CN114634310A - Phosphate laser neodymium glass and preparation method thereof - Google Patents
Phosphate laser neodymium glass and preparation method thereof Download PDFInfo
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- CN114634310A CN114634310A CN202210226420.6A CN202210226420A CN114634310A CN 114634310 A CN114634310 A CN 114634310A CN 202210226420 A CN202210226420 A CN 202210226420A CN 114634310 A CN114634310 A CN 114634310A
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- glass
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- phosphate laser
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Classifications
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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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
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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
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0071—Compositions for glass with special properties for laserable glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Abstract
The invention provides phosphate laser neodymium glass and a preparation method thereof, belonging to the technical field of glass, and the phosphate laser neodymium glass comprises the following components in percentage by mol: p2O550‑65mol％；Al2O33‑10mol％；R2O15-30 mol%, wherein R is one or more of Li, Na and K, and K2The O content is not less than 15 mol%; MO 6-30 mol%, wherein M is one or more of Mg and Ba, and the BaO content is not less than 6 mol%; re2O30.05-2 mol%, wherein Re is one of Nd, Y and La, and Nd2O3The content is not less than 0.05 mol%; nb2O50.2‑1.5mol％；Sb2O30‑1mol％. The thermo-optic coefficient of the glass prepared by the invention is not more than-5 multiplied by 10‑7A stimulated emission cross section of not less than 3.8 × 10 ° C‑20cm2And has wide application prospect.
Description
Technical Field
The invention relates to the technical field of glass, in particular to phosphate laser neodymium glass and a preparation method thereof.
Background
The phosphate glass has moderate phonon energy, high solubility to rare earth ions, excellent spectral performance of the rare earth ions in phosphate matrix glass, high solubility to platinum ions and small nonlinear coefficient, so that the phosphate glass becomes a laser glass medium widely used in large-scale laser devices. The neodymium ions have many absorption peaks in a visible near infrared region, and are preferably pumped by a wide-spectrum light source such as a xenon lamp, and the neodymium ions are four-energy-level systems and are often used as activating ions of a laser gain medium. Phosphate laser neodymium glass is phosphate glass taking neodymium ions as active ions and is widely applied to various laser systems.
Due to the existence of physical processes such as quantum defect, excited state absorption, concentration quenching and the like in the phosphate laser neodymium glass, a part of pumping energy is converted into heat energy and is deposited in the medium, so that the temperature of the medium is increased, and temperature gradient, thermal stress and thermal strain are generated in the laser material, thereby generating a series of thermal effects. The repetition frequency operation of a laser system using phosphate laser neodymium glass as a gain medium can cause the accumulation of the heat effect, and the existence of heat can cause the instantaneous refractive index change of the laser neodymium glass to form an optical path difference, thereby causing the wavefront distortion.
The change of the optical path difference of the laser after passing through the amplifier is mainly caused by three reasons, namely that the first is the end surface deformation of the laser medium caused by thermal expansion; secondly, the refractive index of the neodymium glass sheet is changed due to the thermo-optic effect; the third is the strain induced birefringence effect. In the gain medium, thermally induced wavefront distortion is a combined effect of the three factors. The derivative of the optical path change caused by end face deformation and stress birefringence to the temperature is mostly positive, and the derivative of the optical path change caused by thermo-optic effect to the temperature (thermo-optic coefficient) is positive or negative. Therefore, the thermal distortion effect can be reduced by designing the material with the negative thermo-optic coefficient. The thermo-optic coefficient of the phosphate laser neodymium glass commonly used at present is mostly positive, for example, the thermo-optic coefficient of the N31 type laser neodymium glass is 14 x 10-7/° c, resulting in deterioration of beam quality of the output beam of the laser system.
