CN101693596B - Neodymium ion doping soda-lime-silica based laser glass ceramics and preparation process thereof - Google Patents
Neodymium ion doping soda-lime-silica based laser glass ceramics and preparation process thereof Download PDFInfo
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- CN101693596B CN101693596B CN2009102103853A CN200910210385A CN101693596B CN 101693596 B CN101693596 B CN 101693596B CN 2009102103853 A CN2009102103853 A CN 2009102103853A CN 200910210385 A CN200910210385 A CN 200910210385A CN 101693596 B CN101693596 B CN 101693596B
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Abstract
The invention provides rare-earth ion (Nd3+) doping Na2O-CaO-SiO2 based transparent glass ceramics laser working matter materials. Compositions and mass percentage content of the materials are: Na2O 17.5-20.0%, CaO 26.5-28.0%, SiO2 45.5-50.0%, TiO2+ZrO2 4.0-5.0%, Sb2O3+NH4NO3 3.0-5.0% and Nd2O3 1.0-5.0%. The preparation process of the materials is: (1) proportioning and smelting; (2) molding and annealing; (3) glass cutting; (4) glass heat treatment; (5) glass ceramics cold working; (6) performance test. The glass ceramics materials have both excellent performances of glass and single crystals. Compared with single crystal matrixes, the transparent laser glass ceramics materials have simple production technology, low cost and high doping concentration; compared with glass matrixes, as microcrystalline phases in the glass matrixes are precipitated, thermal conductivity and thermal shock resistance of the materials are improved. Simultaneously, as luminous ions selectively enter the microcrystalline phases, the materials are enabled to have spectral characteristics of crystalloids, fluorescence lines are narrowed, and fluorescence intensity is enhanced.
Description
Technical field
The invention belongs to the inorganic non-metallic materials science field, particularly a kind of transparent glass ceramics working-laser material material and preparation method thereof.
Background technology
Laser, English are Laser (Light Amplification by Stimulated Emission ofRadiation), i.e. stimulated radiation light amplification, and it is a kind of brand-new light source of extensive application.Laser is the extraordinary light that is produced by laser apparatus, and according to the difference of operation material, laser apparatus can be divided into four big classes such as gas, liquid, solid and semi-conductor.In solid laser, working-laser material mainly contains monocrystalline and glass two classes.Glass and monocrystalline respectively have its relative merits as laser host material: monocrystalline thermal conductivity height, gain are high, are applicable to continuously and height repeats sharp penetrating, and shortcoming is that preparation technology duplicates, cost height, doping content are low; Glass fluorescence Spectra live width, physical parameter is adjustable, preparation technology is simple, cost is low, doping content is high, can make large size, is applicable to that high energy pulse swashs to penetrate, and shortcoming is that thermal conductivity is low, and thermal shock resistance is relatively poor.Glass-ceramic (Glass-ceramics) is a kind of type material between pottery and glass, it can gather the advantage of monocrystalline and glass, is expected to become in microchip laser apparatus, fiber amplifier and high-power diode pumping solid laser field the working-laser material material of a new generation.About the existing relevant report of the research of glass-ceramic working-laser material material, mainly concentrate on oxyfluoride system, sulfur halide system etc., rare earth ion doped Na involved in the present invention both at home and abroad
2O-CaO-SiO
2Be transparent glass ceramics working-laser material material, have no precedent relevant report at laser field according to the result for retrieval of Web of Science.
Summary of the invention
The object of the present invention is to provide a kind of rare earth ion (Nd
3+) doping Na
2O-CaO-SiO
2It is transparent glass ceramics working-laser material material and preparation method thereof.This Nd
3+Doping Na
2O-CaO-SiO
2Be that the transparent laser glass ceramic material has that production technique is simple, cost is low, doping content is high and characteristics such as fluorescence intensity height.
The present invention realizes by following technical scheme:
Nd
3+Doping Na
2O-CaO-SiO
2The feed composition and the content (mass percent, down together) that are the transparent laser glass-ceramic are: Na
2O 17.5～20.0%; CaO 26.5～28.0%; SiO
245.5～50.0%; TiO
2+ ZrO
24.0～5.0%, Sb
2O
3+ NH
4NO
33.0～5.0%, Nd
2O
31.0～5.0%.
