CN117303733A - Borosilicate glass and preparation method thereof - Google Patents
Borosilicate glass and preparation method thereof Download PDFInfo
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- CN117303733A CN117303733A CN202311252249.7A CN202311252249A CN117303733A CN 117303733 A CN117303733 A CN 117303733A CN 202311252249 A CN202311252249 A CN 202311252249A CN 117303733 A CN117303733 A CN 117303733A
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- 239000005388 borosilicate glass Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 96
- 239000002245 particle Substances 0.000 claims abstract description 71
- 239000000843 powder Substances 0.000 claims abstract description 49
- 238000002844 melting Methods 0.000 claims abstract description 43
- 230000008018 melting Effects 0.000 claims abstract description 43
- 238000000137 annealing Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000007731 hot pressing Methods 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 8
- 239000008395 clarifying agent Substances 0.000 claims description 7
- 238000004448 titration Methods 0.000 claims description 7
- 238000005352 clarification Methods 0.000 claims description 5
- 235000019402 calcium peroxide Nutrition 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 description 19
- 239000011734 sodium Substances 0.000 description 19
- 230000002829 reductive effect Effects 0.000 description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 229910052796 boron Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000012778 molding material Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 229910021538 borax Inorganic materials 0.000 description 6
- 235000010339 sodium tetraborate Nutrition 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010309 melting process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 239000004328 sodium tetraborate Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000006028 limestone Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000006025 fining agent Substances 0.000 description 3
- 239000006066 glass batch Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- WKIXHBICUJIWNP-UHFFFAOYSA-K calcium;sodium;chloride;sulfate Chemical compound [Na+].[Cl-].[Ca+2].[O-]S([O-])(=O)=O WKIXHBICUJIWNP-UHFFFAOYSA-K 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 210000001808 exosome Anatomy 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- GJJSDZSDOYNJSW-UHFFFAOYSA-N lanthanum(3+);borate Chemical compound [La+3].[O-]B([O-])[O-] GJJSDZSDOYNJSW-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- -1 sodium fluorosilicate Chemical compound 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- ZCXUWYGUGJQPPR-UHFFFAOYSA-N trisodium;borate;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[Na+].[O-]B([O-])[O-] ZCXUWYGUGJQPPR-UHFFFAOYSA-N 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to borosilicate glass and a preparation method thereof. The preparation method of borosilicate glass comprises the following steps: according to the composition requirement of borosilicate glass, siO-containing glass is provided 2 Source and B 2 O 3 A first batch of sources; adding glass powder into the first batch to prepare a second batch, wherein the mass fraction of the glass powder in the second batch is 4% -40%, and the particle size of the glass powder is less than or equal to 75 mu m; and melting, clarifying and annealing the second batch to prepare borosilicate glass. The preparation method has the advantages that when the second batch is melted, the glass powder has low softening temperature and small particle size, is easy to be quickly softened into a liquid phase with certain adhesiveness, and forms a protective layer for wrapping the first batch, so that volatile components in the first batch can be adsorbed and melted in the protective layer, thereby reducing B from the root 2 O 3 The purpose of the volatilization rate.
Description
Technical Field
The invention relates to the technical field of glass, in particular to borosilicate glass and a preparation method thereof.
Background
SiO in borosilicate glass compared to ordinary glass 2 And B is connected with 2 O 3 The glass has the advantages of higher content, lower thermal expansion coefficient, higher thermal shock resistance and higher surface hardness, and better performances in the aspects of thermal stability, chemical stability, optical performance, mechanical performance, processability and the like, and can be applied to the fields of building fireproof glass, instrument glass, medicinal glass, display panel glass, solar vacuum heat collecting tube glass, electronic equipment substrate glass and the like.
B 2 O 3 Is a key component in borosilicate glass, can improve a series of properties of the glass, and has good fluxing property. But during the melting of the glass, B 2 O 3 Is easily volatilized, and causes denaturation and deterioration of molten glass, so that the actual components of borosilicate glass are greatly different from the target components. B (B) 2 O 3 The volatilization of the catalyst not only consumes a large amount of raw materials and reduces the quality of products, but also has great aggressiveness to the kiln and seriously shortens the service life of the kiln.
Disclosure of Invention
Based on the above, it is necessary to provide borosilicate glass and preparation method thereof to overcome B in glass melting process 2 O 3 Is easy to volatilize, and causes the problems of loss of a large amount of raw materials, reduction of product quality and shortening of the service life of the kiln.
The above object of the present invention is achieved by the following technical solutions:
in a first aspect of the invention, there is provided a method for preparing borosilicate glass, comprising the steps of:
according to the composition requirement of borosilicate glass, siO-containing glass is provided 2 Source and B 2 O 3 A first batch of sources;
adding glass powder into the first batch to prepare a second batch, wherein the mass fraction of the glass powder in the second batch is 4% -40%, and the particle size of the glass powder is less than or equal to 75 mu m;
and melting, clarifying and annealing the second batch to prepare the borosilicate glass.
