CN114634310B - Phosphate laser neodymium glass and preparation method thereof - Google Patents
Phosphate laser neodymium glass and preparation method thereof Download PDFInfo
- Publication number
- CN114634310B CN114634310B CN202210226420.6A CN202210226420A CN114634310B CN 114634310 B CN114634310 B CN 114634310B CN 202210226420 A CN202210226420 A CN 202210226420A CN 114634310 B CN114634310 B CN 114634310B
- Authority
- CN
- China
- Prior art keywords
- glass
- less
- content
- phosphate
- laser
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—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
-
- 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, which belong to the technical field of glass, and the mol percent composition of the components comprises: p (P) 2 O 5 50‑65mol％；Al 2 O 3 3‑10mol％；R 2 O15-30 mol%, wherein R is one or more of Li, na and K, and K 2 The O content is not less than 15mol%; MO 6-30mol%, wherein M is one or more of Mg and Ba, and the content of BaO is not less than 6mol%; re (Re) 2 O 3 0.05 to 2mol%, wherein Re is one of Nd, Y and La, and Nd 2 O 3 The content is not less than 0.05mol%; nb (Nb) 2 O 5 0.2‑1.5mol％；Sb 2 O 3 0-1mol%. The thermo-optic coefficient of the glass prepared by the invention is not more than-5 multiplied by 10 ‑7 The stimulated emission cross section is not less than 3.8X10 at/DEGC ‑20 cm 2 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
Phosphate glass is widely used as a laser glass medium in a large-scale laser device due to moderate phonon energy, high solubility for rare earth ions, excellent spectral performance of rare earth ions in phosphate matrix glass, high solubility for platinum ions and small nonlinear coefficient. The neodymium ion has more absorption peaks in the visible near infrared region, a xenon lamp and other broad spectrum light sources are preferably adopted for pumping, and the neodymium ion is a four-energy-level system and is commonly used as an active ion of a laser gain medium. Phosphate laser neodymium glass is phosphate glass with neodymium ions as activating ions, and is widely applied to various laser systems.
Due to the physical processes of 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 deposited in the medium, so that the temperature of the medium is increased, and the temperature gradient, the thermal stress and the thermal strain are generated in the laser material, so that a series of thermal effects are generated. The repetition frequency operation of a laser system using phosphate laser neodymium glass as a gain medium can further cause accumulation of thermal effects, and the existence of heat can cause instantaneous refractive index change of the laser neodymium glass to form optical path difference, thereby causing wave front distortion.
The optical path difference of the laser after passing through the amplifier is changed mainly due to three reasons, namely, the first is that the laser medium generates end face deformation due to thermal expansion; secondly, the refractive index of the neodymium glass sheet is changed due to the thermo-optical effect; the third is the strain induced birefringence effect. In the gain medium, the thermally induced wavefront distortion is a composite effect of the three influencing factors. Wherein the derivative of the optical path change caused by the deformation of the end face and stress birefringence to the temperature is more positive, and the derivative of the optical path caused by the thermo-optical effect to the temperature (thermo-optical coefficient) is positive and negative. Therefore, the thermal distortion effect can be reduced by designing a material having a thermo-optic coefficient of a negative value. The coefficient of thermal-optical coefficient of the phosphate laser neodymium glass commonly used at present is mostly positive, for example, the coefficient of thermal-optical coefficient of the N31 laser neodymium glass is 14 multiplied by 10 -7 And/c, resulting in deterioration of beam quality of the laser system output beam.
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 -7 The stimulated emission cross section is not less than 3.8X10 at/DEGC -20 cm 2 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:
P 2 O 5 50-65mol％；
Al 2 O 3 3-10mol％；
R 2 o15-30 mol%, wherein R is one or more of Li, na and K, and K 2 The O content is not less than 15mol%;
MO 6-30mol%, wherein M is one or more of Mg and Ba, and the content of BaO is not less than 6mol%;
Re 2 O 3 0.05 to 2mol%, wherein Re isOne of Nd, Y and La, and Nd 2 O 3 The content is not less than 0.05mol%;
Nb 2 O 5 0.2-1.5mol％；
Sb 2 O 3 0-1mol％。
as a further improvement of the invention, wherein, K 2 O+Na 2 The O content is not less than 18mol%.
