CN116969673A - High-temperature-resistant laser protective glass material and preparation method thereof - Google Patents
High-temperature-resistant laser protective glass material and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 230000001681 protective effect Effects 0.000 title claims abstract description 33
- 238000002844 melting Methods 0.000 claims abstract description 51
- 230000008018 melting Effects 0.000 claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 239000011812 mixed powder Substances 0.000 claims abstract description 18
- 239000003607 modifier Substances 0.000 claims abstract description 18
- 238000009966 trimming Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000012216 screening Methods 0.000 claims abstract description 17
- 238000005498 polishing Methods 0.000 claims abstract description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000010583 slow cooling Methods 0.000 claims abstract description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 13
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 229910021538 borax Inorganic materials 0.000 claims description 9
- 239000004328 sodium tetraborate Substances 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- -1 cesium peroxide Chemical class 0.000 claims description 6
- 239000006060 molten glass Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 17
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 abstract description 16
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011775 sodium fluoride Substances 0.000 abstract description 8
- 235000013024 sodium fluoride Nutrition 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052596 spinel Inorganic materials 0.000 abstract description 4
- 239000011029 spinel Substances 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 239000012467 final product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 53
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 230000000007 visual effect Effects 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
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
-
- 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
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
-
- 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
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 the technical field of glass preparation, in particular to a high-temperature-resistant laser protective glass material and a preparation method thereof. Which comprises the following steps: cleaning the raw materials, mixing, and crushing and screening to generate mixed powder; placing the mixed powder into a melting furnace for preliminary melting, and adding auxiliary materials and reinforcing agents into the melting furnace to generate glass liquid; adding a modifier and a stabilizer into glass liquid, standing to generate a blank, and pouring the blank into a mould to carry out hot end forming; taking out the formed blank, preheating, heat-preserving annealing and slow cooling, and polishing and trimming to obtain the final product. According to the invention, the stabilizer is added to generate a zinc spinel crystal structure, and sodium fluosilicate is decomposed at high temperature and reacts with sodium carbonate and silicon dioxide to generate products such as sodium fluoride and silicon tetrafluoride during high-temperature reaction, so that the strength and hardness of the glass can be further enhanced by means of the sodium fluoride and the silicon tetrafluoride.
Description
Technical Field
The invention relates to the technical field of glass preparation, in particular to a high-temperature-resistant laser protective glass material and a preparation method thereof.
Background
The laser protective glass is the observation window glass of various laser mechanical equipment, can effectively protect 532nm laser, 1064nm laser and laser beams in a specific wavelength range, can protect the harm of high-energy laser to human eyes, has higher light transmittance to the spectrum peak value of human eye visual sensitivity, and has stronger narrowband absorption or reflection characteristics to visible spectrum range, 1.06 mu m and other places or various specific wavelength lasers.
The invention relates to a glass ceramic material for laser protection and a preparation method thereof, such as CN105712633A, wherein the oxidation composition of base glass is as follows: siO2 (54 wt% to 64 wt%), al2O3 (18 wt% to 22 wt%), li2O (3 wt% to 5 wt%), srO (3 wt% to 5 wt%), mgO (3 wt% to 5 wt%), B2O3 (0.5 wt% to 1.5 wt%), na2O (0.4 wt% to 0.8 wt%), tiO2 (2 wt% to 3 wt%), zrO2 (2 wt% to 3 wt%), er2O3 (2 wt% to 3 wt%), bi2O3 (0.5 wt% to 1.5 wt%), co2O3 (0.2 wt% to 0.4 wt%), sb2O3 (0.1 wt% to 0.3 wt%); the obtained microcrystalline glass has specific absorption capacity at various laser wave bands in the range of 300-1000 nm (except 805-815 nm and 975-985 nm), so that the laser transmittance of the wave bands is lower than 20%, but when the microcrystalline glass is used as the observation window glass of the laser mechanical equipment, a large amount of heat is generated due to the operation of the laser mechanical equipment, when the continuous operation time of the laser mechanical equipment is longer, the environment temperature rises, and the laser protective glass is damaged due to thermal expansion, so that the use effect is poor.
