and the sintering aid is one or more of aluminum oxide, titanium oxide, zirconium oxide, boron oxide and bismuth oxide;
② ball milling
Gd is mixed with2O2Carrying out planetary ball milling on the S ceramic powder and the prepared premixed liquid together to prepare Gd with the solid content of 75-85%2O2S, sizing agent;
thirdly, adding curing agent
Gd after ball milling2O2Adding an initiator accounting for 0.06-0.30 per mill of the mass of the powder and a catalyst accounting for 0.12-0.34 per mill of the mass of the powder into the S slurry, and uniformly mixing for later use;
step two, manufacturing the semi-circular arc super-hydrophobic track
Manufacturing a semi-circular arc-shaped super-hydrophobic rail coated with a super-hydrophobic film, placing the rail on an inclined rack, enabling the inclination angle of the rail to be 25-35 degrees, and attaching the lower part of the inclined plane of the rail by using a heating belt;
step three, Gd2O2Titration forming of S microsphere blank
The selection specification is 24-28#The needle head of the glue dispenser enables the titration needle cylinder to be positioned 18-15 cm above the track, so that the situation that slurry is heated and solidified in advance and blocks a titration needle hole is avoided; gd is mixed with2O2S ceramic slurry is injected into a titration needle cylinder, the inclined plane is controlled to be heated to 150-210 ℃, the size of the ceramic slurry liquid drop is controlled through the air inlet pressure of compressed air and the size of a pinhole, the size of the liquid drop is 0.18-1 mm, the liquid drop drops on a metal track coated with a super-hydrophobic film from the top end of the inclined plane, rolls downwards and is heated and cured (an initiator)And a catalyst under the action of temperature to crosslink the monomer and the crosslinking agent) to Gd2O2S, preparing a microsphere blank; because of the function of the super-hydrophobic film layer, the liquid drops are kept to be ideal spherical liquid drops (the hydrophobic angle is more than 160 degrees);
step four, Gd2O2Preparation of S microsphere blank
Molding Gd2O2Drying the S ball blank at 100-150 ℃ for 10-20 h, degreasing at 600-700 ℃ for 15-25 h, sintering at 1470-1590 ℃ in reducing atmosphere or inert atmosphere, and keeping the temperature at the highest temperature for 3-8 h to obtain Gd2O2S ceramic hollow microspheres.
Further, the dispersant is ammonium polyacrylate or ammonium polycarboxylate.
Further, the monomer is acrylamide or methacrylamide.
Further, the cross-linking agent is N-N' methylene-bis-acrylamide.
Furthermore, a 20L ball milling tank is adopted for planetary ball milling, the selected ball milling tank is made of nylon or polyurethane, and zirconia balls are selected as ball milling media; the diameter of the selected grinding ball is 2-5 mm, and the material ball ratio ranges from 1:1 to 2: 1; the ball milling speed is 100-200 r/min, the ball milling time is 8-20 h, and the ball milled slurry rotates at the room temperature for 20s-1The viscosity value under the condition is 58 to 192 mPas.
Further, the initiator is ammonium persulfate.
Further, the catalyst is tetramethyl ethylenediamine.
Further, the semi-circular arc-shaped super-hydrophobic rail is manufactured by the following specific steps: carrying out sand blasting treatment on the inner surface of the semi-circular arc metal track, coating or depositing a layer of super-hydrophobic film on the inner surface of the track after alcohol scrubbing, wherein the thickness of the film is 10-25 mu m, the super-hydrophobic film is also added with a binder with the mass fraction of 0-5% for firmly adhering the super-hydrophobic coating to the surface of the metal substrate, and a heating tape is attached to the semi-circular arc bottom surface of the track or is wound on the whole semi-circular arc track in a manner of being vertical to the axial direction.
Furthermore, the radius of the semicircular arc-shaped metal track is 50-100 mm, the thickness is 1-3 mm, the length is 10-20 m, the cross section of the semicircular metal track is semicircular, the opening of the semicircular metal track is upward, and the metal track is made of copper, aluminum or stainless steel.
Furthermore, the adhesive is protein glue, resin glue and chlorinated rubber.
The technical solutions in the embodiments of the present invention are clearly and completely described below.