As a further improvement of the invention, the thermo-optic coefficient of the glass is not more than-5×10 -7 /℃。
As a further improvement of the present invention, the stimulated emission section of the glass is not less than 3.8X10 -20 cm 2 。
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 a preheated metal mold; and (3) putting the molten glass injected into the preheated metal mold and the metal mold into an annealing furnace, and obtaining the phosphate neodymium glass after annealing.
As a further development of the invention, the melting temperature is 900-1100 ℃.
As a further development of the invention, the molten glass temperature at the time of casting is 900-1200 ℃.
The invention has the following beneficial effects: the invention prepares the phosphate laser neodymium glass with a heat-light coefficient of negative value, and the heat-light coefficient of the glass is not more than-5 multiplied by 10 -7 The stimulated emission cross section is not less than 3.8X10 at/DEGC -20 cm 2 Besides excellent laser gain characteristics, the high-power neodymium glass has a large negative thermo-optical coefficient, so that the thermal effect in the use process of the laser neodymium glass can be reduced, and the high-power neodymium glass has a wide application prospect in the fields of high-power laser devices, solid lasers, laser ranging and the like.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments 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.
Under the action of high-energy laser, the change of optical path difference generated by thermal effect of the laser glass is caused by the change of refractive index and the change of glass size, and can be characterized by a thermo-optical coefficient W:
where s is the optical path of the laser through the glass, T is the temperature, α 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:
where γ is the polarizability and α is the coefficient of thermal expansion of the glass. As can be seen from the equation, when the temperature increases, on the one hand, the density of the glass decreases due to the thermal expansion of the glass, resulting in a decrease in the refractive index of the glass. On the other hand, the increase in the refractive index of the glass is caused by the increase in the polarization ratio. Thus, the refractive index of glass varies with temperature depending on the sum of the two effects. From the two formulas, the following expression of the thermo-optic coefficient can be deduced:
the visible heat light coefficient is in negative correlation with 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 group of elements, ions of large radius generally have relatively small ion field strengths, resulting in a corresponding glass having a large coefficient of expansion, and a high ion polarizationThe rate. Therefore, when the glass contains more K 2 O、Na 2 O is advantageous in BaO for reducing the thermo-optic coefficient of the glass.
The invention is further illustrated by the following examples:
weighing the 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 molten glass into a preheated metal mould at the temperature of about 900-1200 ℃; and placing the molten glass injected into the preheated metal mold and the metal mold into an annealing furnace, and obtaining the phosphate neodymium glass after annealing, wherein the relevant performance parameters of the phosphate neodymium glass are shown in table 1.
TABLE 1
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (4)
1. The phosphate laser neodymium glass is characterized by comprising the following components in percentage by mole:
P 2 O 5 50-65mol％；
Al 2 O 3 3-10mol％；
R 2 o15-30 mol%, wherein R is one or more of Li, na and K, and K 2 The O content is not less than 15mol%;
MO 6-30mol%, wherein M is one or more of Mg and Ba, and the content of BaO is not less than 6mol%;
Re 2 O 3 0.05 to 2mol%, wherein Re is one of Nd, Y and La, and Nd 2 O 3 The content is not less than 0.05mol%;
Nb 2 O 5 0.2-1.5mol％；
Sb 2 O 3 0-1mol％；
the glass has a thermo-optic coefficient of not more than-5×10 -7 /℃；
The stimulated emission cross section of the glass is not less than 3.8X10 -20 cm 2 ；
Wherein K is 2 O+Na 2 The O content is not less than 18mol%.
2. A method for preparing the phosphate laser neodymium glass according to claim 1, comprising 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 a preheated metal mold; and (3) putting the molten glass injected into the preheated metal mold and the metal mold into an annealing furnace, and obtaining the phosphate neodymium glass after annealing.