Nd
3+Doping Na
2O-CaO-SiO
2The preparation method who is the transparent laser glass-ceramic is:
By above-mentioned Nd
3+Doping Na
2O-CaO-SiO
2The component and the content that are transparent laser glass-ceramic raw material are prepared burden, and even batch mixing is 2～3 hours in planetary ball mill, in 1450 ℃ of fusions 3～4 hours, cast molding.Vitreum after the moulding is eliminated internal stress in 450～500 ℃ of insulations annealing in 1～2 hour, carry out crystallization then and handle, obtain transparent laser glass-ceramic sample, carry out performance test.
This Nd
3+Doping Na
2O-CaO-SiO
2The host glass that is transparent laser glass-ceramic and identical chemical constitution is compared, and fluorescence intensity has improved about 50%, reaches 75% but thickness is the laser glass ceramics of 2mm in Jiang Guang district transmitance, in the transmitance of near infrared light greater than 80%.
A kind of Nd provided by the invention
3+Doping Na
2O-CaO-SiO
2Be the excellent properties that the transparent laser glass-ceramic integrates monocrystalline and glass, compare that this transparent laser glass ceramic material production technique is simple, cost is low, mix the concentration height with single crystal substrate; Compare with glass matrix, because crystallite must be separated out thermal conductivity and the thermal shock resistance that has improved material mutually in the host glass.Simultaneously and since light emitting ionic enter selectively crystallite mutually in, make material have like the crystalline spectral signature, fluorescent line narrows down, the fluorescence intensity grow.
Description of drawings
Fig. 1 is the fluorescent emission curve of glass-ceramic after pristine glass and the thermal treatment
Embodiment
Embodiment 1
A kind of Na
2O-CaO-SiO
2The raw material that is the transparent laser glass-ceramic is formed batching 100g.Measure 18.9%Na
2O, 27.2%CaO, 47.9%SiO
2, 2.5%TiO2+ZrO
2, 0.5%Sb
2O
3, 2%NH
4NO
3, 1%Nd
2O
3
Its preparation method:
(1) glass melting: by above-mentioned Nd
3+Doping Na
2O-CaO-SiO
2Be the component of transparent laser glass-ceramic raw material and content batching, evenly batch mixing was poured corundum crucible into after 3 hours in planetary ball mill, in 1450 ℃ of fusions 4 hours, injected the stainless steel mould of preheating in silicon molybdenum resistance furnace, the melt curing molding of lowering the temperature rapidly.
(2) glass annealing: the vitreum after the moulding is placed in 500 ℃ of retort furnaces insulation 2 hours rapidly, reduce to room temperature with stove then, finally obtain the transparent glass of lilac;
(3) glass cutting: with cutting machine the glasswork for preparing is cut into fritter, be used for follow-up crystallization and thermal treatment;
(4) glass heat is handled: determine the glass crystallization heat treating regime according to the differential thermal analysis result, the fritter sample after the cutting 737 ℃ of thermal treatments 10 hours, is obtained transparent glass ceramics;
(5) glass-ceramic cold working: carry out twin grinding and polishing with the silicon carbide powder of the varying particle size glass-ceramic sample after with thermal treatment, grinding and polishing reaches the optical accuracy requirement, and obtaining the transparent glass ceramics thickness of sample is 2mm;
(6) performance measurement: employing ultraviolet-near infrared spectrometer measurement thickness is that the transmitance of the transparent laser glass-ceramic of 2mm is about 75%; Adopt the fourier fluorescence spectrophotometer to measure the fluorescence spectrum of transparent laser glass-ceramic, as shown in Figure 1, determine that its laser work wavelength is 1062nm, compare with the glass matrix of identical chemical constitution, fluorescent line narrows down, and fluorescence intensity has improved 52%.
Embodiment 2
Na
2O-CaO-SiO
2Be the transparent laser glass-ceramic, raw material: 17.7%Na
2O, 26.0%CaO, 46.3%SiO
2, 4.5%TiO2+ZrO
2, 0.5%Sb
2O
3, 2%NH
4NO
3, 3%Nd
2O
3
Glass heat is handled: sample obtains transparent glass ceramics 720 ℃ of thermal treatments 6 hours;
Other is with embodiment 1.
