CN111302618A - Process method for preparing bismuth-doped quartz glass by sol-gel method - Google Patents
Process method for preparing bismuth-doped quartz glass by sol-gel method Download PDFInfo
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- CN111302618A CN111302618A CN202010094977.XA CN202010094977A CN111302618A CN 111302618 A CN111302618 A CN 111302618A CN 202010094977 A CN202010094977 A CN 202010094977A CN 111302618 A CN111302618 A CN 111302618A
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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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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
- C03B19/066—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction for the production of quartz or fused silica articles
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Abstract
The invention discloses a process method for preparing bismuth-doped quartz glass by a sol-gel method, which comprises the following steps: (1): uniformly mixing and stirring ethyl orthosilicate, deionized water and ethanol according to a certain proportion, and adding a certain proportion of Bi (NO) dissolved by nitric acid3·5H2O and Al (NO)3·9H2O, stirring the mixture by using a magnetic stirrer at normal temperature to obtain bismuth-doped sol; (2) stirring and heating the sol by using a magnetic stirrer to obtain wet gel, drying the wet gel in an oven to remove most of water and ethanol to form blocky dried gel, and ball-milling the blocky dried gel by using a planetary ball mill to form powder; (3) putting the dry gel powder into a degreasing furnace to remove carbides and organic matters in the dry gel powder to obtain bismuth-doped precursor powder; (4) putting presintered precursor powder into vacuum meltingSintering in a smelting furnace to obtain the bismuth-doped quartz glass in a vacuum state. The invention can obviously reduce the sintering temperature of the powder and the prepared bismuth-doped glass has good uniformity.
Description
Technical Field
The invention belongs to the field of quartz glass preparation, and particularly relates to a process method for preparing bismuth-doped quartz glass by a sol-gel method.
Background
The bismuth-doped quartz glass can generate near-infrared luminescence with the half-height width of about 300nm in a near-infrared region, is a novel luminescent material discovered by people in recent years, has the fluorescence life of hundreds of microseconds, and can be used as a gain material of an optical fiber amplifier. According to the research of relevant documents, the working wavelength of the erbium-doped fiber amplifier is fixed and the gain bandwidth is not flat. The substrate material of the thulium-doped optical fiber amplifier is mostly tellurate glass or fluoride glass which is not easy to be welded with the quartz-based transmission optical fiber. The bismuth-doped optical fiber amplifier can realize the optical amplification of the low-loss window of the whole quartz optical fiber through one bismuth-doped quartz-based optical fiber. The ultra-wide emission spectrum and the long fluorescence lifetime make the bismuth-doped silicate glass a potential gain medium for ultra-wide band fiber amplifiers and tunable lasers.
In recent decades, a great deal of research has been conducted on bismuth-doped quartz glass. Most researchers have used high temperature melting methods to make bismuth-doped glasses. The high-temperature melting method is a common method for preparing glass, and is mainly used for mixing raw materials and powder and then carrying out high-temperature melting. However, this method requires firing the powder into glass at high temperature, which causes a large amount of bismuth ions to be volatilized, and the bismuth-doped glass produced is not uniform in composition. How to realize the uniform and high-concentration doping of bismuth is a difficult problem which troubles bismuth-doped glass at present.
Disclosure of Invention
In order to solve the problems, the invention provides a process method for preparing bismuth-doped quartz glass by a sol-gel method.