3. The method of claim 2, wherein the melting temperature is 900-1100 ℃.
4. The method of claim 2, wherein the molten glass temperature at the time of casting is 900-1200 ℃.
Priority Applications (1)
| 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 |
Applications Claiming Priority (1)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114634310A CN114634310A (en) | 2022-06-17 |
| CN114634310B true CN114634310B (en) | 2023-07-18 |
Family
ID=81947432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210226420.6A Active CN114634310B (en) | 2022-03-09 | 2022-03-09 | Phosphate laser neodymium glass and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114634310B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5342333B2 (en) * | 1975-03-18 | 1978-11-10 | ||
| CN102515527B (en) * | 2011-12-08 | 2014-11-05 | 成都光明光电股份有限公司 | Phosphate optical glass |
| CN105753316B (en) * | 2014-12-16 | 2019-02-26 | 成都光明光电股份有限公司 | The phosphate laser neodymium glass of luminescence effect |
| CN104926114B (en) * | 2015-06-18 | 2018-02-16 | 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 |
-
2022
- 2022-03-09 CN CN202210226420.6A patent/CN114634310B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114634310A (en) | 2022-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Stevenson et al. | Fluoride materials for optical applications: Single crystals, ceramics, glasses, and glass–ceramics | |
| Hu et al. | Effect of Er3+ concentration on spectral characteristic and 2.79 μm laser performance of Er: YSGG crystal | |
| Furuse et al. | Transparent ultrafine Yb3+: Y2O3 laser ceramics fabricated by spark plasma sintering | |
| CN111377609B (en) | Preparation method of transparent glass with mid-infrared 3.9 mu m luminescence characteristic at room temperature | |
| Yu et al. | Growth and Characteristics of Yb-doped ${\rm Y} _ {3}{\rm Ga} _ {5}{\rm O} _ {12} $ Laser Crystal | |
| CN110927866B (en) | High-gain rare earth doped germanate glass core composite glass optical fiber and device | |
| Doualan et al. | Latest developments of bulk crystals and thin films of rare-earth doped CaF2 for laser applications | |
| Qian et al. | Efficient 2 μm emission in Er3+/Ho3+ co-doped lead silicate glasses under different excitations | |
| Tang et al. | Silicate-clad highly Er3+/Yb3+ co-doped phosphate core multimaterial fibers | |
| Jiang et al. | Transparent Nd-doped Ca1− xYxF2+ x ceramics prepared by the ceramization of single crystals | |
| Zhao et al. | Concentration effect of Yb3+ ions on the spectroscopic properties of high-concentration Er3+/Yb3+ co-doped phosphate glasses | |
| Wang et al. | Glass‐forming regions and enhanced 2.7 μm emission by Er3+ heavily doping in TeO2–Ga2O3–R2O (or MO) glasses | |
| CN112430847A (en) | Thulium erbium dysprosium tri-doped lead fluoride mid-infrared laser crystal, preparation method and application | |
| CN114634310B (en) | Phosphate laser neodymium glass and preparation method thereof | |
| KR20140068786A (en) | Tuning rare earth ion emission wavelength in phosphate based glasses using cerium oxide | |
| CN101024552B (en) | YB3+ dopped ion fluophosphate laser glass material containing high-valence cationic exide and its preparing method | |
| Wang et al. | Influence of SiO2 on the Stark splitting and spectroscopic properties of Yb3+ in phosphate glass | |
| Jiang et al. | Heat‐driven Tailored for Eliminating Nd3+ Re‐clusters in Nd3+, Gd3+‐codoped SrF2 Laser Ceramic | |
| CN101293737A (en) | Ytterbium fluorine phosphate doped laser glass with high transmission section and preparation method thereof | |
| CN115395356A (en) | Erbium-doped double-clad zirconium fluoride-based glass optical fiber and preparation method thereof | |
| CN109369007B (en) | 2.7-micron luminous high-concentration tellurium-gallium-zinc-doped laser glass and preparation method thereof | |
| CN106483599B (en) | Rare earth ion doped phosphate glass microcrystalline optical fiber | |
| CN116253512B (en) | Germanate glass capable of inhibiting darkening of gamma ray irradiation and preparation method thereof | |
| CN115821387B (en) | Growth method of ultra-high melting point rare earth doped hafnium oxide optical single crystal | |
| Zhang et al. | Preparation, spectroscopic, thermal properties, and laser performances of ordered Nd3+: Ca3TaGa2. 1Al0. 9Si2O14 crystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |