CN114014540B - Preparation process of opal quartz glass - Google Patents
Preparation process of opal quartz glass Download PDFInfo
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- CN114014540B CN114014540B CN202111489392.9A CN202111489392A CN114014540B CN 114014540 B CN114014540 B CN 114014540B CN 202111489392 A CN202111489392 A CN 202111489392A CN 114014540 B CN114014540 B CN 114014540B
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B1/00—Preparing the batches
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
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- 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
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
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Abstract
The invention discloses a preparation process of opal quartz glass, which relates to the technical field of quartz glass preparation and comprises the following steps: raw material purification → high temperature melting treatment → annealing treatment → high temperature melting treatment → drawing forming and annealing treatment → cutting and cleaning to obtain opal quartz glass; the raw materials comprise refined quartz sand; the purification method comprises a mixed acid hot-pressing leaching method; and adding affinity ionic liquid in the purification process. The opal quartz glass prepared by the process has higher radiation energy and better product quality; after the surface of the material is treated, the material has good self-cleaning capability; in addition, the quartz sand obtained by purification in the process has higher purity.
Description
Technical Field
The invention belongs to the technical field of quartz glass preparation, and particularly relates to a preparation process of opal quartz glass.
Background
Because a large number of dense tiny bubbles exist in the opal quartz glass, a glass and gas two-phase system exists in the opal quartz glass, wherein the refractive index of the bubble phase is 1, the refractive index of the quartz phase is 1.55, infrared light and visible light are refracted, reflected and scattered for many times in the two-phase system to form a scattering effect, the penetration rate of the visible light and far infrared light is reduced to 0.5-2% from 95-98% of the original transparent state, and almost most of the two energies are absorbed and converted into molecular vibration of Si-O bonds.
The defects of the quartz glass tube produced by the old production process in China comprise: 1) the opalescence is poor, and the infrared performance is poor due to the poor shape, size and quantity of the micro bubbles and the poor distribution uniformity in the quartz glass tube; 2) the air tightness is poor, and the milky white tube is required to have good air tightness, namely good vacuum sealing property when being used for manufacturing the far infrared radiation heating lamp; 3) the thermal stability is poor. Therefore, the demand for the increasingly developed industrial and agricultural production cannot be satisfied.
Disclosure of Invention
The invention aims to provide a preparation process of opal quartz glass, and the opal quartz glass prepared by the process has higher radiation energy and better product quality; after the surface of the material is treated, the material has good self-cleaning capability; in addition, the quartz sand obtained by purification in the process has higher purity.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a process for producing an opal quartz glass, comprising: raw material purification → high temperature melting treatment → annealing treatment → high temperature melting treatment → drawing forming and annealing treatment → cutting and cleaning to obtain opal quartz glass;
the raw materials comprise refined quartz sand;
the purification method comprises a mixed acid hot-pressing leaching method; and adding an affinity ionic liquid in the purification process. The invention adopts the hot-pressing leaching technology to effectively separate the mineral inclusion and the crystal lattice substitution type impurities at the gaps of the quartz sand crystal structure, reduce the content of impurity metals and remove part of the exposed impurity mineral inclusion and the structure type impurities on the surface and in the cracks. In the purification treatment process of the quartz sand, the affinity ionic liquid is added, has excellent metal chelating capacity, can be combined with various metal ions, can be effectively chelated with the metal ions when the metal ions are leached by mixed acid, and effectively reduces or avoids the leached impurity metal ions as interstitial atoms to compensate lattice charge balance to form lattice impurities, thereby effectively improving the clearance rate of impurity metal elements and improving the purity of the quartz sand. Meanwhile, the prepared high-purity quartz sand is applied to the preparation of the opal quartz glass, the performance of the obtained product is better, and the radiation energy of the opal quartz glass is obviously improved.
Specifically, the preparation process of the opal quartz glass comprises the following steps:
and (3) quartz sand purification pretreatment, namely taking quartz sand, and treating the quartz sand according to a liquid-solid ratio of 3-5 mL: adding 1g of mixed acid solution in a ratio to perform a hot-pressing leaching test, wherein the temperature is 180-220 ℃, the stirring speed is 200-240 r/min, adding affinity ionic liquid after leaching reaction for 2-4 h, and continuing the reaction for 1-3 h; after the leaching reaction is finished, fully washing the quartz sand to be neutral by using diethyl ether and deionized water in sequence, drying and cooling the quartz sand to obtain high-purity quartz sand;
uniformly mixing high-purity quartz sand and crystal sand to obtain a raw material mixture;
taking a raw material mixture for high-temperature melting, wherein the conditions of temperature rise treatment comprise: heating to 1400-1600 ℃ at a heating rate of 20-30 ℃/min, then heating to 1900-2000 ℃ at a heating rate of 3-6 ℃/min, and then keeping the temperature for 1-3 h; the cooling treatment conditions comprise: cooling to 1000-1200 ℃ at a cooling rate of 12-16 ℃/min;
cooling to 800-850 ℃ along with the furnace, and then carrying out annealing treatment: cooling from 750-800 ℃ to 550-600 ℃ at a cooling rate of 3-5 ℃/min;
then, after the temperature is reduced to the normal temperature along with the furnace, repeating the heating and cooling treatment once;
then drawing and forming, then annealing, cooling to normal temperature along with the furnace, and finally cutting and cleaning to obtain the opal quartz glass.
