CN115124248A - Glass powder and preparation method thereof - Google Patents
Glass powder and preparation method thereof Download PDFInfo
- Publication number
- CN115124248A CN115124248A CN202210726797.8A CN202210726797A CN115124248A CN 115124248 A CN115124248 A CN 115124248A CN 202210726797 A CN202210726797 A CN 202210726797A CN 115124248 A CN115124248 A CN 115124248A
- Authority
- CN
- China
- Prior art keywords
- powder
- source compound
- glass
- electron beam
- barium
- 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
- 239000011521 glass Substances 0.000 title claims abstract description 108
- 239000000843 powder Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 55
- 230000008018 melting Effects 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 41
- 238000010894 electron beam technology Methods 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000227 grinding Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010791 quenching Methods 0.000 claims abstract description 14
- 230000000171 quenching effect Effects 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 229910052788 barium Inorganic materials 0.000 claims abstract description 11
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 10
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 239000012768 molten material Substances 0.000 claims abstract description 9
- 239000012634 fragment Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 5
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical group C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 claims description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229940118662 aluminum carbonate Drugs 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 9
- 238000001035 drying Methods 0.000 description 18
- 239000002245 particle Substances 0.000 description 13
- 238000012216 screening Methods 0.000 description 12
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 8
- 238000000635 electron micrograph Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000005337 ground glass Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910003439 heavy metal oxide Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000002444 silanisation Methods 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 125000002362 bornane-2,3-dione group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000004851 dental resin Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011326 mechanical measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000020610 powder formula Nutrition 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- 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
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/02—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Abstract
The invention provides glass powder and a preparation method thereof, and the glass powder comprises the following steps: weighing raw materials, and grinding the raw materials; laying the ground raw material powder on a substrate to obtain a powder layer; under the protection of inert gas, scanning the powder layer by using an electron beam, and irradiating and melting the powder layer by using the electron beam to obtain a molten material, wherein the irradiation density of the electron beam is 4000-6000 kW/m 2 (ii) a Adding the molten state material into water for water quenching to obtain glass fragments, and grinding the glass fragments to obtain the glass powder; wherein, the raw material comprises a first component, silicon dioxide and a boron source compound; the first component is selected from one or more than two of barium source compound, strontium source compound and zirconium source compound. The glass powder provided by the invention is prepared by electron beam melting, and the specific surface area of the formed glass powderUp to 18m 2 More than g, the light transmittance is more than 60 percent, and the flexural strength is more than 80 Mpa.
Description
Technical Field
The invention belongs to the technical field of glass powder, and particularly relates to glass powder and a preparation method thereof.
Background
The fillers of the prior composite resin for dental resin mainly comprise quartz powder, barium powder, strontium powder, zirconium glass powder and ceramic powder, and the fillers have the advantages that the fillers are doped into the resin, and the resin has excellent optical characteristics and X-ray radiation resistance after polymerization. The barium, strontium and zirconium glass powder is added with heavy metal components, and is premixed and heated at high temperature for a long time to ensure uniform mixing in the process of firing the glass, and finally is ground step by step and sieved to prepare powder, wherein the particle size of the final finished product is usually smaller than 0.4-2 mu m.
The heavy metal oxide adopted by the glass powder formula is BaO, ZrO2, SrO2 and the like, the addition content of the heavy metal oxide is 10% -50%, the light transmittance of the glass is increased, the radiation resistance of the glass is increased, the content of aluminum oxide is 10% -50%, the heavy metal oxide is used for building a basic frame of the glass powder, the content of silicon oxide is 10% -50%, the boron content is 10% -30%, the glass powder has a dissolving assisting effect, the melting temperature of the glass can be effectively reduced, and other components are 1% -5%.
The traditional preparation process of the glass powder comprises the following steps:
(1) material preparation and mixing: the components are proportioned according to weight percentage, and the materials are uniformly mixed by adopting general stirring, dry method or wet method.
(2) Melting-water quenching: melting at 1500-1700 deg.C for 4-8hr, wherein the melt is clarified and homogenized at a temperature determined by actual conditions; after the glass melt is formed, the homogenization time is kept for more than 1hr, and the excessive homogenization time can cause the volatilization of glass components to a certain degree; and (3) water quenching after melting: and quenching the obtained melt in deionized water to obtain the glass melt block.
(3) Refining and screening: and drying the obtained glass frit material, drying the glass frit material after dry grinding or wet grinding, screening and sorting the obtained glass powder material, wet grinding the glass powder material in a ball mill, and screening the glass powder material by using a vibrating screening machine.
