CN106082677B - Mix cerium, the high Aluminous Silicate Glass-Ceramics of the ultraviolet cut-on of titanium and preparation method thereof - Google Patents
Mix cerium, the high Aluminous Silicate Glass-Ceramics of the ultraviolet cut-on of titanium and preparation method thereof Download PDFInfo
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- CN106082677B CN106082677B CN201610394546.9A CN201610394546A CN106082677B CN 106082677 B CN106082677 B CN 106082677B CN 201610394546 A CN201610394546 A CN 201610394546A CN 106082677 B CN106082677 B CN 106082677B
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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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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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
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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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
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/30—Doped silica-based glasses containing metals
- C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
- C03C2201/3423—Cerium
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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
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/30—Doped silica-based glasses containing metals
- C03C2201/40—Doped silica-based glasses containing metals containing transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
- C03C2201/42—Doped silica-based glasses containing metals containing transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn containing titanium
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- Crystallography & Structural Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
A kind of to mix cerium, the high Aluminous Silicate Glass-Ceramics of the ultraviolet cut-on of titanium, which is SiO2：40~50mol%, Al2O3：25~35mol%, MgO：5~10mol%, ZnO：0~5mol%；Li2O：0 5mol%, TiO2：5~10mol%, ZrO2：0~5mol%, CeO2：3~8mol%.Made glass thermal conductivity is between 1.0 1.2W/MK, and thermal expansion is 50 60 × 10‑7Between/K.Prepared glass is by grinding, polishing, after crystallite heat treatment, the tunable cut-off to 200 600nm scopes of xenon lamp spectrum can be achieved, the present invention can reduce the xenon lamp conversion thermal efficiency and reach more than 50%, neodymium glass is reduced in the thermal distoftion more than 60% in the case of xenon flash lamp pumping, and then the repeated work frequency of neodymium glass laser is improved, it is expected to be used in hectowatt repetition high-energy neodymium glass laser system from now on.
Description
Technical field
The invention belongs to inorganic non-metallic class photoelectric information and field of functional materials, is related to one kind and is suitable for repetition high-energy
Neodymium glass laser system, and with wave band is ended in the range of adjustable xenon lamp spectrum 200-600nm, mix the high manosil AS of cerium, titanium
Salt devitrified glass and preparation method thereof.
Background technology
Repetition high-energy neodymium glass laser suffers from being widely applied in laser impact intensified, Ti∶Sapphire laser pumping source domain
Demand.But the poor thermomechanical property of neodymium glass, on the one hand makes it can not bear very high heat accumulation, on the other hand can cause tight
The optics thermal distoftion of weight.It is then desired to study suitable pump technology to reduce the thermal accumlation in neodymium glass, and then realize neodymium
The repetition work of amorphous laser.
At present, xenon lamp is the most widely used pump light source in neodymium glass laser.Analyze xenon lamp emission spectrum and neodymium
The absorption spectrum of glass learns that the main output spectrum scope of xenon lamp is 400-1000nm, and the major absorbance peak of neodymium glass is
350nm, 530nm, 580nm, 750nm, 800nm and 870nm or so.Since the laser output wavelength of neodymium glass is 1053nm, no
It is with absorption band that the Excited state of generation is different, and then the contribution to nd glass laser efficiency and heat accumulation efficiency is also different.
In 350nm, the absorption band of 530nm, 580nm, heat is converted into by the pump energy for having more than 50%.
To meet repetition high light beam quality laser demand, different filter glass materials may be selected and realize to xenon lamp spectrum
Adjust.The filter being applied at present in high power neodymium glass laser system is mainly the quartz ampoule for mixing cerium, can only be ended
200-380nm ultraviolet lights (103466942 B of CN, yellow ultraviolet-transmitquartz quartz glass plate and preparation method thereof；CN
104609729 A, navy blue filter ultraviolet quartz tube and preparation method thereof)；And other ultraviolet cut-on filter glasses are also only limitted to
200-400nm wave bands (87105349 A of CN, fluorescent glass absorbing UV and IFR)；It cannot meet repetition high light beam quality neodymium glass
The xenon lamp spectrum regulatory demand of glass laser.In addition, xenon lamp can produce the energy of kJ (kilojoule) magnitude in 400-600nm scopes
Amount, therefore filter glass not only has the function of spectral modulation, should also have sufficiently high thermal shock resistance.
The content of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, there is provided a kind of to mix cerium, the high aluminosilicate of titanium micro-
Crystal glass and preparation method thereof, on the one hand realizes the tunable absorption in 200-600nm scopes, on the other hand increases substantially glass
The surface strength of glass, it is final to obtain the optical filtering microcrystal glass tube or micro- that meet to use in repetition high-energy neodymium glass laser system
Thermal distoftion of the neodymium glass under xenon flash lamp pumping is greatly lowered in crystal glass piece, realization.