In one embodiment, before melting, clarifying and annealing the second batch, the method further comprises the steps of:
and carrying out hot pressing treatment on the second batch to obtain a forming material.
In one embodiment, the temperature of the hot pressing treatment is 400-1100 ℃; and/or the number of the groups of groups,
the pressure of the hot pressing treatment is 0.05-1.1 MPa; and/or the number of the groups of groups,
the time of the hot pressing treatment is 5 min-40 min.
In one embodiment, the second batch has a mean square error of less than or equal to 0.52.
In one embodiment, the first batch material further comprises Al 2 O 3 Source, na 2 O source, K 2 O source, caO source, mgO source and La 2 O 3 One or more of the sources.
In one embodiment, prior to melting, clarifying, and annealing the second batch, the method further comprises the steps of:
and adding a clarifying agent into the second batch.
In one embodiment, the glass frit comprises a composition comprising SiO 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O, caO, mgO and La 2 O 3 One or more of the following.
In one embodiment, the melting temperature is 1600-1700 ℃; and/or the number of the groups of groups,
the melting time is 30-120 min.
In one embodiment, the temperature of the clarification is 1500 ℃ to 1600 ℃; and/or the number of the groups of groups,
the clarification time is 120-240 min.
In one embodiment, the annealing temperature is 600 ℃ to 700 ℃; and/or the number of the groups of groups,
the annealing time is 10-60 min.
In a second aspect, the invention provides borosilicate glass, which is characterized by being prepared by the preparation method of borosilicate glass.
In one embodiment, the borosilicate glass comprises the following components in percentage by mass:
SiO 2 70%~80%；
Al 2 O 3 2%~10%；
B 2 O 3 5%~15%
Na 2 O2%~10%；
CaO2%~8%；
K 2 O0.1%~2%。
the invention has the following beneficial effects:
the invention firstly provides a borosilicate glass containing SiO according to the component requirement of borosilicate glass 2 Source and B 2 O 3 The method comprises the steps of (1) a first batch of a source, and then adding glass powder with the particle size less than or equal to 75 mu m into the first batch to prepare a second batch; when the second batch is melted, the glass powder has low softening temperature and small particle size, is easy to be quickly softened into a liquid phase with certain adhesiveness, and forms a protective layer for wrapping the first batch, so that volatile components in the first batch can be adsorbed and melted in the protective layer, thereby reducing B from the root 2 O 3 The purpose of the volatilization rate; the mass fraction of the glass powder is controlled to be 4% -40%, the glass powder can be used as a filler to fill gaps of raw materials, material layering is reduced, uniformity of the second batch is improved, and therefore, water can not be added additionally to improve uniformity, and the increase of water content to B is avoided 2 O 3 The volatilization rate adversely affects.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The traditional energy-saving way of the glass industry is focused on the aspects of heat preservation of a glass kiln, fuel combustion efficiency improvement, waste heat recycling and the like, but energy saving is omitted from the aspect of improving raw materials. The components, the content, the grain diameter and the like of the glass raw materials are optimized, so that the quality of glass products can be improved, the melting temperature can be reduced, and the thermal efficiency can be greatly improved. Among them, the granulation of the glass batch is an effective means of improving the glass melting efficiency and reducing the energy consumption.
B in the glass batch for producing borosilicate glass 2 O 3 The glass kiln is easy to volatilize in the melting process, so that a large amount of raw materials are lost, the quality of glass products is reduced, and the glass kiln is eroded, so that the service life of the glass kiln is shortened. Conventional techniques are directed to how to reduceB 2 O 3 A series of studies have been made on the problem of the volatilization rate of (a).
There are literature proposals for melting temperature vs. B 2 O 3 The volatilization effect is mainly shown in the low temperature section (before 1000 ℃), when glass liquid is formed, B 2 O 3 The volatilization rate is very small; b is that the melting temperature is 1000 ℃ and the heat preservation time is increased 2 O 3 The volatilization rate is gradually increased, and after the heat preservation time reaches 4 hours, B 2 O 3 The volatilization rate is gradually gentle, so that the heat preservation time is shortened to reduce B 2 O 3 Is volatilized; when boric acid is used as raw material, the dry pressure energy of the batch is effectively reduced to B 2 O 3 Volatilizing, the pressure also affects B 2 O 3 The volatilization rate is most suitable when the pressure is 30 MPa.
It is proposed in the literature that the thermogravimetric curve of the glass batch shows that rare earth oxide La is added 2 O 3 The volatilization amount of boron can be effectively reduced; the mixture of boric acid and lanthanum oxide is heated at 650 ℃ for 4 hours to generate new phase LaBO 3 And part of boric acid and lanthanum oxide remain, and the temperature is raised to 800 ℃ to continue to react to generate La (BO) 2 ) 3 The saturated vapor pressure of lanthanum borate is smaller, so that the volatilization amount of boron can be reduced.