(4) Silanization treatment: and performing silanization treatment on the obtained glass powder under high-speed mixing equipment.
However, the conventional preparation process has the following disadvantages:
(1) the melting temperature is higher, the general melting temperature of the glass powder containing barium, strontium and zirconium is higher, above 1600 ℃, a special high-temperature melting furnace is needed during processing, and if certain fluidity is needed, the temperature of the melting furnace can be further improved;
(2) the yield is low, the continuous production is difficult, and the investment and the process operation difficulty of the continuous production are high due to the high melting temperature, the requirement of a platinum crucible and the requirement of special equipment and tools; moreover, high temperatures result in volatile loss of B2O3 from the composition, affect batch consistency in product performance, and poor glass flow, thus often requiring the use of expensive platinum crucibles for melting.
(3) The uniformity is difficult to ensure, the fluidity of the material melt in the smelting process is very poor, long-time reaction is needed, the temperature is high, the boron volatilization is serious, the system compatibility is very poor, and long time is needed for the fusion of the metal oxide and the glass system.
Disclosure of Invention
The invention aims to provide glass powder based on an electron beam melting technology and a preparation method thereof, so that the defects of high melting point, high cost and difficulty in continuous production of glass prepared by a high-temperature melting method are overcome, and barium, strontium and zirconium glass powder can be rapidly prepared in batches.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of glass powder comprises the following steps:
weighing raw materials, and grinding the raw materials;
laying the ground raw material powder on a substrate to obtain a powder layer;
under the protection of inert gas, scanning the powder layer by using an electron beam, and irradiating and melting the powder layer by using the electron beam to obtain a molten material; the irradiation density of the electron beam is 4000-6000 kW/m 2 ；
Adding the molten state material into water for water quenching to obtain a glass fragment, and grinding the glass fragment to obtain the glass powder;
wherein, the raw material comprises a first component, silicon dioxide and a boron source compound; the first component is selected from one or more than two of barium source compound, strontium source compound and zirconium source compound.
The process of electron beam melting is characterized in that melting is carried out in a high vacuum environment (the melting vacuum degree is generally 10) -3 To 10Pa), the temperature of a molten pool and the distribution thereof are controllable during smelting, the maintaining time of the molten pool can be adjusted in a large range, and the smelting is carried out in a crucible. It can be said that electron beam melting provides an indispensable tool for the production of high melting point glasses.
There are 3 basic processes for electron beam melting: (1) and vacuumizing, namely vacuumizing the material and the cavity. The resistance of an electron injection path is reduced, and the electron beam can act on the surface of the material to the maximum extent; (2) electron beam injection and acceleration. The electron beam is ejected through the electron gun, the initial speed of the electron gun reaches the maximum along with the voltage rise of the electron gun, in addition, a magnetic field is applied to the ejected electrons in the ejection process to ensure that the ejected electrons are ejected to the surface (3) of the material with the maximum precision to move the material, so that the electron beam can be uniformly ejected to the surface of the material, and the material is rotated to ensure that each area can be uniformly heated and melted.
The invention discovers that 4000-6000 kW/m is adopted to prepare the glass powder by the electron beam melting technology 2 The electron beam irradiation density of (2) is improved greatly, so that the specific surface area, the transmittance and the flexural strength of the obtained glass powder are all improved greatly.
Preferably, in the above method for preparing glass frit, the thickness of the powder layer is 0.5-3 mm.
Preferably, in the above method for preparing glass frit, the melting rate of the powder layer is 50 to 1000g/hr, and more preferably 250 to 350 g/hr.
In the electron beam melting technology, the melting power, the melting speed and the material thickness are the most important factors influencing melting, and certain restriction relationship exists among the factors, so that comprehensive consideration is required. The invention discovers that the glass powder obtained by adopting the combination of the electron beam irradiation density, the powder layer thickness and the melting speed has better effects on the specific surface area, the transmittance and the flexural strength.
Preferably, in the above method for producing glass frit, when the powder layer is melted by irradiation with an electron beam, a voltage of an electron gun emitting the electron beam is 50 to 300 kV.
Preferably, in the above method for producing a glass frit, the raw materials comprise, by mass: 5-60% of a first component, 5-60% of silicon dioxide and 1-25% of a boron source compound.