It is to be noted that SiO in the high-purity quartz sand prepared by purifying the raw materials 2 The content is more than 99.9 percent; more preferably, SiO in high purity quartz sand 2 The content is more than 99.99 percent.
The high-temperature melting temperature is 1900-1950 ℃.
The mixed acid solution includes hydrochloric acid with a concentration of 1.5-3M, hydrofluoric acid with a concentration of 0.4-0.7M, and nitric acid with a concentration of 0.3-0.6M.
The addition amount of the affinity ionic liquid is 0.2-1% of the mass of the quartz sand.
It should be noted that, when the leachate obtained in the quartz sand purification pretreatment process is recycled, affinity ionic liquid can be added to chelate and recover each metal ion; the method specifically comprises the following steps: adjusting the pH value of the leachate to be neutral, adding 0.2-1 mg/mL of affinity ionic liquid, stirring for 30-40 min at 60-80 ℃, centrifuging to remove an upper water phase, and washing for 3-5 times by using 4-5 mM acetic acid/sodium acetate buffer solution (pH 4.0-4.5); and then adding a hydrochloric acid solution with the volume equivalent concentration of 5-6M, stirring at 50-70 ℃ for 6-8 h, desorbing metal ions, and recovering.
The mass ratio of the high-purity quartz sand to the crystal sand is 1: 1 to 1.5.
The affinity ionic liquid comprises imidazole cation supported ionic liquid and functional ligand; the imidazole cation supported ionic liquid is obtained by reacting imidazole with 1-bromohexane and 1, 6-dibromohexane; the functional ligand at least comprises DO3A tert-butyl ester.
Functional ligands also include AF-DX 116. The prepared affinity ionic liquid has higher metal chelating capacity and better adsorption effect on various metal ions with different valence states and the like by adopting DO3A tert-butyl ester and AF-DX 116 as functional ligands. Wherein, the adsorption capacity of the ionic liquid prepared by taking AF-DX 116 as the functional ligand alone to metal ions is superior to that of the ionic liquid prepared by taking DO3A tert-butyl ester as the functional ligand alone. The method is applied to the purification treatment process of the quartz sand to prepare the high-purity quartz sand, so that the removal effect of impurity metal elements is obviously enhanced, and the purity of quartz sand products is effectively improved.
The preparation method of the affinity ionic liquid comprises the following steps: the ionic liquid is prepared by substitution reaction of bromoalkane in an imidazole cation supported ionic liquid structure and active hydrogen in a functional ligand structure.
Further, the preparation method of the affinity ionic liquid specifically comprises the following steps:
mixing imidazole and NaH, adding THF, and stirring at 0-2 ℃ for 40-60 min; adding 1-bromohexane at room temperature, and stirring and reacting for 20-24 h; then washing with water, extracting a product with THF, and purifying with a thin-layer chromatography silica gel column to obtain an intermediate product S;
Adding 1, 6-dibromohexane into acetonitrile, heating and refluxing, slowly dropwise adding acetonitrile solution containing 0.1-0.2 g/mL of intermediate product S, and reacting at 90-95 ℃ for 24-30 h; evaporating under reduced pressure to remove the solvent, and washing with anhydrous ether for 3-5 times to obtain the imidazole cation supported ionic liquid;
mixing imidazole cation supported ionic liquid, DO3A tert-butyl ester, AF-DX 116 and potassium carbonate, adding acetonitrile, and reacting for 72-84 h at 90-95 ℃; filtering out solids, evaporating under reduced pressure to remove the solvent, and washing with anhydrous ether for 3-5 times; the product was then dissolved in ultrapure water and excess LiNTf was added 2 And (3) carrying out anion exchange for 6-8 h, then adding dichloromethane for extraction, drying with anhydrous sodium sulfate, evaporating the solvent to dryness, and repeating the operation twice to obtain the affinity ionic liquid.
The mass ratio of imidazole to NaH is 1: 0.3 to 0.5; the solid-to-liquid ratio of imidazole to THF is 0.3-0.5 g/mL; the molar ratio of imidazole to 1-bromohexane was 1: 1 to 1.2.