There is literature on influence B 2 O 3 The multiple process factors of the volatilization rate suggest that the volatilization amount of boron mainly depends on the moisture content of the batch and the melting temperature in the glass melting process, and the influence of the temperature on volatilization mainly appears in a low-temperature section (before 1000 ℃); granulating or briquetting pretreatment of the batch cannot reduce boron volatilization; the formation of borates with higher melting points by pretreatment of the feedstock is an effective method for reducing boron volatilization.
Meanwhile, some reports that the effect of reducing boron volatilization is achieved by controlling parameters such as heating rate, feeding temperature, melting time, clarification time and the like during melting, so that B 2 O 3 The volatilization rate of the catalyst can be controlled within the range of 1% -9%; there are reports of optimizing raw materials, components, contents, hydroxyl absorption coefficients (beta-OH values) and the like of glass.
However, the above-described technique has the following limitations: 1) Tabletting the batch, which inhibits B 2 O 3 The volatilization effect of the boron is limited, and the problem of boron volatilization cannot be fundamentally solved; 2) Adding rare earth oxide La 2 O 3 The method is not suitable for all borosilicate glass, and is also required to be subjected to targeted regulation and control by combining the requirements of the borosilicate glass, such as the use, the performance and the like, and the application range is limited; 3) The boron volatilization reduction effect is also not ideal enough by optimizing the aspects of component adjustment, melting process, charging condition and the like, and the production process is complex and difficult to popularize and realize.
Based on the above, the first aspect of the present invention provides a method for preparing borosilicate glass, so as to solve the problem of B in the glass melting process 2 O 3 The method is easy to volatilize, so that the problems of large consumption of raw materials, reduction of product quality, shortening of the service life of the kiln are solved, and the problems of complex process, poor volatilization inhibiting effect, limited application range and the like of the traditional method for reducing boron volatilization are solved.
In some embodiments, the method of making borosilicate glass comprises the steps of:
according to the composition requirement of borosilicate glass, siO-containing glass is provided 2 Source and B 2 O 3 A first batch of sources;
adding glass powder into the first batch to prepare a second batch, wherein the mass fraction of the glass powder in the second batch is 4% -40%, and the particle size of the glass powder is less than or equal to 75 mu m;
and melting, clarifying and annealing the second batch to prepare the borosilicate glass.
The invention firstly provides a borosilicate glass containing SiO according to the component requirement of borosilicate glass 2 Source and B 2 O 3 The method comprises the steps of (1) a first batch of a source, and then adding glass powder with the particle size less than or equal to 75 mu m into the first batch to prepare a second batch; when the second batch is melted, the glass powder has low softening temperature and small particle size, is easy to be quickly softened into a liquid phase with certain adhesiveness, and forms a protective layer for wrapping the first batch, so that the glass powder is in the first batchIs capable of adsorbing and dissolving in the protective layer, thereby achieving a radical reduction of B 2 O 3 The purpose of the volatilization rate; the mass fraction of the glass powder is controlled to be 4% -40%, the glass powder can be used as a filler to fill gaps of raw materials, material layering is reduced, uniformity of the second batch is improved, and therefore, water can not be added additionally to improve uniformity, and the increase of water content to B is avoided 2 O 3 The volatilization rate adversely affects. In addition, the method is applicable to borosilicate glass with different formulas, has simple process and easy realization, and can be popularized and applied on a large scale.
Illustratively, the mass fraction of the glass frit in the batch may be 4%, 8%, 12%, 16%, 20%, 24%, 28%, 32%, 36%, 40%, etc., and the particle size of the glass frit may be 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, etc.
Optionally, the mass fraction of the glass powder in the second batch is 5% -30%.
Further alternatively, the mass fraction of the glass powder in the second batch is 10% -20%.
In some embodiments, prior to melting, clarifying, and annealing the second batch, the method further comprises the steps of:
and carrying out hot pressing treatment on the second batch to obtain a forming material.
The hot pressing treatment is carried out before melting, clarifying and annealing, so that the glass powder can be tightly combined with all raw materials in the first batch, the purpose that the glass powder wraps the first batch is achieved, and the B is further reduced 2 O 3 Is a volatile rate of (c). After hot pressing treatment, the stacking density of the molding material is increased, the heat conductivity is accelerated, and the melting temperature is reduced, so that the melting efficiency is improved and the melting energy consumption is reduced; meanwhile, the hot pressing treatment can also reduce the phenomenon of material flying in the kiln, reduce a great amount of waste of raw materials, reduce erosion of the material flying to the kiln and prolong the service life of the kiln.
Optionally, the autoclave comprises the step of placing the second batch in a mould.
Further optionally, the mold comprises a graphite mold and/or a ceramic mold.