Further preferably, the feedstock comprises, by mass: 20-40% of the first component, 20-40% of silicon dioxide and 5-15% of a boron source compound. When the first component, the silicon dioxide and the boron source compound in the proportion are compounded to be used as main raw materials, the obtained glass powder has better specific surface area, transmittance and flexural strength.
Preferably, in the above method for preparing glass frit, the raw materials further include, by mass: 5-60% of an aluminum source compound, wherein the aluminum source compound is one or more than two of aluminum oxide, aluminum hydroxide, aluminum carbonate and aluminum nitrate; more preferably, the content of the aluminum source compound is 20 to 40%, and the transmittance can be improved by adding the aluminum source compound in the above proportion.
Preferably, in the above method for preparing glass frit, the raw materials further include, by mass: 0.1-6% of a second component, wherein the second component is arsenic trioxide and/or antimony oxide, preferably, the content of the second component is 0.5-5%, and the light transmittance can be improved and bubbles can be reduced by adding the second component according to the proportion.
Preferably, in the above method for preparing glass frit, the barium source compound is one or more selected from barium carbonate, barium sulfate, barium hydroxide, barium oxide, and barium nitrate;
and/or the strontium source compound is selected from one or more of strontium carbonate, strontium sulfate, strontium hydroxide, strontium oxide and strontium nitrate;
and/or the zirconium source compound is selected from one or more of zirconium nitrate, zirconium oxide, zirconium carbonate and zirconium hydroxide;
and/or the boron source compound is one or more than two of boric acid, borax, boron oxide and sodium borohydride.
Preferably, in the preparation method of the glass powder, the raw material powder is dried at 100-200 ℃ for 3-5 hours before powder spreading.
Preferably, in the above method for producing glass frit, the particle size of the ground raw material powder is 0.1 to 2 μm.
The invention also provides glass powder prepared by the preparation method.
The invention has the following advantages:
the glass powder provided by the invention is prepared by electron beam melting, and the specific surface area of the formed glass powder reaches 18m 2 More than g, the light transmittance is more than 60 percent, and the flexural strength is more than 80 Mpa.
Drawings
FIG. 1 is an electron micrograph of the raw material powder of example 1 before it is melted.
FIG. 2 is an electron micrograph of the raw material powder of example 1 after electron beam melting.
FIG. 3 is an electron micrograph of the raw material powder of example 2 before it is melted.
FIG. 4 is an electron micrograph of the raw material powder of example 2 after electron beam melting.
Detailed Description
The following examples are provided to illustrate the present invention, but are not intended to limit the scope of the present invention.
Example 1
Preparing materials: 33% of barium carbonate, 30% of silicon dioxide, 20% of aluminum oxide, 10% of boric acid, 5% of sodium hydroxide and 2% of cosolvent;
grinding: grinding the above materials with ball mill at 2000rpm for 4hr to obtain powder with particle diameter of 0.1-2 μm;
drying: drying the above materials in oven for 10 hr;
melting: injecting the above materials into an electron beam melting furnace, melting for 4 times, putting into four crucibles each time, the total mass is 1kg, the thickness of the materials is 1mm, and the electron beam density of the melting furnace is 5000kW/m 2 Melting for 4 hr;
water quenching: putting the molten material into cold water for water quenching to obtain glass;
coarse grinding of glass: putting the obtained glass into a jaw crusher to prepare glass powder with the particle size of 10-500 mu m;
finely grinding glass powder: putting the obtained coarse ground glass powder into a vibration mill to prepare glass powder with the grain diameter of 0.4-2 mu m;
drying: drying the obtained sand-milled material in an oven for 10 hr;
surface treatment: carrying out surface treatment on the obtained glass powder by using a silane coupling agent under high-speed dispersion;
screening: and screening the treated glass powder to obtain the barium glass powder.
FIG. 1 is an electron micrograph of the raw material powder of example 1 before it is melted. FIG. 2 is an electron micrograph of the raw material powder of example 1 after electron beam melting. By comparison, it can be understood that under the above electron beam melting conditions, the raw material powder becomes a molten material.