The solid-to-liquid ratio of the 1, 6-dibromohexane to the acetonitrile is 0.8-1.2 g/mL; the molar ratio of the intermediate product S to the 1, 6-dibromohexane is 1: 13 to 15.
The molar ratio of the imidazole cation supported ionic liquid to DO3A tert-butyl ester to AF-DX 116 is 1: 0.5-1: 0.5 to 0.8; the molar ratio of the potassium carbonate to the imidazole cation supported ionic liquid is 6-7: 1; the solid-to-liquid ratio of the imidazole cation supported ionic liquid to acetonitrile is 0.015-0.03 g/mL.
Still another object of the present invention is to provide the use of the above-mentioned affinity ionic liquid in the preparation process of opal quartz glass.
Still another object of the present invention is to provide the use of the affinity ionic liquid as a carrier, a catalyst, or an extractant.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a hot-pressing leaching technology is adopted to effectively separate the mineral inclusion and the crystal lattice substitution type impurities at the gaps of the quartz sand crystal structure, and the affinity ionic liquid is added, so that the mineral inclusion and the crystal lattice substitution type impurities can be combined with various metal ions, the removal rate of impurity metal elements is effectively improved, and the purity of the quartz sand is improved. The prepared affinity ionic liquid has higher metal chelating capacity by adopting DO3A tert-butyl ester and AF-DX 116 as functional ligands; the adsorption capacity of the ionic liquid prepared by independently using AF-DX 116 as a functional ligand to metal ions is superior to that of the ionic liquid prepared by independently using DO3A tert-butyl ester as a functional ligand; the method is applied to the purification treatment process of the quartz sand to prepare the high-purity quartz sand, so that the removal effect of impurity metal elements is obviously enhanced, and the purity of quartz sand products is improved. Meanwhile, the obtained high-purity quartz sand is applied to the preparation of the opal quartz glass, so that a product with better performance is obtained, and the radiation energy of the opal quartz glass is higher.
Therefore, the invention provides a preparation process of the opal quartz glass, and the opal quartz glass prepared by the process has higher radiation energy and better product quality; after the surface of the material is treated, the material has good self-cleaning capability; in addition, the quartz sand obtained by purification in the process has higher purity.
Drawings
FIG. 1 shows the results of the relative radiation intensity test in test example 3 of the present invention (a-comparative example 1, b-example 4, c-example 5, d-example 1).
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
the quartz sand used in the embodiment of the invention is purchased from Zhangpu county Hongxiang quartz sand Co., Ltd, and the product is obtained by screening, strong magnetic separation, flotation, roasting and water quenching of raw ore, has the particle size of 40-100 meshes and is made of SiO 2 The content is more than or equal to 98.9 percent. The crystal sand is obtained from Fucai mineral products Limited company in east China sea county, has particle size of 40-100 meshes and is made of SiO 2 ≥99.99％。
Preparation of the organosilicon binder used in the examples of the invention:
according to the mol ratio of 1: 1, adding anhydrous ethanol (the molar ratio of the anhydrous ethanol to the methyltriethoxysilane is 36.5: 1) into the methyltriethoxysilane and the phenyltrimethoxysilane, and stirring for 30 min; then, hydrochloric acid (the molar ratio of the hydrochloric acid to the methyltriethoxysilane is 0.005: 1) and water (the molar ratio of the hydrochloric acid to the methyltriethoxysilane is 4.5: 1) with the concentration of 1M are slowly dropped into the mixture, and the mixture is placed at 80 ℃ for reflux reaction for 8 hours to obtain the organic silicon adhesive.