The purpose of the present invention, is achieved by the following technical solution：
It is a kind of to mix cerium, the high Aluminous Silicate Glass-Ceramics of the ultraviolet cut-on of titanium, it is characterized in that the molar percentage group of the glass
Become：
SiO2：40~50mol%, Al2O3：25~35mol%, MgO：5~10mol%, ZnO：0~5mol%；Li2O：
0-5mol%, TiO2：5~10mol%, ZrO2：0~5mol%, CeO2：3~8mol%.
It is a kind of to mix cerium, the preparation method of the high Aluminous Silicate Glass-Ceramics of the ultraviolet cut-on of titanium, comprise the following steps：
1. calculating the percentage by weight of glass by the molar percentage that host glass forms, raw material is then weighed, is mixed
Uniformly, mixture is formed；
2. the mixture is put into crucible, it is placed in 1500~1600 DEG C of silicon molybdenum rod furnace and is melted, melts
When the change time is 2~8 small；
3. anneal：Glass pouring is put into after going out to be had warmed up into the Muffle furnace of glass transformation temperature, when insulation 3 is small after, with 5~
10 DEG C/h of rate of temperature fall is down to 200 DEG C, then cools to room temperature with the furnace；
4. the host glass after annealing is warming up to 750~850 DEG C, when insulation 8~16 is small, then proceed to be warming up to 900
~1050 DEG C, when insulation 2~8 is small, obtain nano crystalline glass.
The devitrified glass has the tunable cut-off to xenon lamp spectrum 200-600nm scopes, suitable for repetition high-energy neodymium
Optical filtering component in glass laser system.
The technique effect of the present invention：
The present invention in high alumina silicate glass by adding substantial amounts of cerium oxide and titanium oxide, by the UV absorption of glass
Wave band extends to 500nm；By being introduced while titanium oxide and zirconium oxide, increase the overall crystallization property of glass, on the one hand will
The UV absorption wave band of devitrified glass extends to 600nm, is on the other hand obviously improved the thermal shock resistance of glass.
Prepared by the present invention is used for the devitrified glass filter to xenon lamp spectrum progress ultraviolet cut-on, it can be achieved that right
The tunable cut-off of xenon lamp spectrum 400-600nm scopes；
The present invention, which prepares glass, by ion exchange, controlled micro crystallization processing, can increase substantially the thermal shock resistance of glass,
Significantly extend the service life of devitrified glass filtering device and use working frequency.
Brief description of the drawings
Fig. 1 is the H103 resin after 1 glass of system embodiment and controlled micro crystallization processing in visible-range；
Fig. 2 filters pipe with commonly mixing cerium quartz ampoule in repetition high-energy neodymium glass laser made of 1 glass of embodiment
In to the thermal efficiency influence contrast.
Specific implementation method
Embodiment 1
A kind of devitrified glass filter that ultraviolet cut-on is carried out to xenon lamp spectrum, the glass have to xenon lamp spectrum 400-
The tunable cut-off of 600nm scopes.
One, preparation processes：
The first step：It is formulated as (by mole meter)：
Second step：
Formula dispensing is given by the first step, raw material is sufficiently mixed uniformly；,
3rd step：At 1500 DEG C, mixture is divided 4~6 times and is added to quartz crucible/corundum crucible, platinum earthenware
In crucible, with fusion method be melted 4 it is small when；
4th step：When small to glass metal clarification 6 at 1550 DEG C；
6th step：When progress mechanical agitation 9 is small；
7th step：Obtained glass metal is poured into graphite or cast iron die and is shaped；
8th step：After when insulation 4 is small at 750 DEG C in Muffle furnace, conventional annealing processing is carried out；
9th step：The glass of acquisition is cut, fine grinding, after polishing, carry out soda acid combine processing 3.5 it is small when；
Tenth step：To glass sample 800 DEG C insulation 24 it is small when, be warming up to 950 DEG C insulation 10 it is small when.
Embodiment 2
Test and application are same as Example 1, and simply preparation process is different, as follows：
Preparation process：
The first step：It is formulated as (by mole meter)：
Second step：
Formula dispensing is given by the first step, raw material is sufficiently mixed uniformly；,
3rd step：At 1550 DEG C, mixture is divided 4~6 times and is added to quartz crucible/corundum crucible, platinum earthenware
In crucible, with fusion method be melted 4 it is small when；
4th step：When small to glass metal clarification 6 at 1580 DEG C；
6th step：When progress mechanical agitation 9 is small；
7th step：Obtained glass metal is poured into graphite or cast iron die and is shaped；
8th step：After when insulation 4 is small at 800 DEG C in Muffle furnace, conventional annealing processing is carried out；
9th step：The glass of acquisition is cut, fine grinding, after polishing, carry out soda acid combine processing 3.5 it is small when；；
Tenth step：To glass sample 850 DEG C insulation 24 it is small when, be warming up to 1050 DEG C insulation 10 it is small when.
Other implementations are identical with embodiment 1,2, and simply the formula in preparation process is different.It is listed below
Component.