Example 2
Preparing materials: 35% of strontium carbonate, 30% of silicon dioxide, 20% of aluminum oxide and 15% of borax;
grinding: grinding the above materials with ball mill at 2000rpm for 4hr to obtain powder with particle diameter of 0.1-2 μm;
drying: drying the above materials in oven for 10 hr;
melting: injecting the above materials into an electron beam melting furnace, adding into eight crucibles at two times, the total mass is 2kg, the thickness of the materials is 1mm, the electron beam density of the melting furnace is 5000kW/m2, and the melting time is 6 hr;
water quenching: putting the molten material into cold water for water quenching to obtain glass;
coarse grinding of glass: putting the obtained glass into a jaw crusher to prepare glass with the particle size of 10-500 mu m;
finely grinding glass powder: putting the obtained coarse ground glass powder into a vibration mill to prepare glass powder with the grain diameter of 0.4-2 mu m;
drying: drying the obtained sand-milled material in an oven for 10 hr;
surface treatment: carrying out surface treatment on the obtained glass powder by using a silane coupling agent under high-speed dispersion;
screening: and screening the treated glass powder to obtain the strontium glass powder.
FIG. 3 is an electron micrograph of the raw material powder before it is melted. FIG. 4 is an electron microscope image of the raw material powder after electron beam melting. By comparison, it can be understood that under the above electron beam melting conditions, the raw material powder becomes a molten material.
Example 3
Preparing materials: 35% of zirconium nitrate, 40% of silicon dioxide and 25% of borax;
grinding: grinding the above materials with ball mill at 2000rpm for 4hr to obtain powder with particle diameter of 0.1-2 μm;
and (3) drying: drying the above materials in oven for 10 hr;
melting: injecting the above materials into an electron beam melting furnace, adding into eight crucibles at two times, the total mass is 2kg, the thickness of the materials is 2mm, the electron beam density of the melting furnace is 5000kW/m2, and the melting time is 8 hr;
water quenching: putting the molten material into cold water for water quenching to obtain glass;
coarse grinding of glass: putting the obtained glass into a jaw crusher to prepare glass powder with the particle size of 10-500 mu m;
finely grinding glass powder: putting the obtained coarse ground glass powder into a vibration mill to prepare glass powder with the grain diameter of 0.4-2 mu m;
drying: drying the obtained sand-milled material in an oven for 10 hr;
surface treatment: carrying out surface treatment on the obtained glass powder by using a silane coupling agent under high-speed dispersion;
screening: and screening the treated glass powder to obtain the zirconium glass powder.
Comparative example 1
Compared with example 1, the difference is that high-temperature melting is adopted instead of electron beam melting.
Preparing materials: 33% of barium carbonate, 30% of silicon dioxide, 20% of aluminum oxide, 10% of boric acid, 5% of sodium hydroxide and 2% of cosolvent;
grinding: grinding the above materials with ball mill at 2000rpm for 4hr to obtain powder with particle diameter of 0.1-2 μm;
drying: drying the above materials in oven for 10 hr;
melting: injecting the above materials into a glass melting furnace, melting for 15hr at 1700-;
water quenching: putting the molten material into cold water for water quenching to obtain glass;
coarse grinding of glass: putting the obtained glass into a jaw crusher to prepare glass with the particle size of 10-500 mu m;
finely grinding glass powder: putting the obtained coarse ground glass powder into a vibration mill to prepare glass powder with the grain diameter of 0.4-2 mu m;
drying: drying the obtained sand-milled material in an oven for 10 hr;
surface treatment: carrying out surface treatment on the obtained glass powder by using a silane coupling agent under high-speed dispersion;
screening: and screening the treated glass powder to obtain the barium glass powder.
Test examples
1. Measuring the particle size by using a laser particle size instrument;
2. carrying out specific surface area test on the particle surface by using a BET specific surface area test method;
3. mixing the obtained glass powder with light-cured resin (the mixing ratio of the resin to the glass powder is 7: 3), and measuring the transmittance of a cured resin sample by using an ultraviolet spectrophotometer; the light-cured resin is a resin monomer BisGMA, and the photoinitiator is camphorquinone;
4. and mixing the obtained glass powder with the light-cured resin, and performing mechanical measurement on a cured resin sample by using a mechanical testing machine.
TABLE 1
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. The preparation method of the glass powder is characterized by comprising the following steps:
weighing raw materials, and grinding the raw materials;
laying the ground raw material powder on a substrate to obtain a powder layer;
under the protection of inert gas, scanning the powder layer by using an electron beam, and irradiating and melting the powder layer by using the electron beam to obtain a molten material; the irradiation density of the electron beam is 4000-6000 kW/m 2 ；
Adding the molten state material into water for water quenching to obtain a glass fragment, and grinding the glass fragment to obtain the glass powder;
wherein, the raw material comprises a first component, silicon dioxide and a boron source compound; the first component is selected from one or more than two of barium source compound, strontium source compound and zirconium source compound.