In order to reduce the thermal expansion rate of the laser protective glass to avoid expansion damage, a high-temperature-resistant laser protective glass material and a preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant laser protective glass material and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the above object, one of the objects of the present invention is to provide a high temperature resistant laser protective glass material, comprising the following raw materials in parts by weight:
27-41 parts of silicon dioxide, 10-22 parts of boric acid, 15-22 parts of aluminum oxide, 6-12 parts of auxiliary materials, 8-11 parts of reinforcing agents, 11-17 parts of calcium oxide, 8-12 parts of modifying agents and 2-7 parts of stabilizing agents;
the modifier comprises borax and sodium fluosilicate, and the weight ratio of the borax to the sodium fluosilicate is 3:1;
the stabilizer comprises zinc oxide and sodium carbonate, and the weight ratio of the zinc oxide to the sodium carbonate is 1:5.
As a further improvement of the technical scheme, the auxiliary material comprises dichromate, ferric oxide and nickel oxide, and the weight ratio of the dichromate to the ferric oxide to the nickel oxide is 1:2:1.
As a further improvement of the technical scheme, the strengthening agent comprises nickel oxide and cesium peroxide, and the weight ratio of the nickel oxide to the cesium peroxide is 1:1.
The second object of the present invention is to provide a method for preparing the high temperature resistant laser protective glass material, comprising the following steps:
s1, cleaning raw materials, mixing silicon dioxide, boric acid, aluminum oxide and calcium oxide, and then crushing and screening to generate mixed powder;
s2, placing the mixed powder into a melting furnace for preliminary melting, and adding auxiliary materials and reinforcing agents into the melting furnace to generate glass liquid;
s3, pouring a modifier and a stabilizer into the molten glass, standing to generate a blank, and pouring the blank into a mold to perform hot end forming;
s4, taking out the formed blank, preheating, carrying out heat preservation annealing and slow cooling, and polishing and trimming to finish the preparation of the glass.
As a further improvement of the technical scheme, in the step S1, powder with uniform granularity is produced after crushing by a crusher and screening, and the granularity diameter of the powder ranges from 2mm to 6mm.
As a further improvement of the technical scheme, in the S2, the melting temperature ranges from 1200 ℃ to 1600 ℃ and the melting time ranges from 5 hours to 9 hours.
As a further improvement of the technical scheme, in the step S2, stirring and mixing are needed when auxiliary materials and reinforcing agents are added, and the stirring rotation speed range is 15-50rpm/min.
As a further improvement of the technical scheme, in the step S3, the standing time ranges from 4 hours to 8 hours.
As a further improvement of the technical scheme, in the step S3, the hot end forming temperature is 600-1000 ℃.
As a further improvement of the technical scheme, in the step S4, the grinding amount during grinding and trimming is in the range of 0.5-3.0mm.
According to the invention, the heat resistance of glass can be improved by adding the modifier, borax is converted to form diboron trioxide during preparation of the glass, and further the melting point and stability of the glass are improved by virtue of the borate crystal structure of boron oxide at high temperature, the physical property of the glass can be improved by virtue of sodium fluosilicate, the heat stability of the glass is further improved by virtue of chemical bonds generated by sodium fluosilicate, aluminum fluoride is generated by combining with aluminum in the glass during preparation of the glass, and further the heat resistance of the glass is improved, zinc oxide can adjust the transparency of the glass, the refractive index of the glass is reduced, the laser protection effect is improved, zinc oxide can generate a zinc spinel ZnO-Al 2O3 crystal structure with aluminum trioxide, the structural strength of the glass is improved, the heat stability of the glass at high temperature is ensured, carbon dioxide gas is generated by high-temperature melting during preparation of sodium carbonate, the glass becomes amorphous solid, and in addition, during high-temperature reaction of the glass, sodium fluosilicate is decomposed at high temperature with sodium carbonate and silicon dioxide to generate products such as sodium fluoride and silicon tetrafluoride, and the strength and hardness of the glass can be further enhanced by virtue of sodium fluoride and silicon tetrafluoride.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the high-temperature-resistant laser protective glass material and the preparation method thereof, the stabilizer is added, so that a zinc spinel crystal structure can be generated, bubbles in glass liquid can be eliminated when glass is prepared, sodium fluosilicate is decomposed at high temperature and reacts with sodium carbonate and silicon dioxide to generate products such as sodium fluoride and silicon tetrafluoride when the high-temperature reaction is carried out, and the strength and hardness of the glass can be further enhanced by means of the sodium fluoride and the silicon tetrafluoride.