Example 1:
preparation of affinity ionic liquid:
according to the mass ratio of 1: mixing imidazole and NaH according to the proportion of 0.42, adding THF (the solid-to-liquid ratio of imidazole to THF is 0.4g/mL), and stirring for 50min at 0 ℃; adding 1-bromohexane (the molar ratio of imidazole to 1-bromohexane is 1: 1.1) at room temperature, and stirring for reacting for 24 hours; then washing with water, extracting a product with THF, and purifying with a thin-layer chromatography silica gel column to obtain an intermediate product S;
adding 1, 6-dibromohexane into acetonitrile (the solid-liquid ratio is 1.1g/mL), heating and refluxing, slowly and dropwise adding an acetonitrile solution containing 0.16g/mL intermediate product S (the molar ratio of the intermediate product S to the 1, 6-dibromohexane is 1: 14), and reacting for 24h at 90 ℃; evaporating under reduced pressure to remove the solvent, and washing with anhydrous ether for 4 times to obtain imidazole cation supported ionic liquid; 1 H NMR(400MHz，CDCl 3 )：10.21(s，1H，Py-H)，7.82(s，1H，Py-H)，7.60(s，1H，Py-H)，4.62(t，2H，N + -CH 2 )，4.17(t，2H，N-CH 2 )，3.64(t，2H，Br-CH 2 )，2.0～1.0(16H，-CH 2 )，0.89(t，3H，-CH 3 )；
mixing imidazole cation supported ionic liquid, DO3A tert-butyl ester, AF-DX 116 and potassium carbonate, adding acetonitrile, and reacting at 90 ℃ for 72 hours; filtering to remove solid, evaporating under reduced pressure to remove solvent, and washing with anhydrous ether for 5 times; the product was then dissolved in ultrapure water and excess LiNTf was added 2 Carrying out anion exchange for 6h, then adding dichloromethane for extraction, drying with anhydrous sodium sulfate, evaporating the solvent to dryness, and repeating the operation twice to obtain an affinity ionic liquid; in the preparation process, the molar ratio of the imidazole cation supported ionic liquid to DO3A tert-butyl ester to AF-DX 116 is 1: 0.78: 0.62; the molar ratio of the potassium carbonate to the imidazole cation supported ionic liquid is 6.6: 1; the solid-to-liquid ratio of the imidazole cation supported ionic liquid to the acetonitrile is 0.023 g/mL.
A preparation process of opal quartz glass comprises the following steps:
and (3) carrying out purification pretreatment on quartz sand, taking the quartz sand, and treating the quartz sand according to a liquid-solid ratio of 4.2 mL: adding 1g of mixed acid solution according to the proportion to perform a hot-pressing leaching test, wherein the temperature is 200 ℃, the stirring speed is 200r/min, the leaching reaction is performed for 3.5h, the affinity ionic liquid (the addition amount is 0.5 percent of the mass of the quartz sand) is added, and the reaction is continued for 2.5 h; after the leaching reaction is finished, fully washing the quartz sand to be neutral by using diethyl ether and deionized water in sequence, drying and cooling the quartz sand to obtain high-purity quartz sand; the mixed acid solution comprises: hydrochloric acid of 2M concentration, hydrofluoric acid of 0.5M concentration, nitric acid of 0.5M concentration;
uniformly mixing high-purity quartz sand and crystal sand according to the mass ratio of 1:1.2 to obtain a raw material mixture;
taking a raw material mixture for high-temperature melting, wherein the conditions of temperature rise treatment comprise: heating to 1500 ℃ at the heating rate of 25 ℃/min, then heating to 1950 ℃ at the heating rate of 5 ℃/min, and then keeping the temperature for 2 hours; the cooling treatment conditions comprise: cooling to 1000 ℃ at a cooling rate of 15 ℃/min;
and (3) cooling to 810 ℃ along with the furnace, and then carrying out annealing treatment: cooling from 800 ℃ to 580 ℃ at a cooling rate of 4 ℃/min;
then, after the temperature is reduced to the normal temperature along with the furnace, repeating the heating and cooling treatment once;
Then drawing and forming, carrying out annealing treatment (the parameters are consistent with those of the annealing treatment), cooling to normal temperature along with the furnace, and finally cutting and cleaning to obtain the opal quartz glass.
Example 2:
the difference between the preparation of the affinity ionic liquid and example 1 is: the molar ratio of the imidazole cation supported ionic liquid to the DO3A tert-butyl ester to the AF-DX 116 is 1: 0.6: 0.55.
the preparation process of the opal quartz glass is different from that of the example 1 in that: the liquid-solid ratio of the mixed acid solution to the quartz sand is 5 mL: 1g of a compound; the addition amount of the affinity ionic liquid is 0.36 percent of the mass of the quartz sand.
Example 3:
the difference between the preparation of the affinity ionic liquid and example 1 is: the molar ratio of the imidazole cation supported ionic liquid to the DO3A tert-butyl ester to the AF-DX 116 is 1: 0.9: 0.7.
the preparation process of the opal quartz glass is different from that of the example 1 in that: the liquid-solid ratio of the mixed acid solution to the quartz sand is 3.2 mL: 1g of a compound; the addition amount of the affinity ionic liquid is 0.7 percent of the mass of the quartz sand.
Example 4:
the difference between the preparation of the affinity ionic liquid and example 1 is: DO3A tert-butyl ester is adopted to replace AF-DX 116 in the preparation process.
Compared with the nuclear magnetic hydrogen spectrum of the imidazole cation supported ionic liquid, the obviously more characteristic peaks in the nuclear magnetic hydrogen spectrum of the affinity ionic liquid prepared by the embodiment comprise: a high intensity signal peak at 1.31ppm, which is the signal peak for methyl hydrogen in the DO3A tert-butyl ester structure; the above results show that the affinity ionic liquid of this example was successfully prepared.