The technical scheme of the invention is as follows:
a process method for preparing bismuth-doped quartz glass by a sol-gel method comprises the following steps:
(1) according to deionized water: anhydrous ethanol: the molar ratio of ethyl orthosilicate is 1: 1: 4, respectively measuring and taking out a certain volume of solution. Pouring tetraethoxysilane into absolute ethyl alcohol, and stirring the mixture at room temperature by using a magnetic stirrer to uniformly disperse tetraethoxysilane in the absolute ethyl alcohol;
(2) adding Bi (NO) to deionized water in sequence3·5H2O and Al (NO)3·9H2O, stirring by using a glass rod;
(3) adding nitric acid into the beaker filled with the mixed solution in the step (2) while stirring until the mixed solution is Bi (NO)3·5H2O and Al (NO)3·9H2Completely dissolving O to form a colorless transparent solution;
(4) slowly dripping the solution formed in the step (3) into the solution formed in the step (1) by using a dropper;
(5) stirring the solution obtained in the step (4) at a medium speed by using a magnetic stirrer, and finally forming wet gel by the uniform sol;
(6) putting the wet gel formed in the step (5) into an oven to be dried for more than 12 hours until most of water and ethanol in the wet gel volatilize to form a blocky xerogel;
(7) and (4) ball-milling the dried gel formed in the step (6) by using a planetary ball mill to form dried gel powder, wherein the rotating speed is 300r/min, and the time is 10 h.
(8) Putting the dry gel powder into a degreasing furnace, heating to 600 ℃, and removing carbon and organic matters in the dry gel powder to obtain bismuth-doped precursor powder;
(9) putting the precursor powder obtained in the step (8) into a planetary ball mill for ball milling again, wherein the rotating speed is 200r/min, and the time is 2 h;
(10) and (4) putting the precursor powder in the step (9) into a vacuum smelting furnace for sintering, and heating to 1600-1700 ℃ in a vacuum state for 2 hours to obtain the bismuth-doped quartz glass.
The invention has the following beneficial effects:
the invention adopts a sol-gel method to prepare glass precursor powder with uniformly doped bismuth, and the bismuth-doped quartz glass with uniform components is fired at a relatively low temperature.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
The raw materials used in the examples are conventional raw materials.
Example 1
The invention provides a process method for preparing bismuth-doped quartz glass by a sol-gel method, which comprises the following steps:
(1) according to deionized water: anhydrous ethanol: the molar ratio of ethyl orthosilicate is 1: 1: 4, respectively measuring and taking out a certain volume of deionized water, absolute ethyl alcohol and ethyl orthosilicate. Pouring tetraethoxysilane into absolute ethyl alcohol, and stirring the mixture at room temperature by using a magnetic stirrer to uniformly disperse tetraethoxysilane in the absolute ethyl alcohol;
(2) sequentially adding the mixture into deionized water according to a molar ratio of 0.3: 2.2 of Bi (NO)3·5H2O and Al (NO)3·9H2O, stirring by using a glass rod;
(3) adding nitric acid into the beaker filled with the mixed solution in the step (2) while stirring until the mixed solution is Bi (NO)3·5H2O and Al (NO)3·9H2Completely dissolving O to form a colorless transparent solution;
(4) slowly dripping the solution formed in the step (3) into the solution formed in the step (1) by using a dropper;
(5) stirring the solution obtained in the step (4) at a medium speed by using a magnetic stirrer, and finally forming wet gel by the uniform sol;
(6) putting the wet gel formed in the step (5) into an oven to be dried for more than 12 hours until most of water and ethanol in the wet gel volatilize to form a blocky xerogel;
(7) ball-milling the dried gel formed in the step (6) by using a planetary ball mill to form dried gel powder, wherein the rotating speed is 300r/min, and the time is 10 h;
(8) putting the dry gel powder into a degreasing furnace, heating to 600 ℃, and removing carbon and organic matters in the dry gel powder to obtain bismuth-doped precursor powder;
(9) putting the precursor powder obtained in the step (8) into a planetary ball mill for ball milling again, wherein the rotating speed is 200r/min, and the time is 2 h;
(10) putting the precursor powder in the step (9) into a vacuum smelting furnace for sintering, and heating to 1600-1700 ℃ in a vacuum stateFor 2 hours, to obtain the final product of 0.15 mol% Bi2O3The transparent gain glass of (1);
(11) when the gain glass is applied to laser, the near infrared luminescence peak value of a sample under the excitation of light of 700nm is about 1135nm, and the full width at half maximum of fluorescence is about 130 nm.