Performance measurement: fluorescence intensity has improved 56%.
Claims (3)
1. neodymium ion doping soda-lime-silica based laser glass ceramics, it is characterized in that: described laser glass ceramics is with rare earth ion Nd
3+Doping Na
2O-CaO-SiO
2Be transparent glass ceramics, the working-laser material material of formation, wherein, Nd
3+Doping Na
2O-CaO-SiO
2Be that transparent laser glass-ceramic feed composition and mass percentage content are: Na
2O 17.5～20.0%, CaO26.5～28.0%, SiO
245.5～50.0%, TiO
2+ ZrO
24.0～5.0%, Sb
2O
3+ NH
4NO
33.0～5.0%, Nd
2O
31.0～5.0%, each component concentration sum is 100%.
2. laser glass ceramics according to claim 1, it is characterized in that: described laser glass ceramics is 75% at the visible and near-infrared band average transmittances of 400～1200nm, its laser work wavelength is 1062nm, compare with the glass matrix of identical chemical constitution, fluorescence intensity has improved 50%.
3. the preparation method of a neodymium ion doping soda-lime-silica based laser glass ceramics is characterized in that: with rare earth ion Nd
3+Doping Na
2O-CaO-SiO
2Be transparent glass ceramics, concrete preparation method is:
(1) glass batch mixing, melting: Nd
3+Doping Na
2O-CaO-SiO
2Be that the component of transparent laser glass-ceramic raw material and mass percentage content are by Na
2O 17.5～20.0%, and CaO 26.5～28.0%, SiO
245.5～50.0%, TiO
2+ ZrO
24.0～5.0%, Sb
2O
3+ NH
4NO
33.0～5.0%, Nd
2O
31.0～5.0%, each component concentration sum is 100% batching, evenly batch mixing was poured corundum crucible into after 3 hours in planetary ball mill, in 1450 ℃ of fusions 4 hours, injected the stainless steel mould of preheating in silicon molybdenum resistance furnace, the melt curing molding of lowering the temperature rapidly;
(2) glass annealing: the glass block after the moulding is placed in 500 ℃ of retort furnaces insulation 2 hours rapidly, cool to room temperature then with the furnace, finally obtain the lilac transparent glass;
(3) glass cutting: with cutting machine the glass block of preparation is cut into the goods of desired size and shape, be used for follow-up crystallization and thermal treatment;
(4) glass heat is handled: determine the glass crystallization heat treating regime according to the experimental result of differential thermal analysis, the fritter sample after the cutting 730 ℃ of thermal treatments 10 hours, is obtained transparent glass ceramics;
(5) glass-ceramic cold working: carry out twin grinding and polishing with the silicon carbide powder of the varying particle size glass-ceramic sample after with thermal treatment, grinding and polishing reaches the optical accuracy requirement, and finally obtaining the transparent glass ceramics thickness of sample is 2mm;
(6) performance test: adopting ultraviolet-near infrared spectrometer to measure thickness is the transmitance of the transparent laser glass-ceramic of 2mm; Adopt the fourier fluorescence spectrophotometer to measure the fluorescence spectrum of transparent laser glass-ceramic, determine its operation wavelength.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102103853A CN101693596B (en) | 2009-11-02 | 2009-11-02 | Neodymium ion doping soda-lime-silica based laser glass ceramics and preparation process thereof |
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|---|---|---|---|
| CN2009102103853A CN101693596B (en) | 2009-11-02 | 2009-11-02 | Neodymium ion doping soda-lime-silica based laser glass ceramics and preparation process thereof |
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| CN101693596B true CN101693596B (en) | 2011-06-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014166083A1 (en) * | 2013-04-10 | 2014-10-16 | 中国科学院福建物质结构研究所 | White-light led containing new solid-state transparent fluorescent material and preparation method therefor |
-
2009
- 2009-11-02 CN CN2009102103853A patent/CN101693596B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014166083A1 (en) * | 2013-04-10 | 2014-10-16 | 中国科学院福建物质结构研究所 | White-light led containing new solid-state transparent fluorescent material and preparation method therefor |
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| CN101693596A (en) | 2010-04-14 |
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