Disclosure of Invention
The invention aims to provide phosphate laser neodymium glass and a preparation method thereof, wherein the thermo-optic coefficient of the glass is not more than-5 multiplied by 10-7A stimulated emission cross section of not less than 3.8 × 10 at/° C-20cm2And has wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides phosphate laser neodymium glass which comprises the following components in percentage by mole:
P2O5 50-65mol％；
Al2O3 3-10mol％；
R2o15-30 mol%, wherein R is one or more of Li, Na and K, and K2The O content is not less than 15 mol%;
MO 6-30 mol%, wherein M is one or more of Mg and Ba, and the BaO content is not less than 6 mol%;
Re2O30.05-2 mol%, wherein Re is one of Nd, Y and La, and Nd2O3The content is not less than 0.05 mol%;
Nb2O5 0.2-1.5mol％；
Sb2O3 0-1mol％。
as a further improvement of the invention, wherein K2O+Na2The O content is not less than 18 mol%.
As a further improvement of the invention, the glass has a thermo-optic coefficient of not more than-5X 10-7/℃。
As a further improvement of the present invention, the glass has a stimulated emission cross section of not less than 3.8X 10-20cm2。
The invention further provides a preparation method of the phosphate laser neodymium glass, which comprises the following steps: weighing raw materials corresponding to each component of the glass in proportion, fully mixing, adding into a platinum crucible, melting, clarifying, homogenizing and cooling; pouring molten glass into the preheated metal mold; and putting the molten glass injected into the preheated metal mold and the metal mold into an annealing furnace together, and annealing to obtain the phosphate neodymium glass.
As a further improvement of the invention, the melting temperature is 900-1100 ℃.
As a further improvement of the invention, the temperature of the molten glass during pouring is 900-1200 ℃.
The invention has the following beneficial effects: the invention prepares phosphate laser neodymium glass with a negative thermo-optic coefficient, and the thermo-optic coefficient of the glass is not more than-5 multiplied by 10-7A stimulated emission cross section of not less than 3.8 × 10 at/° C-20cm2Besides excellent laser gain characteristics, the laser neodymium glass has a large negative thermo-optic coefficient, so that the heat effect of the laser neodymium glass in the using process can be reduced, and the laser neodymium glass has wide application prospects in the fields of high-power laser devices, solid lasers, laser ranging and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Under the condition of not considering thermal stress, the optical path difference change generated by the thermal effect of the laser glass under the action of high-energy laser is caused by refractive index change and glass size change, and can be characterized by a thermo-optic coefficient W:
wherein s is the optical path of the laser through the glass, T is the temperature, alpha is the coefficient of thermal expansion, n is the refractive index of the glass, and dn/dT is the temperature coefficient of refractive index. The temperature coefficient of refractive index can be expressed as:
wherein γ is the polarizability, and α is the thermal expansion coefficient of the glass. As can be seen from the formula, when the temperature rises, on the one hand the density of the glass decreases due to thermal expansion of the glass, resulting in a decrease in the refractive index of the glass. On the other hand, the refractive index of the glass increases due to the increase in polarizability. The change in the refractive index of the glass with temperature therefore depends on the sum of the two effects mentioned above. From the above two equations, the following expression for the thermo-optic coefficient can be derived:
the visible thermo-optic coefficient is inversely related to the expansion coefficient and the polarizability. In order to reduce the thermo-optic coefficient, the designed glass needs to have a higher expansion coefficient and a higher polarizability. For the same family elements, ions with large radii generally have relatively small ionic field strength, so that the corresponding glass has a large expansion coefficient and high ionic polarizability. Therefore, when the glass contains a large amount of K2O、Na2The addition of BaO to the glass is advantageous in reducing the thermo-optic coefficient of the glass.
The invention is further illustrated by the following examples:
weighing raw materials corresponding to the glass components in the embodiment in proportion, fully mixing, adding into a platinum crucible, melting at 900-1100 ℃, clarifying, homogenizing and cooling; pouring the molten glass into the preheated metal mold at the temperature of 900-; and (3) putting the molten glass injected into the preheated metal mold and the metal mold into an annealing furnace, annealing to obtain the neodymium phosphate glass, and testing the relevant performance parameters of the neodymium phosphate glass as shown in table 1.
TABLE 1
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. The phosphate laser neodymium glass is characterized by comprising the following components in percentage by mol:
P2O5 50-65mol％；
Al2O3 3-10mol％；
R2o15-30 mol%, wherein R is one or more of Li, Na and K, and K2The O content is not less than 15 mol%;
MO 6-30 mol%, wherein M is one or more of Mg and Ba, and the BaO content is not less than 6 mol%;
Re2O30.05-2 mol%, wherein Re is one of Nd, Y and La, and Nd2O3The content is not less than 0.05 mol%;
Nb2O5 0.2-1.5mol％；
Sb2O3 0-1mol％。
2. the phosphate laser neodymium glass according to claim 1, wherein K is K2O+Na2The O content is not less than 18 mol%.
3. The phosphate laser neodymium glass according to claim 1, wherein the glass has a thermo-optic coefficient of not more than-5 x 10-7/℃。
4. The phosphate laser neodymium glass according to claim 1, wherein the stimulated emission cross section of the glass is not less than 3.8 x 10-20cm2。
5. A method for preparing the phosphate laser neodymium glass according to any one of claims 1 to 4, comprising the steps of: weighing raw materials corresponding to each component of the glass in proportion, fully mixing, adding into a platinum crucible, melting, clarifying, homogenizing and cooling; pouring molten glass into the preheated metal mold; and putting the molten glass injected into the preheated metal mold and the metal mold into an annealing furnace together, and annealing to obtain the phosphate neodymium glass.
6. The method as claimed in claim 5, wherein the melting temperature is 900-1100 ℃.
7. The method as claimed in claim 5, wherein the temperature of the molten glass during the casting is 900-1200 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210226420.6A CN114634310B (en) | 2022-03-09 | 2022-03-09 | Phosphate laser neodymium glass and preparation method thereof |
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| CN202210226420.6A CN114634310B (en) | 2022-03-09 | 2022-03-09 | Phosphate laser neodymium glass and preparation method thereof |
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| CN114634310A true CN114634310A (en) | 2022-06-17 |
| CN114634310B CN114634310B (en) | 2023-07-18 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239645A (en) * | 1975-03-18 | 1980-12-16 | Hoya Glass Works, Ltd. | Phosphate base laser glasses |
| CN102515527A (en) * | 2011-12-08 | 2012-06-27 | 成都光明光电股份有限公司 | Phosphate optical glass |
| CN104926114A (en) * | 2015-06-18 | 2015-09-23 | 成都光明光电有限责任公司 | Phosphate laser neodymium glass |
| CN105753316A (en) * | 2014-12-16 | 2016-07-13 | 成都光明光电股份有限公司 | Thermooptic effect-free phosphate laser neodymium glass |
| CN106746611A (en) * | 2017-01-05 | 2017-05-31 | 中国科学院上海光学精密机械研究所 | With the larger phosphate laser neodymium glass for bearing hot light path coefficient and high-gain |
-
2022
- 2022-03-09 CN CN202210226420.6A patent/CN114634310B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239645A (en) * | 1975-03-18 | 1980-12-16 | Hoya Glass Works, Ltd. | Phosphate base laser glasses |
| CN102515527A (en) * | 2011-12-08 | 2012-06-27 | 成都光明光电股份有限公司 | Phosphate optical glass |
| CN105753316A (en) * | 2014-12-16 | 2016-07-13 | 成都光明光电股份有限公司 | Thermooptic effect-free phosphate laser neodymium glass |
| CN108840564A (en) * | 2014-12-16 | 2018-11-20 | 成都光明光电股份有限公司 | The phosphate laser neodymium glass of luminescence effect |
| CN104926114A (en) * | 2015-06-18 | 2015-09-23 | 成都光明光电有限责任公司 | Phosphate laser neodymium glass |
| CN106746611A (en) * | 2017-01-05 | 2017-05-31 | 中国科学院上海光学精密机械研究所 | With the larger phosphate laser neodymium glass for bearing hot light path coefficient and high-gain |
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| CN114634310B (en) | 2023-07-18 |
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