The preparation process of the opal quartz glass is different from that of the example 1 in that: the affinity ionic liquid was prepared in this example.
Example 5:
the difference between the preparation of the affinity ionic liquid and example 1 is: AF-DX 116 is adopted to replace DO3A tert-butyl ester in the preparation process.
Compared with the nuclear magnetic hydrogen spectrum of the imidazole cation supported ionic liquid, the obviously more characteristic peaks in the nuclear magnetic hydrogen spectrum of the affinity ionic liquid prepared by the embodiment comprise: a signal peak of hydrogen on a benzene ring appears within the range of 7.50-8.10 ppm; signal peaks of hydrogen on a pyridine ring appear at 8.18 ppm and 7.30-7.42 ppm; the above results show that the affinity ionic liquid of this example was successfully prepared.
The preparation process of the opal quartz glass is different from that of the example 1 in that: affinity ionic liquids were prepared as described in this example.
Example 6:
preparing functional organic silicon:
in a molar ratio of 1: 1.1, mixing chloromethyltrimethoxysilane and triethylamine, slowly adding 7-denitrified-2' -deoxyadenosine (the molar ratio of the chloromethyltrimethoxysilane to the chloromethyltrimethoxysilane is 1: 1), heating to 79 ℃, carrying out reflux reaction for 7 hours, carrying out suction filtration, reduced pressure distillation and purification to obtain the functionalized organosilicon (the structure is shown as follows); the whole reaction process is protected by nitrogen and is strictly waterproof.
1 H NMR(400MHz，DMSO-d6)：8.30(s，1H，Py-H)，7.42(d，1H，Py-H)，6.08(d，1H，Py-H)，6.01、4.52、3.60(3H，-CH)，4.07(s，1H，-NH)，3.55～3.62(2H，-OH)，3.43(s，9H，-CH 3 )，3.60～3.80、2.34～2.60(4H，-CH 2 )，2.44(s，2H，Si-CH 2 )。HRMS(ESI)：Calcd for C 15 H 24 N 4 O 6 Si,m/z[M+H] + ,584.12。
Preparation of the silicone polymer emulsion: the emulsion is prepared by an emulsion polymerization method, and the raw materials comprise methyl triethoxysilane, phenyl trimethoxysilane and functionalized organosilicon. The preparation method comprises the following steps: taking a silicon source, and carrying out emulsion polymerization under the action of an emulsifier SDBS and a catalyst strong potassium oxide to obtain an organic silicon polymer emulsion, wherein the silicon source comprises methyl triethoxysilane, phenyl trimethoxysilane and functionalized organic silicon.
Specifically, the preparation of the silicone polymer emulsion in this embodiment includes:
the molar ratio of the raw materials is 0.025: 1, mixing an emulsifier SDBS and a catalyst potassium hydroxide, adding deionized water (the molar ratio of the emulsifier SDBS to the catalyst potassium hydroxide is 25: 0.01), stirring to form a uniform mixed solution, heating to 50 ℃, stirring for 12min, slowly dropping a silicon source (the molar ratio of methyltriethoxysilane, phenyltrimethoxysilane to functionalized organosilicon is 1: 0.5: 0.4), and reacting at room temperature for 8 hours to obtain an organosilicon polymer emulsion; wherein the molar ratio of the silicon source to the potassium hydroxide is 25.6: 1. according to the invention, the functional organic silicon is obtained by modifying chloromethyl trimethoxy silane with 7-denitrification-2' -deoxyadenosine, is used as one of polymerization monomers to be compounded with other components, the organic silicon polymer emulsion is prepared by an emulsion polymerization method, and then the emulsion is coated on the surface of the opal quartz glass to form a coating, so that the hydrophobic property is better, the self-cleaning capability of the coating is effectively improved, and the dirt deposition on the surface of the opal quartz glass is prevented; and the formed coating has more stable mechanical property, can still be firmly attached to the surface of the substrate after being rubbed for many times, and has good performance.
The preparation of the affinity ionic liquid was the same as in example 1.
The preparation process of the opal quartz glass is different from that of the example 1 in that: adopting a dipping and pulling method to carry out organic silicon polymer coating treatment on the surface of the obtained opal quartz glass, which comprises the following steps:
cleaning a substrate, namely putting opal quartz glass into a sodium hydroxide solution with the concentration of 0.1M, heating for 2 hours at the temperature of 80 ℃, washing for 2 times by using distilled water, then sequentially cleaning for 20min by using absolute ethyl alcohol and deionized water, and drying for later use;
and putting the washed opal quartz glass into the organic silicon polymer emulsion, standing for 5min, pulling a coated film at the speed of 14cm/min, forming a liquid film with uniform thickness on the surface of the substrate, putting the substrate in the air for 30min, immersing the substrate in the organic silicon adhesive, pulling the substrate for 3 times at the same speed, then putting the substrate in the air for 30min, transferring the substrate into a blast drying oven, and drying the substrate for 3h at the temperature of 50 ℃.