Optionally, the diameter of the molding material is 20 mm-40 mm, and the thickness is 10 mm-30 mm. Illustratively, the molding compound may have a diameter of 20mm, 22mm, 24mm, 26mm, 28mm, 30mm, 32mm, 34mm, 36mm, 38mm, 40mm, etc., and a thickness of 10mm, 12mm, 14mm, 16mm, 18mm, 20mm, 22mm, 24mm, 26mm, 28mm, 30mm, etc.
Optionally, the temperature of the hot pressing treatment is 400-1100 ℃. Illustratively, the heat press treatment may be performed at a temperature of 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, or the like.
Further alternatively, the temperature of the hot pressing treatment is 600 ℃ to 900 ℃.
Optionally, the pressure of the hot pressing treatment is 0.05-1.1 MPa. Illustratively, the autoclave is 0.05MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa, 0.55MPa, 0.6MPa, 0.65MPa, 0.7MPa, 0.75MPa, 0.8MPa, 0.85MPa, 0.9MPa, 0.95MPa, 1MPa, 1.05MPa or 1.1MPa, etc.
Further alternatively, the pressure of the hot pressing treatment is 0.1-0.9 MPa.
Optionally, the time of the hot pressing treatment is 5 min-40 min. Illustratively, the time of the autoclave is 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, or the like.
Further alternatively, the time of the hot pressing treatment is 10 min-30 min.
The temperature, the pressure and the time of the hot pressing treatment are controlled, so that the purpose of tightly wrapping other components by the glass powder can be realized, and factors such as overhigh temperature, overlong pressure and overlong time can be prevented from causing B 2 O 3 Negative impact of volatility.
In some embodiments, the second batch has a mean square error of less than or equal to 0.52. Illustratively, the second batch may have a mean square error of 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, or 0.52, etc.
The uniformity of powder mixing of the second batch material affects the melting speed and uniformity of the glass, and the measurement methods include titration, conductivity, optical reflection density and X-ray fluorescence spectroscopy. Wherein, the titration method is to take n samples (n is more than or equal to 3) at different points of the second batch, respectively dissolve in hot water, filter, then add phenolphthalein indicator, titrate with standard hydrochloric acid solution, and convert the total alkalinity of titration into Na 2 CO 3 To represent, thereby, the uniformity is measured by the mean deviation or mean square error of the n sample results. In the invention, after the glass powder is added into the first batch, the mean square error of the total titration alkalinity of the second batch can be controlled within 0.52, and the second batch has better uniformity, thereby being beneficial to accelerating the melting speed of borosilicate glass and improving the uniformity thereof.
In some embodiments, the first batch material further comprises Al 2 O 3 Source, na 2 O source, K 2 O source, caO source, mgO source and La 2 O 3 One or more of the sources.
It is understood that the borosilicate glass may be one or more of low alkali borosilicate glass, alkaline earth borosilicate glass, transition metal doped borosilicate glass, and rare earth doped borosilicate glass. Wherein the main body of borosilicate glass is SiO 2 And B 2 O 3 The intermediate is Al 2 O 3 The exosome is selected from one or more of alkali metal oxides, alkaline earth metal oxides, transition metal oxides, and rare earth metal oxides, including but not limited to: na (Na) 2 O、K 2 O, caO, mgO and La 2 O 3 . Therefore, the raw materials of the first batch can be regulated and controlled according to the component requirements of borosilicate glass.
Optionally, the SiO 2 Sources include quartz sand and/or silicate; wherein the silicate comprises one or more of sodium silicate, potassium silicate, aluminum silicate and calcium silicate.
Optionally, the SiO 2 In the source, the mass fraction of particles with the particle diameter of 75-550 μm is more than or equal to 92%, and the particle diameter is less than or equal to 75 μmThe mass fraction of the particles is less than or equal to 8 percent.
Optionally, the B 2 O 3 Sources include borax and/or boric acid; wherein the borax comprises sodium borate decahydrate (Na 2 B 4 O 7 ·10H 2 O), sodium borate pentahydrate (Na) 2 B 4 O 7 ·5H 2 O) and anhydrous sodium borate (Na 2 B 4 O 7 ) One or more of the following.
Optionally, the B 2 O 3 In the source, the mass fraction of particles with the particle diameter of 550-3350 μm is more than or equal to 82%, the mass fraction of particles with the particle diameter of less than or equal to 550 μm is less than or equal to 10%, and the mass fraction of particles with the particle diameter of less than or equal to 1000 μm is less than or equal to 8%.
Optionally, the Al 2 O 3 Sources include alumina and/or aluminum hydroxide.
Optionally, the Al 2 O 3 In the source, the mass fraction of particles with the particle diameter of 25-150 μm is more than or equal to 79%, the mass fraction of particles with the particle diameter of less than or equal to 25 μm is less than or equal to 20%, and the mass fraction of particles with the particle diameter of less than or equal to 150 μm is less than or equal to 1%.