2. The method for producing glass frit according to claim 1, wherein the thickness of the powder layer is 0.5 to 3 mm.
3. The method for producing glass frit according to claim 1 or 2, wherein the melting rate of the powder layer is 50 to 1000g/hr, preferably 250 to 350 g/hr.
4. The method for producing glass frit according to claims 1 to 3, wherein the raw materials comprise, based on the total mass: 5-60% of a first component, 5-60% of silicon dioxide and 1-25% of a boron source compound.
5. The method for producing glass frit according to claim 4, wherein the raw materials comprise, by mass: 20-40% of the first component, 20-40% of silicon dioxide and 5-15% of a boron source compound.
6. The method for producing glass frit according to any one of claims 1 to 5, wherein the raw materials further comprise, in terms of total mass: 5-60% of an aluminum source compound, wherein the aluminum source compound is one or more than two of aluminum oxide, aluminum hydroxide, aluminum carbonate and aluminum nitrate, and preferably, the content of the aluminum source compound is 20-40%.
7. The method for producing glass frit according to any one of claims 1 to 6, wherein the raw materials further comprise, based on the total mass: 0.1-6% of a second component, wherein the second component is arsenic trioxide and/or antimony oxide, and preferably, the content of the second component is 0.5-5%.
8. The method for producing glass frit according to any one of claims 1 to 7, wherein the barium source compound is one or more selected from barium carbonate, barium sulfate, barium hydroxide, barium oxide, and barium nitrate;
and/or the strontium source compound is selected from one or more of strontium carbonate, strontium sulfate, strontium hydroxide, strontium oxide and strontium nitrate;
and/or the zirconium source compound is selected from one or more of zirconium nitrate, zirconium oxide, zirconium carbonate and zirconium hydroxide;
and/or the boron source compound is one or more than two of boric acid, borax, boron oxide and sodium borohydride.
9. The method for preparing glass powder according to any one of claims 1 to 8, wherein the raw material powder is dried at 100 to 200 ℃ for 3 to 5 hours before powder spreading.
10. A glass frit produced by the production method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210726797.8A CN115124248A (en) | 2022-06-23 | 2022-06-23 | Glass powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210726797.8A CN115124248A (en) | 2022-06-23 | 2022-06-23 | Glass powder and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115124248A true CN115124248A (en) | 2022-09-30 |
Family
ID=83380573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210726797.8A Pending CN115124248A (en) | 2022-06-23 | 2022-06-23 | Glass powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115124248A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115636590A (en) * | 2022-10-08 | 2023-01-24 | 中建材玻璃新材料研究院集团有限公司 | Antibacterial glass powder, preparation method thereof and plastic antibacterial material |
| CN116177886A (en) * | 2023-02-23 | 2023-05-30 | 日鸿半导体材料（南通）有限公司 | Glass powder with high light transmittance and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1208091A (en) * | 1968-01-23 | 1970-10-07 | Zeiss Stiftung | Improvements in or relating to glass |
| JPH11314937A (en) * | 1997-11-27 | 1999-11-16 | Toray Ind Inc | Inorganic fine powder, photosensitive paste, member of display panel and its production |
| CN101684033A (en) * | 2008-09-28 | 2010-03-31 | 四川虹欧显示器件有限公司 | Medium glass powder for plasma display panel and preparation method thereof |
| CN102574204A (en) * | 2009-08-10 | 2012-07-11 | Bego布雷默戈尔德施雷格爱威尔海姆.赫伯斯特两合公司 | Ceramic or glass-ceramic article and methods for producing such article |
| WO2018162261A1 (en) * | 2017-03-10 | 2018-09-13 | Pro-Beam Ag & Co. Kgaa | Electron beam installation and method for working powdered material |
| CN108650883A (en) * | 2016-01-15 | 2018-10-12 | 贺利氏添加剂生产有限公司 | By the method for glassy metal increasing material manufacturing three-dimension object |
| CN114367669A (en) * | 2021-12-15 | 2022-04-19 | 重庆材料研究院有限公司 | Preparation method of TaW10 alloy spherical powder for 3D printing |
| CN114404303A (en) * | 2021-12-30 | 2022-04-29 | 辽宁爱尔创生物材料有限公司 | Fluorescent glass inorganic filler and preparation method and application thereof |