2. According to the high-temperature-resistant laser protective glass material and the preparation method thereof, when the modifier is added to prepare glass, borax is converted to form a borate crystal structure, so that the melting point and stability of the glass are improved, while sodium fluosilicate can improve the physical properties of the glass and can be combined with aluminum in the glass to generate aluminum fluoride when the glass is prepared, and further the heat resistance of the glass is improved.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
One of the purposes of this embodiment is to provide a high temperature resistant laser protective glass material, which comprises the following raw materials in parts by weight: 27-41 parts of silicon dioxide, 10-22 parts of boric acid, 15-22 parts of aluminum oxide, 6-12 parts of auxiliary materials, 8-11 parts of reinforcing agents, 11-17 parts of calcium oxide, 8-12 parts of modifying agents and 2-7 parts of stabilizing agents;
the modifier comprises borax and sodium fluosilicate, and the weight ratio of the borax to the sodium fluosilicate is 3:1;
the stabilizer comprises zinc oxide and sodium carbonate, and the weight ratio of the zinc oxide to the sodium carbonate is 1:5;
further, the auxiliary materials comprise dichromate, ferric oxide and nickel oxide, the weight ratio of the dichromate, the ferric oxide and the nickel oxide is 1:2:1, the glass material can strengthen the performance of protecting specific light rays by adding auxiliary agents, for example, the dichromate can protect gray, dark blue and other visible light, the ferric oxide can absorb ultraviolet rays, infrared rays and the like, and the nickel oxide can absorb infrared rays and part of visible light.
Still further, the strengthening agent comprises nickel oxide and cesium peroxide, and the weight ratio of the nickel oxide to the cesium peroxide is 1:1, and the hardness and the strength of the glass can be increased by adding the strengthening agent.
Referring to fig. 1, a second purpose of this embodiment is to further provide a preparation method for preparing the above-described high-temperature-resistant laser protective glass material, which comprises the following specific steps:
s1, cleaning raw materials, mixing 27-41 parts by weight of silicon dioxide, 10-22 parts by weight of boric acid, 15-22 parts by weight of aluminum oxide and 11-17 parts by weight of calcium oxide, crushing and screening to generate mixed powder, crushing by a crusher and screening to generate powder with uniform granularity, wherein the particle size diameter range of the powder is 2-6mm, and the mode of crushing to generate powder can ensure uniform mixing of the raw materials and accelerate the mixing and melting speed of the materials;
s2, placing the mixed powder into a melting furnace for preliminary melting, adding 6-12 parts by weight of auxiliary materials and 8-11 parts by weight of reinforcing agents into the melting furnace to generate glass liquid, wherein the melting temperature is 1200-1600 ℃, the melting time is 5-9 hours, the materials are melted to facilitate the conversion of the materials into liquid, the subsequent shaping of the glass is carried out, stirring and mixing are required when the auxiliary materials and the reinforcing agents are added, the stirring rotation speed is 15-50rpm/min, and the auxiliary materials and the reinforcing agents are uniformly dispersed in the molten materials in a stirring and mixing mode;
s3, adding 8-12 parts by weight of modifier and 2-7 parts by weight of stabilizer into glass liquid, standing to generate a blank, pouring the blank into a mould, and performing hot end forming, wherein the standing time range is 4-8 hours, so that the modifier, the stabilizer and components in the blank can be fully contacted and reacted through long-term standing, the hot end forming temperature range is 600-1000 ℃, and glass has higher fluidity at higher temperature, thereby facilitating the forming of the glass;
s4, taking out the formed blank, preheating, heat-preserving annealing and slow cooling, polishing and trimming to finish the preparation of glass, wherein the polishing and trimming grinding quantity ranges from 0.5mm to 3.0mm, and the polishing and trimming can remove textures generated during shaping.