Optionally, the Na 2 The O source includes one or more of sodium silicate, sodium carbonate, and sodium bicarbonate.
Optionally, the Na 2 In the O source, the mass fraction of particles with the particle diameter of 550-3350 μm is more than or equal to 83%, the mass fraction of particles with the particle diameter of less than or equal to 550 μm is less than or equal to 14%, and the mass fraction of particles with the particle diameter of less than or equal to 1000 μm is less than or equal to 3%.
Optionally, the CaO source includes one or more of dolomite, quicklime, and limestone.
Optionally, in the CaO source, the mass fraction of particles with the particle size of 150-830 μm is more than or equal to 92%, and the mass fraction of particles with the particle size of less than or equal to 150 μm is less than or equal to 8%.
Optionally, the K 2 The O source includes one or more of potassium carbonate and potassium bicarbonate.
Optionally, the K 2 In the O source, the mass fraction of particles with the particle diameter of 150-830 μm is more than or equal to 58%, and the mass fraction of particles with the particle diameter of 830-1700 μm is less than or equal to 30%.
In some embodiments, prior to melting, clarifying, and annealing the second batch, the method further comprises the steps of:
and adding a clarifying agent into the second batch.
As will be appreciated, fining agents are components that facilitate bubble elimination in the molten glass during fining.
Optionally, the fining agent includes one or more of tin oxide, antimony oxide, cerium oxide, sodium sulfate, barium sulfate, calcium sulfate sodium chloride, ammonium chloride, calcium fluoride, and sodium fluorosilicate.
Further optionally, the fining agent includes one or more of tin oxide and sodium chloride.
Optionally, the mass fraction of the clarifying agent in the second batch is 0.1% -1%.
Further alternatively, the mass fraction of the clarifying agent in the second batch is 0.4% -0.6%.
In some embodiments, the composition of the glass frit comprises SiO 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O, caO, mgO and La 2 O 3 One or more of the following.
It will be appreciated that the composition of the glass frit may or may not be the same as that of the borosilicate glass, as long as the components of the second batch after addition of the glass frit meet the compositional requirements of the borosilicate glass. In some specific embodiments, the components and the content of the glass powder are the same as those of the borosilicate glass, so that waste materials generated in the borosilicate glass production process can be recovered, the utilization rate of raw materials is improved, and the production cost of the borosilicate glass is reduced.
In some embodiments, the glass frit comprises the following components in mass fraction:
SiO 2 70%~80%；
Al 2 O 3 2%~10%；
B 2 O 3 5%~15%；
Na 2 O2%~10%；
CaO2%~8%；
K 2 O0.1%~2%。
optionally, the glass powder comprises the following components in percentage by mass:
SiO 2 72%~78%；
Al 2 O 3 4%~7%；
B 2 O 3 8%~12%；
Na 2 O4%~7%；
CaO3%~6%；
K 2 O0.2%~1%。
further optionally, the glass powder comprises the following components in percentage by mass:
SiO 2 74%~76%；
Al 2 O 3 5%~6%；
B 2 O 3 9%~10%；
Na 2 O5%~6%；
CaO4%~5%；
K 2 O0.5%~0.8%。
optionally, the temperature of the melting is 1600 ℃ to 1700 ℃, such as 1600 ℃, 1610 ℃, 1620 ℃, 1630 ℃, 1640 ℃, 1650 ℃, 1660 ℃, 1670 ℃, 1680 ℃, 1690 ℃, 1700 ℃, and the like.
Optionally, the melting time is 30 min-120 min, for example, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min, etc.
Optionally, the temperature of the clarification is 1500 ℃ to 1600 ℃, such as 1500 ℃, 1510 ℃, 1520 ℃, 1530 ℃, 1540 ℃, 1550 ℃, 1560 ℃, 1570 ℃, 1580 ℃, 1590 ℃, 1600 ℃, and the like.
Optionally, the clarifying time is 120 min-240 min, for example, 120min, 130min, 140min, 150min, 160min, 170min, 180min, 190min, 200min, 210min, 220min, 230min or 240min, etc.
Optionally, the annealing temperature is 600 ℃ to 700 ℃, such as 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃, or the like.
Optionally, the annealing time is 10 min-60 min, for example, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, etc.
In a second aspect, the invention provides borosilicate glass, which is prepared by the preparation method of borosilicate glass.