Glass prepared by above-described embodiment has in the tunable cut-off of 200-600nm spectral regions, can inhibit xenon lamp and exists
Inefficient pumping of the 200-600nm scopes to neodymium glass rod, and then reduce the thermal distoftion in gain media.As shown in Figure 2, exist
Increase the devitrified glass prepared by embodiment 1 in neodymium-doped laser glass laser to filter pipe, reduce the thermal efficiency 50% of xenon lamp with
On；Introduced while additionally by titanium oxide and zirconium oxide, increase the overall crystallization property of glass, and then be obviously improved glass
Thermal shock resistance, under 1700 Joule energy pumpings, the pipe that filters is not burst.
Prepared by the present invention is used for the crystallite filter glass in the tunable cut-off of 200-600nm spectral regions, can be big
Thermal distoftion in amplitude reduction gain media；
The present invention prepares glass and can be handled by controlled micro crystallization, increases substantially the thermal shock resistance of glass, extends crystallite
The service life of glass filter part and use working frequency.
Claims (3)
1. a kind of mix cerium, the high Aluminous Silicate Glass-Ceramics of the ultraviolet cut-on of titanium, the molar percentage composition of the glass is characterized in that
For：SiO2：40~50mol%, Al2O3：25~35mol%, MgO：5~10mol%, ZnO：0~5mol%；Li2O：0-
5mol%, TiO2：5~10mol%, ZrO2：0~5mol%, CeO2：3~8mol%.
2. according to claim 1 mix cerium, the high Aluminous Silicate Glass-Ceramics of the ultraviolet cut-on of titanium, it is characterised in that have pair
The tunable cut-off of xenon lamp spectrum 200-600nm scopes, the optical filtering member device suitable for repetition high-energy neodymium glass laser system
Part.
3. mix cerium, the preparation method of the high Aluminous Silicate Glass-Ceramics of the ultraviolet cut-on of titanium described in claim 1, it is characterised in that
Comprise the following steps：
1. calculating the percentage by weight of glass by the molar percentage that host glass forms, raw material is then weighed, is uniformly mixed,
Form mixture；
2. the mixture is put into crucible, it is placed in 1500~1600 DEG C of silicon molybdenum rod furnace and is melted, during fusing
Between for 2~8 it is small when；
3. anneal：Glass pouring is put into after going out to be had warmed up into the Muffle furnace of glass transformation temperature, insulation 3 it is small when after, with 5~10
DEG C/h rate of temperature fall be down to 200 DEG C, then cool to room temperature with the furnace；
4. the host glass after annealing is warming up to 750~850 DEG C, when insulation 8~16 is small, then proceed to be warming up to 900~
1050 DEG C, when insulation 2~8 is small, obtain nano crystalline glass.
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| CN201610394546.9A CN106082677B (en) | 2016-06-06 | 2016-06-06 | Mix cerium, the high Aluminous Silicate Glass-Ceramics of the ultraviolet cut-on of titanium and preparation method thereof |
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| CN107171168A (en) * | 2017-07-25 | 2017-09-15 | 秦树军 | It is a kind of to improve the spectrum body of laser photoelectricity conversion efficiency and optical quality |
| CN110698061A (en) * | 2019-11-07 | 2020-01-17 | 成都为光科技有限公司 | Samarium and cerium doped infrared absorption low-expansion aluminum borate glass and preparation method thereof |
| CN112038468A (en) * | 2020-09-17 | 2020-12-04 | 有研稀土新材料股份有限公司 | Red LED optical device |
Citations (3)
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|---|---|---|---|---|
| US4162921A (en) * | 1977-01-05 | 1979-07-31 | Firsov Vitaly M | Glass-crystalline material and method of producing same |
| RU2374190C1 (en) * | 2008-04-22 | 2009-11-27 | Федеральное государственное унитарное предприятие "Обнинское научно-производственное предприятие "Технология" | Glass-ceramic material |
| CN102503145A (en) * | 2011-10-26 | 2012-06-20 | 中国科学院上海光学精密机械研究所 | Cobalt-ytterbium-erbium co-doped nanometer microcrystalline glass and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000313639A (en) * | 1999-02-25 | 2000-11-14 | Nippon Sheet Glass Co Ltd | Crystallized glass and method for producing the same, and substrate using the same and used for information recording medium, information recording medium and information recording device |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4162921A (en) * | 1977-01-05 | 1979-07-31 | Firsov Vitaly M | Glass-crystalline material and method of producing same |
| RU2374190C1 (en) * | 2008-04-22 | 2009-11-27 | Федеральное государственное унитарное предприятие "Обнинское научно-производственное предприятие "Технология" | Glass-ceramic material |
| CN102503145A (en) * | 2011-10-26 | 2012-06-20 | 中国科学院上海光学精密机械研究所 | Cobalt-ytterbium-erbium co-doped nanometer microcrystalline glass and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Crystallization behavior and microwave dielectric property of MgO-Al2O3-SiO2-TiO2-CeO2 glass-ceramic;Jiangang Wang等;《Journal of Alloys and Compounds》;20071007;第464卷;第440-445页 * |
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