According to the invention, the heat resistance of glass can be improved by adding the modifier, borax is converted to form diboron trioxide during preparation of the glass, and further the melting point and stability of the glass are improved by virtue of the borate crystal structure of boron oxide at high temperature, the physical property of the glass can be improved by virtue of sodium fluosilicate, the heat stability of the glass is further improved by virtue of chemical bonds generated by sodium fluosilicate, aluminum fluoride is generated by combining with aluminum in the glass during preparation of the glass, and further the heat resistance of the glass is improved, zinc oxide can adjust the transparency of the glass, the refractive index of the glass is reduced, the laser protection effect is improved, zinc oxide can generate a zinc spinel ZnO-Al 2O3 crystal structure with aluminum trioxide, the structural strength of the glass is improved, the heat stability of the glass at high temperature is ensured, carbon dioxide gas is generated by high-temperature melting during preparation of sodium carbonate, the glass becomes amorphous solid, and in addition, during high-temperature reaction of the glass, sodium fluosilicate is decomposed at high temperature with sodium carbonate and silicon dioxide to generate products such as sodium fluoride and silicon tetrafluoride, and the strength and hardness of the glass can be further enhanced by virtue of sodium fluoride and silicon tetrafluoride.
According to the differences of the raw material consumption and the process parameters in the preparation process, the high-temperature-resistant laser protective glass material provided by the invention is further described by the following specific examples.
Example 1
S1, cleaning raw materials, mixing 27 parts by weight of silicon dioxide, 10 parts by weight of boric acid, 22 parts by weight of aluminum oxide and 17 parts by weight of calcium oxide, crushing and screening to generate mixed powder, crushing by a crusher and screening to generate powder with uniform granularity, wherein the particle size diameter of the powder is 2mm;
s2, placing the mixed powder into a melting furnace for preliminary melting, adding 6 parts by weight of auxiliary materials and 11 parts by weight of reinforcing agents into the melting furnace to generate glass liquid, wherein the melting temperature is 1600 ℃, the melting time is 5 hours, stirring and mixing are required when the auxiliary materials and the reinforcing agents are added, and the stirring rotation speed is 15rpm/min;
s3, adding 12 parts by weight of modifier and 7 parts by weight of stabilizer into the glass liquid, standing to generate a blank, pouring the blank into a die, and performing hot end forming, wherein the standing time is 4 hours, and the hot end forming temperature is 600 ℃;
s4, taking out the formed blank, preheating, carrying out heat preservation annealing and slow cooling, polishing and trimming to finish the preparation of glass, wherein the grinding amount is 3.0mm when polishing and trimming.
Example 2
S1, cleaning raw materials, mixing 32 parts by weight of silicon dioxide, 15 parts by weight of boric acid, 18 parts by weight of aluminum oxide and 14 parts by weight of calcium oxide, crushing and screening to generate mixed powder, crushing by a crusher and screening to generate powder with uniform granularity, wherein the particle size diameter of the powder is 4mm;
s2, placing the mixed powder into a melting furnace for preliminary melting, adding 8 parts by weight of auxiliary materials and 8 parts by weight of reinforcing agents into the melting furnace to generate glass liquid, wherein the melting temperature is 1400 ℃, the melting time is 7 hours, stirring and mixing are required when the auxiliary materials and the reinforcing agents are added, and the stirring rotation speed is 30rpm/min;
s3, adding 10 parts by weight of modifier and 5 parts by weight of stabilizer into the glass liquid, standing to generate a blank, pouring the blank into a die, and performing hot end forming, wherein the standing time is 6 hours, and the hot end forming temperature is 800 ℃;
s4, taking out the formed blank, preheating, carrying out heat preservation annealing and slow cooling, polishing and trimming to finish the preparation of glass, wherein the grinding amount is 2.0mm when polishing and trimming.
Example 3
S1, cleaning raw materials, mixing 41 parts by weight of silicon dioxide, 22 parts by weight of boric acid, 15 parts by weight of aluminum oxide and 11 parts by weight of calcium oxide, crushing and screening to generate mixed powder, crushing by a crusher and screening to generate powder with uniform granularity, wherein the particle size diameter of the powder is 6mm;
s2, placing the mixed powder into a melting furnace for preliminary melting, adding 12 parts by weight of auxiliary materials and 8 parts by weight of reinforcing agents into the melting furnace to generate glass liquid, wherein the melting temperature is 1200 ℃, the melting time is 9 hours, stirring and mixing are required when the auxiliary materials and the reinforcing agents are added, and the stirring rotation speed is 50rpm/min;
s3, adding 8 parts by weight of modifier and 2 parts by weight of stabilizer into the glass liquid, standing to generate a blank, pouring the blank into a die, and performing hot end forming, wherein the standing time is 8 hours, and the hot end forming temperature is 1000 ℃;
s4, taking out the formed blank, preheating, carrying out heat preservation annealing and slow cooling, polishing and trimming to finish the preparation of glass, wherein the grinding amount is 0.5mm during polishing and trimming.
TABLE 1 comparison of raw material amounts in examples 1-3
Table 2 comparative process parameters in examples 1-3
Comparative example 1
The comparative example adopts the preparation method of example 1, only lacks the modifier, and the rest is unchanged, and the specific steps are as follows:
s1, cleaning raw materials, mixing 27 parts by weight of silicon dioxide, 10 parts by weight of boric acid, 22 parts by weight of aluminum oxide and 17 parts by weight of calcium oxide, crushing and screening to generate mixed powder, crushing by a crusher and screening to generate powder with uniform granularity, wherein the particle size diameter of the powder is 2mm;
s2, placing the mixed powder into a melting furnace for preliminary melting, adding 6 parts by weight of auxiliary materials and 11 parts by weight of reinforcing agents into the melting furnace to generate glass liquid, wherein the melting temperature is 1600 ℃, the melting time is 5 hours, stirring and mixing are required when the auxiliary materials and the reinforcing agents are added, and the stirring rotation speed is 15rpm/min;
s3, pouring 7 parts by weight of stabilizer into the glass liquid, standing to generate a blank, pouring the blank into a die, and performing hot end forming, wherein the standing time is 4 hours, and the hot end forming temperature is 600 ℃;
s4, taking out the formed blank, preheating, carrying out heat preservation annealing and slow cooling, polishing and trimming to finish the preparation of glass, wherein the grinding amount is 3.0mm when polishing and trimming.
Comparative example 2
The comparative example adopts the preparation method of example 2, only lacks the modifier, and the rest is unchanged, and the specific steps are similar to those of comparative example 1, and the comparative example is not repeated.
Comparative example 3
The comparative example adopts the preparation method of example 3, only lacks the modifier, and the rest is unchanged, and the specific steps are similar to those of comparative example 1, and the comparative example is not repeated.
Comparative example 4
The comparative example uses the preparation method of example 1, only lacks the stabilizer, and the rest is unchanged, and the specific steps are as follows:
s1, cleaning raw materials, mixing 27 parts by weight of silicon dioxide, 10 parts by weight of boric acid, 22 parts by weight of aluminum oxide and 17 parts by weight of calcium oxide, crushing and screening to generate mixed powder, crushing by a crusher and screening to generate powder with uniform granularity, wherein the particle size diameter of the powder is 2mm;
s2, placing the mixed powder into a melting furnace for preliminary melting, adding 6 parts by weight of auxiliary materials and 11 parts by weight of reinforcing agents into the melting furnace to generate glass liquid, wherein the melting temperature is 1600 ℃, the melting time is 5 hours, stirring and mixing are required when the auxiliary materials and the reinforcing agents are added, and the stirring rotation speed is 15rpm/min;
s3, adding 12 parts by weight of modifier into the glass liquid = and standing to generate a blank, pouring the blank into a mould to perform hot end forming, wherein the standing time is 4 hours, and the hot end forming temperature is 600 ℃;
s4, taking out the formed blank, preheating, carrying out heat preservation annealing and slow cooling, polishing and trimming to finish the preparation of glass, wherein the grinding amount is 3.0mm when polishing and trimming.
Comparative example 5
The comparative example adopts the preparation method of example 2, only lacks the stabilizing agent, and the rest is unchanged, and the specific steps are similar to those of comparative example 4, and the comparative example is not repeated.
Comparative example 6
The comparative example adopts the preparation method of example 3, only lacks the stabilizing agent, and the rest is unchanged, and the specific steps are similar to those of comparative example 4, and the comparative example is not repeated.
TABLE 3 comparison of raw material amounts in comparative examples 1-6
Table 4 comparative process parameters in comparative examples 1-6
Comparative example 7
The preparation method of example 1 is adopted in this comparative example, the particle size diameter is set to 8mm, the rest is unchanged, the specific steps are similar to those of example 1, and the detailed description of this comparative example is omitted.
Comparative example 8
The preparation method of example 1 is adopted in this comparative example, the melting temperature is set to 1000 ℃, the rest is unchanged, the specific steps are similar to those of example 1, and the description of this comparative example is omitted.
Comparative example 9
The preparation method of example 1 is adopted in this comparative example, the melting time is set to 10h, the rest is unchanged, the specific steps are similar to those of example 1, and the description of this comparative example is omitted.
Comparative example 10
The preparation method of the example 2 is adopted in the comparative example, the stirring rotation speed is set to be 60rpm/min, the rest is unchanged, the specific steps are similar to those of the example 2, and the comparative example is not repeated.
Comparative example 11
The preparation method of example 2 is adopted in the comparative example, the standing time is set to be 2 hours, the rest is unchanged, the specific steps are similar to those of example 2, and the comparative example is not repeated.
Comparative example 12
The preparation method of example 3 is adopted in this comparative example, the forming temperature is set to 500 ℃, the rest is unchanged, the specific steps are similar to those of example 3, and the description of this comparative example is omitted.
Comparative example 13
The preparation method of example 3 is adopted in the comparative example, the grinding amount is set to be 5.0mm, the rest is unchanged, the specific steps are similar to those of example 3, and the comparative example is not repeated.
Table 5 comparison of amounts of raw materials used in comparative examples 7 to 13
Table 6 comparative Process parameter comparison in comparative examples 7-13
Test examples
The preparation of the laser protective glass was carried out according to the methods provided in examples 1 to 3 and comparative examples 1 to 13, respectively, and the average thermal expansion coefficient of the laser protective glass at 20 to 400℃was measured according to GB/T16920-2015 "measurement of average linear thermal expansion coefficient of glass", and the measured values were filled in Table 7.