Example 2
The invention provides a process method for preparing bismuth-doped quartz glass by a sol-gel method, which comprises the following steps:
(1) according to deionized water: anhydrous ethanol: the molar ratio of ethyl orthosilicate is 1: 1: 4, respectively measuring and taking out a certain volume of deionized water, absolute ethyl alcohol and ethyl orthosilicate. Pouring tetraethoxysilane into absolute ethyl alcohol, and stirring the mixture at room temperature by using a magnetic stirrer to uniformly disperse tetraethoxysilane in the absolute ethyl alcohol;
(2) sequentially adding the mixture into deionized water according to a molar ratio of 0.6: 2.2 of Bi (NO)3·5H2O and Al (NO)3·9H2O, stirring by using a glass rod;
(3) adding nitric acid into the beaker filled with the mixed solution in the step (2) while stirring until the mixed solution is Bi (NO)3·5H2O and Al (NO)3·9H2Completely dissolving O to form a colorless transparent solution;
(4) slowly dripping the solution formed in the step (3) into the solution formed in the step (1) by using a dropper;
(5) stirring the solution obtained in the step (4) at a medium speed by using a magnetic stirrer, and finally forming wet gel by the uniform sol;
(6) putting the wet gel formed in the step (5) into an oven to be dried for more than 12 hours until most of water and ethanol in the wet gel volatilize to form a blocky xerogel;
(7) ball-milling the dried gel formed in the step (6) by using a planetary ball mill to form dried gel powder, wherein the rotating speed is 300r/min, and the time is 10 h;
(8) putting the dry gel powder into a degreasing furnace, heating to 600 ℃, and removing carbon and organic matters in the dry gel powder to obtain bismuth-doped precursor powder;
(9) putting the precursor powder obtained in the step (8) into a planetary ball mill for ball milling again, wherein the rotating speed is 200r/min, and the time is 2 h;
(10) and (4) putting the precursor powder in the step (9) into a vacuum smelting furnace for sintering, and heating to 1600-1700 ℃ in a vacuum state for 2 hours to obtain the bismuth-doped quartz glass.
Example 3
The invention provides a process method for preparing bismuth-doped quartz glass by a sol-gel method, which comprises the following steps:
(1) according to deionized water: anhydrous ethanol: the molar ratio of ethyl orthosilicate is 1: 1: 4, respectively measuring and taking out a certain volume of deionized water, absolute ethyl alcohol and ethyl orthosilicate. Pouring tetraethoxysilane into absolute ethyl alcohol, and stirring the mixture at room temperature by using a magnetic stirrer to uniformly disperse tetraethoxysilane in the absolute ethyl alcohol;
(2) adding deionized water into the mixture in a molar ratio of 0.9: 2.2 of Bi (NO)3·5H2O and Al (NO)3·9H2O, stirring by using a glass rod;
(3) adding nitric acid into the beaker filled with the mixed solution in the step (2) while stirring until the mixed solution is Bi (NO)3·5H2O and Al (NO)3·9H2Completely dissolving O to form a colorless transparent solution;
(4) slowly dripping the solution formed in the step (3) into the solution formed in the step (1) by using a dropper;
(5) stirring the solution obtained in the step (4) at a medium speed by using a magnetic stirrer, and finally forming wet gel by the uniform sol;
(6) putting the wet gel formed in the step (5) into an oven to be dried for more than 12 hours until most of water and ethanol in the wet gel volatilize to form a blocky xerogel;
(7) ball-milling the blocky xerogel formed in the step (6) by using a planetary ball mill to form xerogel powder, wherein the rotating speed is 300r/min, and the time is 10 h;
(8) putting the dry gel powder into a degreasing furnace, heating to 600 ℃, and removing carbon and organic matters in the dry gel powder to obtain bismuth-doped precursor powder;
(9) putting the precursor powder obtained in the step (8) into a planetary ball mill for ball milling again, wherein the rotating speed is 200r/min, and the time is 2 h;
(10) and (4) putting the precursor powder in the step (9) into a vacuum smelting furnace for sintering, and heating to 1600-1700 ℃ in a vacuum state for 2 hours to obtain the bismuth-doped quartz glass.