-
2022
- 2022-06-23 CN CN202210726797.8A patent/CN115124248A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1208091A (en) * | 1968-01-23 | 1970-10-07 | Zeiss Stiftung | Improvements in or relating to glass |
| JPH11314937A (en) * | 1997-11-27 | 1999-11-16 | Toray Ind Inc | Inorganic fine powder, photosensitive paste, member of display panel and its production |
| CN101684033A (en) * | 2008-09-28 | 2010-03-31 | 四川虹欧显示器件有限公司 | Medium glass powder for plasma display panel and preparation method thereof |
| CN102574204A (en) * | 2009-08-10 | 2012-07-11 | Bego布雷默戈尔德施雷格爱威尔海姆.赫伯斯特两合公司 | Ceramic or glass-ceramic article and methods for producing such article |
| CN108650883A (en) * | 2016-01-15 | 2018-10-12 | 贺利氏添加剂生产有限公司 | By the method for glassy metal increasing material manufacturing three-dimension object |
| WO2018162261A1 (en) * | 2017-03-10 | 2018-09-13 | Pro-Beam Ag & Co. Kgaa | Electron beam installation and method for working powdered material |
| CN114367669A (en) * | 2021-12-15 | 2022-04-19 | 重庆材料研究院有限公司 | Preparation method of TaW10 alloy spherical powder for 3D printing |
| CN114404303A (en) * | 2021-12-30 | 2022-04-29 | 辽宁爱尔创生物材料有限公司 | Fluorescent glass inorganic filler and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115636590A (en) * | 2022-10-08 | 2023-01-24 | 中建材玻璃新材料研究院集团有限公司 | Antibacterial glass powder, preparation method thereof and plastic antibacterial material |
| CN115636590B (en) * | 2022-10-08 | 2024-03-12 | 中建材玻璃新材料研究院集团有限公司 | Antibacterial glass powder, preparation method thereof and plastic antibacterial material |
| CN116177886A (en) * | 2023-02-23 | 2023-05-30 | 日鸿半导体材料（南通）有限公司 | Glass powder with high light transmittance and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115124248A (en) | Glass powder and preparation method thereof | |
| KR102551614B1 (en) | Glass composition, glass with low inclusion content, manufacturing method thereof and application thereof | |
| US7687418B2 (en) | X-ray opaque glass, method for the production and use thereof | |
| WO2004109816A2 (en) | Encapsulant for opto-electronic devices and method for making it | |
| WO2018008379A1 (en) | Composite ceramic powder, sealing material, and composite ceramic powder production method | |
| CN112250303A (en) | High-strength radiation-proof glass and preparation method and application thereof | |
| KR20080085070A (en) | Bismuth-based sealing material and bismuth-based paste material | |
| CN114105525B (en) | Flame-retardant glass fiber composite material and preparation method thereof | |
| WO2017183490A1 (en) | Ceramic powder, composite powder material, and sealing material | |
| CN112250298B (en) | Radiation-proof glass and preparation method and application thereof | |
| CN113233761B (en) | Glass capable of improving thermal shock resistance and preparation method thereof | |
| KR101162040B1 (en) | Glass composition for sealing of and display panel comprising the same | |
| CN113149429B (en) | High borosilicate glass containing metal nanoparticles and preparation method thereof | |
| DE112018007251T5 (en) | Opaque quartz glass and process for its manufacture | |
| KR101900674B1 (en) | Ceramic long fiber and ceramic short fiber using slag, base material for the same, insulation using the same, and method of fabricating of the same | |
| TWI751146B (en) | Manufacturing method of ceramic powder | |
| CN111087173A (en) | Negative expansion filler and preparation method and application thereof | |
| JP3418640B2 (en) | Method for producing doped quartz glass | |
| JP2019202902A (en) | Glass, glass filler, and resin mixture | |
| CN114180832B (en) | Ultraviolet radiation resistant intermediate wave transparent infrared glass and preparation method and application thereof | |
| KR101964114B1 (en) | Ceramic fiber using slag and rock method of fabricating of the same | |
| Ding et al. | Preparation, structures, thermal properties and sintering behaviors of B2O3-SiO2-ZnO-BaO-Al2O3 glass | |
| CN1036645C (en) | Optical glass mixing with base-ball moleculae and its preparation method | |
| CN114196234B (en) | Soft silicon micro powder and preparation method thereof | |
| JP2017197426A (en) | Composite powder material |
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 |