Table 7 comparison of thermal expansion coefficients of the laser cover glasses of examples and comparative examples
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As can be seen from Table 7, the average thermal expansion coefficients of the laser protective glasses prepared in examples 1 to 3 and comparative examples 1 to 13 are smaller than those of the laser protective glasses prepared in comparative examples, and the average thermal expansion coefficients of the laser protective glasses prepared in examples are lower than 5.93X10 -6 The average thermal expansion coefficient of the laser protective glass prepared by adopting the comparative examples with different raw material amounts and process parameters is increased, so that the average thermal expansion coefficient of the prepared laser protective glass is lower under the working condition of the embodiment.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are only preferred embodiments of the present invention, and are not intended to limit the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The preparation method of the high-temperature-resistant laser protective glass material is characterized by comprising the following steps of:
s1, cleaning raw materials, mixing 27-41 parts by weight of silicon dioxide, 10-22 parts by weight of boric acid, 15-22 parts by weight of aluminum oxide and 11-17 parts by weight of calcium oxide, and crushing and screening to generate mixed powder;
s2, placing the mixed powder into a melting furnace for preliminary melting, and adding 6-12 parts by weight of auxiliary materials and 8-11 parts by weight of reinforcing agents into the melting furnace to generate molten glass;
s3, adding 8-12 parts by weight of modifier and 2-7 parts by weight of stabilizer into the molten glass, standing to generate a blank, and pouring the blank into a die to perform hot end forming;
s4, taking out the formed blank, preheating, carrying out heat preservation annealing and slow cooling, and polishing and trimming to finish the preparation of glass;
the modifier comprises borax and sodium fluosilicate, and the weight ratio of the borax to the sodium fluosilicate is 3:1;
the stabilizer comprises zinc oxide and sodium carbonate, and the weight ratio of the zinc oxide to the sodium carbonate is 1:5.
2. The method for preparing a high temperature resistant laser protective glass material according to claim 1, wherein: in the step S1, the powder with uniform granularity is produced after crushing by a crusher and screening, and the granularity diameter range of the powder is 2-6mm.
3. The method for preparing a high temperature resistant laser protective glass material according to claim 1, wherein: in the step S2, the auxiliary material comprises dichromate, ferric oxide and nickel oxide, and the weight ratio of the dichromate to the ferric oxide to the nickel oxide is 1:2:1.
4. The method for preparing a high temperature resistant laser protective glass material according to claim 1, wherein: in the step S2, the reinforcing agent comprises nickel oxide and cesium peroxide, and the weight ratio of the nickel oxide to the cesium peroxide is 1:1.
5. The method for preparing a high temperature resistant laser protective glass material according to claim 1, wherein: in the step S2, the melting temperature ranges from 1200 ℃ to 1600 ℃ and the melting time ranges from 5 hours to 9 hours.
6. The method for preparing a high temperature resistant laser protective glass material according to claim 1, wherein: in the step S2, stirring and mixing are needed when auxiliary materials and reinforcing agents are added, and the stirring rotating speed range is 15-50rpm/min.
7. The method for preparing a high temperature resistant laser protective glass material according to claim 1, wherein: in the step S3, the standing time ranges from 4 hours to 8 hours.
8. The method for preparing a high temperature resistant laser protective glass material according to claim 1, wherein: in the step S3, the forming temperature of the hot end is 600-1000 ℃.
9. The method for preparing a high temperature resistant laser protective glass material according to claim 1, wherein: in the step S4, the grinding amount range is 0.5-3.0mm during grinding and trimming.
10. The high temperature resistant laser protective glass material prepared by the preparation method according to any one of claims 1 to 9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310961065.1A CN116969673B (en) | 2023-08-01 | High-temperature-resistant laser protective glass material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310961065.1A CN116969673B (en) | 2023-08-01 | High-temperature-resistant laser protective glass material and preparation method thereof |
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| CN116969673A true CN116969673A (en) | 2023-10-31 |
| CN116969673B CN116969673B (en) | 2024-07-09 |
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| JP2007039281A (en) * | 2005-08-03 | 2007-02-15 | Maeda Kogyo Kk | Ultraviolet-absorbing glass for liquid crystal display illumination and glass tube |
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| CN113979635A (en) * | 2021-11-23 | 2022-01-28 | 清远忠信世纪电子材料有限公司 | Low-expansion-coefficient glass fiber |
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| GB1493456A (en) * | 1976-05-27 | 1977-11-30 | Corning Ltd | Production of opal glass |
| JP2007039281A (en) * | 2005-08-03 | 2007-02-15 | Maeda Kogyo Kk | Ultraviolet-absorbing glass for liquid crystal display illumination and glass tube |
| CN110436778A (en) * | 2019-07-26 | 2019-11-12 | 深圳阳光环球玻璃有限公司 | A kind of orthopaedics reparation bioactive glass material preparation method |
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