Claims (4)
1. A process method for preparing bismuth-doped quartz glass by a sol-gel method is characterized by comprising the following steps:
(1) according to deionized water: anhydrous ethanol: the molar ratio of ethyl orthosilicate is 1: 1: 4, respectively measuring out solutions with preset volumes; pouring tetraethoxysilane into absolute ethyl alcohol, and stirring the mixture at room temperature by using a magnetic stirrer to uniformly disperse tetraethoxysilane in the absolute ethyl alcohol;
(2) adding Bi (NO) to deionized water in sequence3·5H2O and Al (NO)3·9H2O, stirring by using a glass rod;
(3) adding nitric acid into the beaker filled with the mixed solution in the step (2) while stirring until the mixed solution is Bi (NO)3·5H2O and Al (NO)3·9H2Completely dissolving O to form a colorless transparent solution;
(4) slowly dripping the solution formed in the step (3) into the solution formed in the step (1) by using a dropper;
(5) stirring the solution obtained in the step (4) at a medium speed by using a magnetic stirrer, and finally forming wet gel by the uniform sol;
(6) putting the wet gel formed in the step (5) into an oven to be dried for more than 12 hours until most of water and ethanol in the wet gel volatilize to form a blocky xerogel;
(7) ball-milling the dried gel formed in the step (6) by using a planetary ball mill to form dried gel powder, wherein the rotating speed is 300r/min, and the time is 10 h;
(8) putting the dry gel powder into a degreasing furnace, heating to 600 ℃, and removing carbon and organic matters in the dry gel powder to obtain bismuth-doped precursor powder;
(9) putting the precursor powder obtained in the step (8) into a planetary ball mill for ball milling again, wherein the rotating speed is 200r/min, and the time is 2 h;
(10) and (4) putting the precursor powder in the step (9) into a vacuum smelting furnace for sintering, and heating to 1600-1700 ℃ in a vacuum state for 2 hours to obtain the bismuth-doped quartz glass.
2. The process for preparing bismuth-doped quartz glass according to claim 1, wherein Bi (NO)3·5H2O and Al (NO)3·9H2The O molar ratio is 0.3: 2.2.
3. the process for preparing bismuth-doped quartz glass according to claim 1, wherein Bi (NO)3·5H2O and Al (NO)3·9H2The O molar ratio is 0.6: 2.2.
4. the process for preparing bismuth-doped quartz glass according to claim 1, wherein Bi (NO)3·5H2O and Al (NO)3·9H2The molar ratio of O is 0.9: 2.2.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1129334A (en) * | 1997-03-06 | 1999-02-02 | Mitsubishi Cable Ind Ltd | Silica glass doped with bismuth, its production, optical fiber using its glass, and optical amplifier |
| JP2002252397A (en) * | 2001-02-22 | 2002-09-06 | Japan Science & Technology Corp | Optical fiber and optical amplifier |
| CN101508520A (en) * | 2009-03-11 | 2009-08-19 | 昆明理工大学 | Bismuth doped phosphosilicate glass and method of producing the same |
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2020
- 2020-02-17 CN CN202010094977.XA patent/CN111302618A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1129334A (en) * | 1997-03-06 | 1999-02-02 | Mitsubishi Cable Ind Ltd | Silica glass doped with bismuth, its production, optical fiber using its glass, and optical amplifier |
| JP2002252397A (en) * | 2001-02-22 | 2002-09-06 | Japan Science & Technology Corp | Optical fiber and optical amplifier |
| CN101508520A (en) * | 2009-03-11 | 2009-08-19 | 昆明理工大学 | Bismuth doped phosphosilicate glass and method of producing the same |
Non-Patent Citations (1)
| Title |
|---|
| 祁康成主编: "《发光原理与发光材料》", 29 February 2012, 电子科技大学出版社 * |
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Application publication date: 20200619 |