Example 7:
the functionalized silicone, silicone polymer emulsion was prepared as in example 6.
The preparation of the affinity ionic liquid was the same as in example 6.
The preparation process of the opal quartz glass is different from that of the example 6 in that: opal quartz glass was prepared as in example 4.
Example 8:
the functionalized silicone, silicone polymer emulsion was prepared as in example 6.
The preparation of the affinity ionic liquid was the same as in example 6.
The preparation process of the opal quartz glass is different from that of the example 6 in that: opal quartz glass was prepared as in example 5.
Example 9:
the functionalized silicone was prepared as in example 6.
The preparation of the affinity ionic liquid was the same as in example 6.
The silicone polymer emulsion was prepared in contrast to example 6: during the preparation process, phenyl trimethoxy silane is adopted to replace functional organic silicon.
The preparation process of the opal quartz glass is different from that of the example 6 in that: a silicone polymer emulsion was prepared as in this example.
Comparative example 1:
the preparation process of the opal quartz glass is different from that of the example 1 in that: affinity ionic liquid is not added in the purification pretreatment process of the quartz sand.
Test example 1:
test of Metal chelating Performance
8mg of affinity ionic liquid was added to 200. mu.L of Li at the same concentration (100mM) + 、Cu 2+ 、Mn 2+ 、Al 3+ Stirring at 80 ℃ for 30min, centrifuging to remove the upper aqueous phase, and washing 3 times with 5mM acetic acid/sodium acetate buffer solution (pH 4.0); then 200 mul of hydrochloric acid solution with the concentration of 5M is added, the mixture is stirred for 6h at 70 ℃, metal ions combined with the ligand are desorbed into the water solution, and the content of the metal ions is detected by a flame method of an atomic absorption spectrophotometer.
The results of the above tests on the affinity ionic liquids prepared in examples 1 to 5 are shown in Table 1:
TABLE 1 results of the Metal chelating ability test
From the analysis in table 1, it can be seen that the affinity ionic liquid prepared in example 1 is compatible with Li + 、Cu 2+ 、Mn 2+ 、Al 3+ The chelating ability of the ionic liquid is obviously better than that of the ionic liquid prepared in the examples 4 and 5, and the result shows that the affinity ionic liquid prepared by simultaneously using DO3A tert-butyl ester and AF-DX 116 as functional ligands can obviously improve the binding ability of the ionic liquid to metal ions. Example 5 performed better than example 4, indicating that the chelating ability of the affinity ionic liquid prepared using AF-DX 116 as the functional ligand was better than that of the affinity ionic liquid prepared using DO3A tert-butyl ester as the functional ligand.
Test example 2:
characterization of Quartz Sand purification results
Determination of content of impurity metal element
Sample dissolution: taking 1g of quartz sand sample, putting the quartz sand sample into a clean and dry polytetrafluoroethylene crucible with a cover, and adding 5mL of HF, 3mL of HCl and 2mL of HNO 3 Dissolving in a 35 ℃ constant-temperature water bath for 12 hours, taking out the crucible, placing on an electric heating plate, heating to evaporate the mixed acid solution to be nearly dry, adding 5mL of hydrochloric acid, boiling, and cooling; and transferring the liquid into a 10mL volumetric flask, and performing constant volume by adopting secondary deionized water to obtain a sample to be measured. And testing Fe, K, Na, Ca, Mg and Mn elements in the quartz sand by adopting a flame atomic absorption spectrometry, and testing the content of Al elements by adopting a graphite furnace flame atomic absorption spectrometry. The test method is used for determining the contents of Al, Fe, K, Na, Ca, Mg, Mn and other elements by using a flame atomic absorption spectrometry method in a water and wastewater monitoring and analyzing method in China, and is also used for referencing corresponding national and industrial standards. The concrete preparation and operation methods refer to corresponding sections in methods for monitoring and analyzing water and wastewater (fourth edition), GB/T23837-09, GB/T11911-89 and GB/T11904-89. Before testing, standard solution is prepared according to the standard, and a standard curve is determined and drawn.
The results of the above tests on the high purity quartz sand prepared in comparative example 1 and examples 1 to 5 are shown in tables 2 and 3:
table 2 impurity removal rate test results
From the analysis in table 2, it can be seen that the removal rate of each impurity element of the high-purity quartz sand prepared in example 1 is significantly higher than that of the high-purity quartz sand prepared in examples 4 and 5, which indicates that the affinity ionic liquid prepared by using DO3A tert-butyl ester and AF-DX 116 as functional ligands is applied to the purification process of quartz sand, and has a compounding effect with a mixed acid solution and the like, so that the removal capacity of each impurity element of the quartz sand is significantly improved. The effect of example 5 is better than that of example 4, which shows that the affinity ionic liquid prepared by using AF-DX 116 as a functional ligand is better than that of the affinity ionic liquid prepared by using DO3A tert-butyl ester as a functional ligand when the affinity ionic liquid is applied to a quartz sand purification process.