Example 1:
preparation of Gd2O2Method for preparing S ceramic hollow microsphere
Taking Gd with the average particle size of 1 mu m2O21000g of S powder, and weighing quantitative water according to the target solid content of 85% to prepare a premixed solution. Acrylamide accounting for 2.80 percent of the powder, N-N' methylene bisacrylamide accounting for 0.43 percent of the powder, ammonium polycarboxylate accounting for 1.6 percent of the powder, cotton fiber reinforcing agent accounting for 0.5 percent of the powder, calcium sulfate pore-forming agent accounting for 20 percent of the powder and bismuth oxide sintering aid accounting for 1.6 percent of the powder are added into water, and the mixture is continuously stirred for 20min to prepare the premixed solution containing the pore-forming agent and the sintering aid. Gd is mixed with2O2Adding the S powder and the premixed solution into a 20L planetary ball milling tank, wherein the ball milling tank is a polyurethane tank, and the ball milling medium is ZrO with the diameter of 5mm2The material-to-ball ratio (mass ratio) of the balls is 2: 1. The ball milling speed is set to 200r/min, the slurry has good fluidity after 15h ball milling, and the viscosity value is measured to be 121 mPa.s (room temperature, 20s of rotation speed)-1). Adding ammonium persulfate accounting for 0.25 per mill of the powder and tetramethylethylenediamine accounting for 0.15 per mill of the powder into the slurry after ball milling, and stirring for 10min by using a mechanical rod to obtain Gd suitable for titration2O2And (S) slurry.
Injecting the slurry into a charging barrel in a self-made titration forming device, and selecting 26#The dispensing syringe is used for adjusting the air pressure of compressed air to keep the diameter of the liquid drop to be about 0.37 mm. Adding 1.5% of protein adhesive into the super-hydrophobic coating, coating the mixture on the surface of a sandblasted aluminum semi-circular arc track, heating the track panel with the hydrophobic film layer to about 200 ℃, keeping the temperature, and Gd2O2S liquid drops are continuously titrated from the upper end of the track and roll down to a collecting tank at the lowest position to obtain solidified Gd with the diameter of 0.18-0.35 mm2O2And (4) preparing an S microsphere ball blank.
Gd after molding2O2Drying S microsphere blank at 150 deg.C for 10h, degreasing at 700 deg.C for 25h, and maintaining at 1500 deg.C for 7h to obtain product with diameter of 0.15-0.30 mm and density of 1.33g/cm3Gd of (2)2O2S ceramic hollow microspheres.
While there have been shown and described what are at present considered the fundamental principles of the invention, its essential features and advantages, it will be understood by those skilled in the art that the invention is not limited by the embodiments described above, which are merely illustrative of the principles of the invention, but various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (10)
1. A method for preparing gadolinium oxysulfide ceramic hollow microspheres is characterized by comprising the following steps: the method comprises the following steps:
step one, Gd2O2Preparation of S ceramic slurry
Preparation of premix
Selecting Gd with an average particle size of 1-2 mu m2O2S ceramic powder, preparing a premixed liquid of slurry with the solid content of 75-85% by using a gel casting process, wherein the premixed liquid comprises a water solvent and additives, the content of the water solvent accounts for 17.64-33.33% of the mass of the powder, and the additives added into the water solvent account for the mass of the powder in a proportion that: 0.50-2.12% of dispersing agent, 1.05-5.50% of monomer, 0.05-0.51% of cross-linking agent, 0.05-0.10% of blank reinforcing agent, 18.8-27.4% of closed-cell pore-forming agent and 0.9-2.0% of sintering aid, wherein a magnetic rotor or a mechanical stirring rod is used for stirring all the time in the process of preparing the premixed solution so as to uniformly mix all the additives in the aqueous solvent;
the blank reinforcing agent is cotton fibers, the closed pore-forming agent is one or more of calcium sulfate, calcium hydroxide, calcium carbonate and aluminum sulfate, and the sintering aid is one or more of aluminum oxide, titanium oxide, zirconium oxide, boron oxide and bismuth oxide;
② ball milling
Gd is added2O2Carrying out planetary ball milling on the S ceramic powder and the prepared premixed liquid together to prepare Gd with the solid content of 75-85 percent2O2S sizing agent;
thirdly, adding curing agent
Gd after ball milling2O2Adding an initiator accounting for 0.06-0.30 per mill of the mass of the powder and a catalyst accounting for 0.12-0.34 per mill of the mass of the powder into the S slurry, and uniformly mixing for later use;
step two, manufacturing the semi-circular arc super-hydrophobic track
Manufacturing a semi-circular arc-shaped super-hydrophobic rail coated with a super-hydrophobic film, placing the rail on an inclined rack, enabling the inclination angle of the rail to be 25-35 degrees, and attaching the lower part of the inclined plane of the rail by using a heating belt;
step three, Gd2O2Titration forming of S microsphere blank
The selection specification is 24-28#The needle head of the dispenser is positioned 18-15 cm above the track, and Gd is added2O2S ceramic slurry is injected into a titration needle cylinder, the inclined plane is controlled to be heated to 150-210 ℃, the size of ceramic slurry liquid drops is controlled through the air inlet pressure of compressed air and the size of a pinhole, the size of the liquid drops is 0.18-1 mm, the liquid drops drop on a metal track coated with a super-hydrophobic film from the top end of the inclined plane, roll downwards and are heated and cured into Gd2O2S, preparing a microsphere blank;
step four, Gd2O2Preparation of S microsphere blank
Molding Gd2O2Drying the S ball blank at 100-150 ℃ for 10-20 h, degreasing at 600-700 ℃ for 15-25 h, sintering at 1470-1590 ℃ in reducing atmosphere or inert atmosphere, and keeping the temperature at the highest temperature for 3-8 h to obtain Gd2O2S ceramic hollow microspheres.
2. The method for preparing gadolinium oxysulfide ceramic hollow microspheres according to claim 1, characterized in that: the dispersant is ammonium polyacrylate or ammonium polycarboxylate.
3. The method for preparing gadolinium oxysulfide ceramic hollow microspheres according to claim 1, characterized in that: the monomer is acrylamide or methacrylamide.
4. The method for preparing gadolinium oxysulfide ceramic hollow microspheres according to claim 1, characterized in that: the cross-linking agent is N-N' methylene bisacrylamide.
5. The method for preparing gadolinium oxysulfide ceramic hollow microspheres according to claim 1, characterized in that: the planetary ball milling adopts a 20L ball milling tank, the selected ball milling tank is made of nylon or polyurethane, and a ball milling medium is selected as zirconia balls; the diameter of the selected grinding ball is 2-5 mm, and the material ball ratio ranges from 1:1 to 2: 1; the ball milling speed is 100-200 r/min, the ball milling time is 8-20 h, and the ball milled slurry rotates at the room temperature for 20s-1The viscosity value under the condition is 58-192 mPas.
6. The method for preparing gadolinium oxysulfide ceramic hollow microspheres according to claim 1, characterized in that: the initiator is ammonium persulfate.
7. The method for preparing gadolinium oxysulfide ceramic hollow microspheres according to claim 1, characterized in that: the catalyst is tetramethyl ethylenediamine.
8. The method for preparing gadolinium oxysulfide ceramic hollow microspheres according to claim 1, characterized in that: the method comprises the following specific steps of: carrying out sand blasting treatment on the inner surface of the semi-circular arc metal track, coating or depositing a layer of super-hydrophobic film on the inner surface of the track after alcohol scrubbing, wherein the thickness of the film is 10-25 mu m, the super-hydrophobic film is also added with a binder with the mass fraction of 0-5% for firmly adhering the super-hydrophobic coating to the surface of the metal substrate, and a heating tape is attached to the semi-circular arc bottom surface of the track or is wound on the whole semi-circular arc track in a manner of being vertical to the axial direction.
9. The method for preparing gadolinium oxysulfide ceramic hollow microspheres according to claim 8, wherein: the semi-circular arc-shaped metal track has the radius of 50-100 mm, the thickness of 1-3 mm, the length of 10-20 m, the cross section of the semi-circular arc-shaped metal track is semi-circular, the opening of the semi-circular arc-shaped metal track is upward, and the metal track is made of copper, aluminum or stainless steel.
10. The method for preparing gadolinium oxysulfide ceramic hollow microspheres according to claim 8, wherein: the binder is protein glue, resin glue or chlorinated rubber.
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