In some embodiments, the borosilicate glass comprises the following components in mass fraction:
SiO 2 70%~80%；
Al 2 O 3 2%~10%；
B 2 O 3 5%~15%
Na 2 O2%~10%；
CaO2%~8%；
K 2 O0.1%~2%。
optionally, the borosilicate glass comprises the following components in percentage by mass:
SiO 2 72%~78%；
Al 2 O 3 4%~7%；
B 2 O 3 8%~12%
Na 2 O4%~7%；
CaO3%~6%；
K 2 O0.2%~1%。
further optionally, the borosilicate glass comprises the following components in percentage by mass:
SiO 2 74%~76%；
Al 2 O 3 5%~6%；
B 2 O 3 9%~10%
Na 2 O5%~6%；
CaO4%~5%；
K 2 O0.5%~0.8%。
the present invention will be described in further detail with reference to specific examples. In the following specific examples and comparative examples, the raw materials used, unless otherwise specified, were all commercially available products; the instruments used, unless otherwise specified, are all commercially available products; the processes used, unless otherwise indicated, are all routine choices for the person skilled in the art. The following specific examples and comparative examples use the following raw materials:
quartz sand: the mass fraction of particles with the particle diameter of 75-550 μm is more than or equal to 92%, and the mass fraction of particles with the particle diameter of less than or equal to 75 μm is less than or equal to 8%;
aluminum hydroxide: the mass fraction of particles with the particle diameter of 25-150 mu m is more than or equal to 79%, the mass fraction of particles with the particle diameter of less than or equal to 25 mu m is less than or equal to 20%, and the mass fraction of particles with the particle diameter of less than or equal to 150 mu m is less than or equal to 1%;
borax: the mass fraction of particles with the particle diameter of 550-3350 mu m is more than or equal to 82%, the mass fraction of particles with the particle diameter of less than or equal to 550 mu m is less than or equal to 10%, and the mass fraction of particles with the particle diameter of less than or equal to 1000 mu m is less than or equal to 8%;
soda ash (sodium carbonate): the mass fraction of particles with the particle diameter of 550-3350 mu m is more than or equal to 83%, the mass fraction of particles with the particle diameter of less than or equal to 550 mu m is less than or equal to 14%, and the mass fraction of particles with the particle diameter of less than or equal to 1000 mu m is less than or equal to 3%;
limestone: the mass fraction of particles with the particle diameter of 150-830 μm is more than or equal to 92%, and the mass fraction of particles with the particle diameter of less than or equal to 150 μm is less than or equal to 8%;
potassium carbonate: the mass fraction of particles with the particle diameter of 150-830 mu m is more than or equal to 58%, and the mass fraction of particles with the particle diameter of 830-1700 mu m is less than or equal to 30%;
the particle size of the glass powder is less than or equal to 75 mu m, and the glass powder comprises the following components: siO (SiO) 2 ，75%；Al 2 O 3 ，5.4%；B 2 O 3 ，9.5%；Na 2 O，5%；CaO，4.4%；K 2 O，0.7%。
The borosilicate glass comprises the following target components: siO (SiO) 2 ，75%；Al 2 O 3 ，5.4%；B 2 O 3 ，9.5%；Na 2 O，5%；CaO，4.4%；K 2 O，0.7%。
Example 1
Preparing quartz sand, aluminum hydroxide, borax, sodium carbonate, limestone and potassium carbonate according to target components of borosilicate glass, and uniformly mixing to prepare a first batch; adding glass powder and a clarifying agent into the first batch to prepare a second batch, wherein the mass fraction of the glass powder in the second batch is 4%, and the mass fraction of the clarifying agent in the second batch is 0.5%; melting the second batch at 1650 ℃ for 1h, clarifying at 1550 ℃ for 3h, and annealing at 660 ℃ for 0.5h to prepare borosilicate glass.
Example 2
This embodiment differs from embodiment 1 in that: the mass fraction of the glass frit in the second batch was 5%.
Example 3
This embodiment differs from embodiment 1 in that: the mass fraction of the glass powder in the second batch is 10%.
Example 4
This embodiment differs from embodiment 1 in that: the mass fraction of the glass powder in the second batch is 30%.
Example 5
This embodiment differs from embodiment 1 in that: the mass fraction of the glass powder in the second batch is 40%.
Example 6
This embodiment differs from embodiment 1 in that: the mass fraction of the glass powder in the second batch is 10%, and the second batch is subjected to hot pressing treatment before melting.
Preparing quartz sand, aluminum hydroxide, borax, sodium carbonate, limestone and potassium carbonate according to target components of borosilicate glass, and uniformly mixing to prepare a first batch; adding glass powder into the first batch to prepare a second batch, wherein the mass fraction of the glass powder in the second batch is 4%; placing the second batch in a mould, and hot-pressing at 600 ℃ and 0.1MPa for 10min to obtain a forming material; melting the molding material at 1650 ℃ for 1h, clarifying at 1550 ℃ for 3h, and annealing at 660 ℃ for 0.5h to obtain borosilicate glass.
Example 7
This embodiment differs from embodiment 6 in that: the conditions for the hot pressing treatment are hot pressing at 600 ℃ and 0.5MPa for 30min.
Example 8
This embodiment differs from embodiment 6 in that: the conditions for the hot pressing treatment are hot pressing at 600 ℃ and 0.9MPa for 20min.