TABLE 3 SiO 2 Purity test results
| Sample (I) | SiO 2 Content/% |
| Comparative example 1 | 99.311 |
| Example 1 | 99.990 |
| Example 2 | 99.972 |
| Example 3 | 99.983 |
| Example 4 | 99.628 |
| Example 5 | 99.804 |
From the analysis in table 3, it can be seen that the purity of the high-purity quartz sand prepared in example 1 is significantly higher than that of the high-purity quartz sand prepared in examples 4 and 5, and the result shows that the affinity ionic liquid prepared by using DO3A tert-butyl ester and AF-DX 116 as functional ligands is applied to a quartz sand purification process, has a compounding effect with a mixed acid solution and the like, can effectively improve the purity of quartz sand products, and is better applied to the preparation of opal quartz tube glass. The effect of example 5 is better than that of example 4, which shows that the affinity ionic liquid prepared by using AF-DX 116 as a functional ligand is applied to the purification process of quartz sand, and the improvement effect on the purity of the quartz sand is higher than that of the affinity ionic liquid prepared by using DO3A tert-butyl ester as a functional ligand.
Test example 3:
characterization of opal Quartz glass
Determination of relative radiation intensity
Ni is filled in a milky quartz tube by adopting standard electrical technology 80 Cr 20 The heating wire, i.e. constitutes the thermal element. The samples were then tested for spectral emissivity and relative light radiation intensity on an infrared radiation detector of the HFY-1 type.
The above-described tests were performed on the opal silica glasses prepared in comparative example 1, and examples 4 to 5, and the results are shown in fig. 1. Analysis in the figure shows that the relative radiation intensity of the opal quartz glass prepared in example 1 is obviously higher than that of the opal quartz glass prepared in examples 4 and 5, and the fact that the affinity ionic liquid prepared by using DO3A tert-butyl ester and AF-DX 116 as functional ligands is applied to a quartz sand purification process to obtain high-purity quartz sand and then prepare the opal quartz glass is presumed to improve the relative radiation intensity of the opal quartz glass effectively by improving the internal structure, bubble distribution, content and the like of the opal quartz glass. The effect of example 5 is better than that of example 4, which shows that the affinity ionic liquid prepared by using AF-DX 116 as a functional ligand is applied to a quartz sand purification process to prepare opal quartz glass, and the improvement effect on the radiation performance of the glass is higher than that of the affinity ionic liquid prepared by using DO3A tert-butyl ester as a functional ligand.
Test example 4:
characterization of coating Properties
Water contact Angle test
The contact angle of a water drop on the surface of a coating is measured by using an SL 200B contact angle measuring instrument manufactured by Solon Tech company, the size of the water drop is controlled by controlling a microsyringe and is dripped on the surface of the coating, a contact image of the water drop on the surface of the coating is obtained by a computer, and then the contact angle is obtained by a single circle cutting fitting method.
The above-described test was carried out on the surfaces of the opal quartz glasses obtained in example 6 and example 9, and the results are shown in table 4:
table 4 water contact angle test results
| Sample (I) | Water contact angle/° c |
| Example 6 | 159.7 |
| Example 9 | 143.2 |
From the analysis in table 4, it can be seen that the water contact angle of the opal quartz glass surface prepared in example 6 is significantly larger than that of the opal quartz glass surface prepared in example 9, which indicates that the functionalized organosilicon obtained by modifying with 7-deaza-2 '-deoxyadenosine is compounded with other components to prepare the organosilicon polymer emulsion, and the organosilicon polymer emulsion is coated on the surface of the glass substrate, so that the obtained coating has more excellent hydrophobic property, and the adhesion of pollutants on the surface of the coating can be effectively reduced due to the presence of 7-deaza-2' -deoxyadenosine modified siloxane, thereby enhancing the self-cleaning capability of the coating.
Mechanical stability test
Taking a piece of 1000-mesh sand paper, and enabling the coating to face the rough surface of the sand paper; a200 g weight was placed on the sandpaper to increase the friction between the sandpaper and the coating. When testing, the sample is moved back and forth 10cm along the ruler to define a friction test cycle, 30 cycles are performed, and then the contact angle of the surface of the sample is tested, and the mechanical stability is characterized by the reduction rate of the contact angle.