Example 9
This embodiment differs from embodiment 6 in that: the conditions for the hot pressing treatment were hot pressing at a temperature of 750℃and a pressure of 0.1MPa for 30 minutes.
Example 10
This embodiment differs from embodiment 6 in that: the conditions for the hot pressing treatment are hot pressing at 750 ℃ and 0.5MPa for 20min.
Example 11
This embodiment differs from embodiment 6 in that: the conditions for the hot pressing treatment are hot pressing at a temperature of 750 ℃ and a pressure of 0.9MPa for 10min.
Example 12
This embodiment differs from embodiment 6 in that: the conditions for the hot pressing treatment are hot pressing at 900 ℃ and 0.1MPa for 20min.
Example 13
This embodiment differs from embodiment 6 in that: the conditions for the hot pressing treatment are hot pressing at 900 ℃ and 0.5MPa for 10min.
Example 14
This embodiment differs from embodiment 6 in that: the conditions for the hot pressing treatment are hot pressing at 900 ℃ and 0.9MPa for 30min.
Comparative example 1
The second batch of this comparative example was not added with glass frit, and otherwise was consistent with example 1.
Comparative example 2
The second batch of this comparative example was not added with glass frit and water was added at a mass fraction of 0.05%, otherwise identical to example 1.
Test case
(1) Uniformity: taking 20 samples at different points of the second batch, respectively dissolving in hot water, filtering, adding phenolphthalein indicator, titrating with standard hydrochloric acid solution, and converting total alkalinity into Na 2 CO 3 To show, the mean square error of total alkalinity of titration of 20 samples was calculated, and the results are shown in table 1; wherein, the smaller the mean square error of total alkalinity of titration is, the better the uniformity of the second batch is.
（2）B 2 O 3 Volatilization rate: b in borosilicate glass was tested according to "determination of 7 diboron trioxide" in GB/T1549-2008 method for chemical analysis of fiber glass 2 O 3 Actual content and calculate B 2 O 3 The results of the volatilization amount and volatilization rate of (2) are shown in Table 1.
(3) Appearance: if the borosilicate glass had a large number of bubbles, the appearance of the borosilicate glass was noted as NG (not good), and if not, the appearance of the borosilicate glass was noted as OK, and the results are shown in table 1.
As can be seen from Table 1, in comparative example 1, the second batch had no glass frit and water added thereto, and the uniformity of the second batch was the worst, B 2 O 3 The volatilization rate is also relatively high. Comparative example 2 with 5% water, the uniformity of the second batch was significantly improved, but B 2 O 3 The volatilization rate increased from 12.1% to 13.7%, which indicates that the addition of moisture to the second batch, while beneficial to improving the uniformity of the second batch, also promotes B 2 O 3 Is volatilized.
In examples 1-5, the uniformity of the second batch material gradually increased with increasing mass fraction of glass frit in the second batch material, while B 2 O 3 The volatilization rate is gradually reduced, and the minimum volatilization rate can reach 6.3%; wherein the mass fraction of the glass powder is optimally 10%, and secondly, 5% or 30%; the uniformity of the second batch is poor when the mass fraction of the glass powder is 4%, and more small bubbles appear on the appearance surface of the glass when the mass fraction of the glass powder is 40%. This isThe glass powder is added into the second batch under the condition of no hot pressing treatment, which not only can obviously improve the uniformity of the second batch, but also can greatly reduce B 2 O 3 But too high a content of glass frit may affect the appearance of the product.
In examples 6 to 14, the second batch contained 10% glass frit by mass, and the uniformity of the second batch was in the range of 0.12 to 0.17; then the second batch is put into a die for hot pressing treatment to form a forming material with the diameter of 20 mm-40 mm and the thickness of 10 mm-30 mm, and finally the B borosilicate glass is prepared 2 O 3 The volatilization rate is kept in the range of 1.6% -8.4%; among them, the optimum hot pressing conditions were hot pressing at a temperature of 750℃and a pressure of 0.9MPa for 10min (i.e., example 11), followed by hot pressing at a temperature of 600℃and a pressure of 0.9MPa for 20min (i.e., example 8).
By adding glass powder and cooperatively matching with hot pressing treatment, B 2 O 3 The volatilization of the volatile components is obviously inhibited, basically only a small amount of volatilization is carried out on the surface layer of the molten glass liquid in the early stage of melting, because the glass powder can be rapidly softened into a liquid state with adhesiveness at the temperature of 600-800 ℃ in the hot pressing process, and a protective layer for wrapping the first batch is formed, so that B 2 O 3 The volatile components are adsorbed into the protective layer, and B is blocked directly from the source 2 O 3 And volatilizing the light raw materials.
In addition, the hot press treatment of the second batch material has the following effects:
1) Greatly reduces the energy consumption of melting treatment: for a glass melting furnace with 200t capacity, the specific heat capacity c of the second batch material was 9.66×10 2 J/(kg×k), hot pressing temperature 600 ℃, initial temperature 30 ℃, q=cm+t=1.1×10 can be calculated 11 J, wherein Q is the heat saved by the melting treatment, c is the specific heat capacity of the second batch, m is the melting mass, and T is the difference between the hot pressing temperature and the initial temperature.
2) Remarkably improves the melting rate: the density of the second batch is ρ 1 =1.2g/cm 3 Density of molding materialDegree ρ 2 =2.0g/cm 3 The stacking gap between the molding materials is larger than that between the second batch materials, and the difference between the stacking densities of the molding materials and the second batch materials is ρ 3 =0.5g/cm 3 Note that if the rate of increase in the melting rate is M, then m= (ρ) 2 −ρ 1 −ρ 3 ）/ρ 1 =25%; because the density of the obtained molding material is obviously increased after the glass powder is added and hot pressing treatment is carried out, the heat conduction rate is faster, and the final melting rate is obviously improved.
3) The utilization rate of raw materials is improved: for a glass melting furnace with the capacity of 200t, in the traditional method, a waste collection system can collect more than 1t of second batch material as waste every day, so that a large amount of resources are wasted; by adopting the preparation method, the waste collection system can only collect waste below 0.2t every day, 80% of waste can be reduced, and the raw material utilization rate is high.
4) Prolonging the service life of the kiln: the second batch is fed into the kiln, so that the phenomenon of material flying tends to occur, and the material flying easily erodes the grids of the kiln under the action of high temperature, so that the service life of the grids is reduced; after the hot pressing treatment, the material flying phenomenon is effectively inhibited when the molding material is fed into a kiln for melting, in particular to B 2 O 3 The volatilization rate of the components with strong equal aggressivity is also greatly reduced, the service life of the grid body can be prolonged by 3-4 times, the service life is prolonged by 3-4 years, and the service life of the kiln crown is prolonged by 2 years.
TABLE 1 comparison of the Properties of borosilicate glasses
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is, therefore, indicated by the appended claims, and the description may be intended to interpret the contents of the claims.
Claims (12)
1. The preparation method of borosilicate glass is characterized by comprising the following steps:
according to the composition requirement of borosilicate glass, siO-containing glass is provided 2 Source and B 2 O 3 A first batch of sources;
adding glass powder into the first batch to prepare a second batch, wherein the mass fraction of the glass powder in the second batch is 4% -40%, and the particle size of the glass powder is less than or equal to 75 mu m;
and melting, clarifying and annealing the second batch to prepare the borosilicate glass.
2. The method of making borosilicate glass according to claim 1, wherein said second batch material is melted, clarified, and annealed prior to said step of:
and carrying out hot pressing treatment on the second batch to obtain a forming material.
3. The method for preparing borosilicate glass according to claim 2, wherein the temperature of the hot press treatment is 400 ℃ to 1100 ℃; and/or the number of the groups of groups,
the pressure of the hot pressing treatment is 0.05-1.1 MPa; and/or the number of the groups of groups,
the time of the hot pressing treatment is 5 min-40 min.
4. The method for preparing borosilicate glass according to any one of claims 1 to 3, wherein the mean square error of the total titration alkalinity of the second batch is less than or equal to 0.52.
5. The method of making borosilicate glass according to claim 4, wherein said first batch material further comprises Al 2 O 3 Source, na 2 O source, K 2 O source, caO source, mgO source and La 2 O 3 One or more of the sources.
6. The method of making borosilicate glass according to claim 5, wherein prior to melting, fining and annealing said second batch material, further comprising the steps of:
and adding a clarifying agent into the second batch.
7. The method for producing borosilicate glass according to claim 6, wherein said glass frit comprises SiO 2 、Al 2 O 3 、B 2 O 3 、Na 2 O、K 2 O, caO, mgO and La 2 O 3 One or more of the following.
8. The method for producing borosilicate glass according to any one of claims 1 to 3 and 5 to 7, wherein the melting temperature is 1600 ℃ to 1700 ℃; and/or the number of the groups of groups,
the melting time is 30-120 min.
9. The method for preparing borosilicate glass according to claim 8, wherein the temperature of said fining is 1500 ℃ to 1600 ℃; and/or the number of the groups of groups,
the clarification time is 120-240 min.
10. The method for preparing borosilicate glass according to claim 9, wherein the annealing temperature is 600 ℃ to 700 ℃; and/or the number of the groups of groups,
the annealing time is 10-60 min.
11. Borosilicate glass, characterized in that it is produced by the method for producing borosilicate glass according to any one of claims 1 to 10.
12. The borosilicate glass according to claim 11, wherein said borosilicate glass comprises the following components in mass fraction:
SiO 2 70%~80%；
Al 2 O 3 2%~10%；
B 2 O 3 5%~15%；
Na 2 O2%~10%；
CaO2%~8%；
K 2 O0.1%~2%。
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