The above tests were carried out on the opal quartz glass surfaces obtained in example 6 and example 9, and the results are shown in table 5:
table 5 stability test results
| Sample(s) | Reduction rate/%) |
| Example 6 | 6.3 |
| Example 9 | 10.7 |
From the analysis in table 5, it can be seen that the contact angle reduction rate of the opal quartz glass surface prepared in example 6 is significantly lower than that of the opal quartz glass surface prepared in example 9, which indicates that the functionalized organosilicon obtained by modifying with 7-deaza-2' -deoxyadenosine is compounded with other components to prepare the organosilicon polymer emulsion, and the organosilicon polymer emulsion is coated on the surface of the glass substrate, so that the obtained coating has more excellent mechanical stability, and the coating still adheres well to the surface of the substrate, and maintains excellent superhydrophobic performance.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (6)
1. A process for producing an opal quartz glass, comprising: raw material purification → high temperature melting treatment → annealing treatment → high temperature melting treatment → drawing forming and annealing treatment → cutting and cleaning to obtain opal quartz glass;
the raw materials comprise refined quartz sand;
the raw material purification method comprises a mixed acid hot-pressing leaching method; adding affinity ionic liquid in the raw material purification process;
the affinity ionic liquid comprises imidazole cation supported ionic liquid and functional ligand; the imidazole cation supported ionic liquid is obtained by reacting imidazole with 1-bromohexane and 1, 6-dibromohexane; the functional ligand at least comprises DO3A tert-butyl ester; the functional ligand also includes AF-DX 116.
2. The process for producing an opal silica glass according to claim 1, wherein: SiO after the raw material is purified 2 The content is more than 99.9 percent.
3. The process for producing an opal silica glass according to claim 1, wherein: the high-temperature melting temperature is 1900-1950 ℃.
4. The process for producing an opal silica glass according to claim 1, wherein: the mixed acid comprises hydrochloric acid with the concentration of 2.5-4M, hydrofluoric acid with the concentration of 0.4-0.7M and nitric acid with the concentration of 0.3-0.6M.
5. The process for producing an opal quartz glass according to claim 1, wherein: the affinity ionic liquid is prepared from bromoalkane in an imidazole cation supported ionic liquid structure and active hydrogen in a functional ligand structure through substitution reaction.
6. Use of the affinity ionic liquid of claim 1 in a process for the preparation of opal quartz glass.
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| US4804422A (en) * | 1986-02-06 | 1989-02-14 | U.S. Philips Corporation | Method of purifying quartz sand |
| CN102674372A (en) * | 2012-05-04 | 2012-09-19 | 武汉理工大学 | Purification method for high-purity quartz with ultra-low metal elements |
| CN106064819A (en) * | 2016-06-01 | 2016-11-02 | 安徽晶晶石英科技有限公司 | A kind of quartz deposit prepares the method for glass sand |
| CN107555442A (en) * | 2017-09-19 | 2018-01-09 | 江苏凯达石英股份有限公司 | A kind of method that glass sand is refined using common quartz sand |
| CN107626437A (en) * | 2017-09-19 | 2018-01-26 | 江苏凯达石英股份有限公司 | A kind of glass sand preparation method of ultra-low metals content |
| CN111874914A (en) * | 2020-07-24 | 2020-11-03 | 武汉理工大学 | Method for preparing 4N high-purity quartz sand by taking pegmatite quartz as raw material |
| CN113735128A (en) * | 2021-08-16 | 2021-12-03 | 武汉理工大学 | Preparation method of high-purity quartz sand |
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2021
- 2021-12-08 CN CN202111489392.9A patent/CN114014540B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4804422A (en) * | 1986-02-06 | 1989-02-14 | U.S. Philips Corporation | Method of purifying quartz sand |
| CN102674372A (en) * | 2012-05-04 | 2012-09-19 | 武汉理工大学 | Purification method for high-purity quartz with ultra-low metal elements |
| CN106064819A (en) * | 2016-06-01 | 2016-11-02 | 安徽晶晶石英科技有限公司 | A kind of quartz deposit prepares the method for glass sand |
| CN107555442A (en) * | 2017-09-19 | 2018-01-09 | 江苏凯达石英股份有限公司 | A kind of method that glass sand is refined using common quartz sand |
| CN107626437A (en) * | 2017-09-19 | 2018-01-26 | 江苏凯达石英股份有限公司 | A kind of glass sand preparation method of ultra-low metals content |
| CN111874914A (en) * | 2020-07-24 | 2020-11-03 | 武汉理工大学 | Method for preparing 4N high-purity quartz sand by taking pegmatite quartz as raw material |
| CN113735128A (en) * | 2021-08-16 | 2021-12-03 | 武汉理工大学 | Preparation method of high-purity quartz sand |
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