CN106242272B - A kind of doping Bi3+SiO2- CaO-MgO based laser glass and preparation method thereof - Google Patents
A kind of doping Bi3+SiO2- CaO-MgO based laser glass and preparation method thereof Download PDFInfo
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- CN106242272B CN106242272B CN201610644111.5A CN201610644111A CN106242272B CN 106242272 B CN106242272 B CN 106242272B CN 201610644111 A CN201610644111 A CN 201610644111A CN 106242272 B CN106242272 B CN 106242272B
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
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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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- 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
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
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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
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/0071—Compositions for glass with special properties for laserable glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/58—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with metals in non-oxide form, e.g. CdSe
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Abstract
A kind of doping Bi3+SiO2- CaO-MgO based laser glass is related to fiber optic materials technical field, which is made of base and dopant, and base includes SiO2, CaO and MgO, dopant is containing Bi3+Compound, Bi3+Molal quantity account for base total mole number 3%-8%.The laser glass is in SiO2Bi is adulterated in-CaO-MgO systems matrix3+, generated under the excitation of launch wavelength 800nm~1100nm laser near-infrared luminous, and luminous efficiency is high, the bandwidth that shines is very wide.The present invention also provides a kind of doping Bi3+SiO2The preparation method of-CaO-MgO based laser glass, be to specified raw material than raw material heating, pour into mold, molding, again using the annealing of specific process conditions, cooling, which can give full play to the luminescent effect of Bi ions, and production efficiency is high, at low cost.
Description
Technical field
The present invention relates to fiber optic materials technical fields, in particular to a kind of doping Bi3+SiO2- CaO-MgO systems swash
Light glass and preparation method thereof.
Background technology
Nobel Prize in physics winner Gao Kun professors have just been put forward for the first time the (letter of low-loss optical fiber early in 1966
Claim optical fiber) concept, later he produce first optical fiber in the world, make information superhighway the whole world grow rapidly.
Window wave-length coverage based on low-loss optically fiber communication is 1200~1600nm, and fiber amplifier refers to applying to light
In fiber communication circuit, realize signal amplification a kind of new all optical amplifier, fiber amplifier have Raman fiber amplifiers and
A variety of rare-earth ion activated fiber amplifiers such as Er, Tm, Pr.But the near-infrared luminous source of rare earth ion is in 4f orbital energy levels
Between transition can occur, this transition is shown narrow luminous bandwidth by the shielding of outer layer 6s, 5d orbital electron, to make
The window wave-length coverage of rare earth ion doped optical fiber amplifier is narrow, for example, the wave-length coverage of conventional C-band be 1530~
The window wave-length coverage for mixing Pr fiber amplifiers of 1565nm, O wave band is 1280~1320nm, and S-band mixes Tm fiber amplifiers
The window wave-length coverage of device TDFA is 1420~1520nm.
Therefore, it even if by existing rare earth ion doped optical fiber amplifier in parallel or being together in series, can not realize entire
The light amplification of optical communicating waveband.If the fiber amplifier of ultra wide band can be developed, that is, use an optical fiber, a pumping source
The light amplification of entire optical communicating waveband is can be achieved with, this can undoubtedly bring a new revolution to optical communication field.
Japanese Scientists Fujimoto in 2001 is found that near-infrared wave in main group metal Bi ion-doped glass for the first time
The broad-band illumination of section, and propose that it is applied to the foreground of broadband optical fiber amplifier.Russian scientist Dianov in 2005 etc. exists
The laser that wavelength is 1150~1300nm is realized in the optical fiber of Bi ion dopings for the first time to export.Then, other main group metals from
The broad-band illumination characteristic of sub (s, p electron configuration, including Bi, Te, Pb, Sn, Sb etc.) is gradually found.Scientist's discovery, main group
S, p valence electron of metal ion are in the outermost layer of electronic shell, strong with coordination field interactions, are easy to be formed similar to transition gold
Belong to the broad-band illumination of ion, and its emission wavelength extends near infrared region, there is major application foreground.
But up to the present, doping main group metal Bi ions luminescent material near-infrared luminous luminous efficiency, shine
Bandwidth is all bad, and main cause is that the Effective Doping concentration of Bi ions is not high, and the Bi ionoluminescences quantum efficiency after adulterating is not
Enough ideals, therefore develop that new to mix Bi ion broad-band illumination materials necessary.
Invention content
The purpose of the present invention is to provide a kind of doping Bi3+SiO2- CaO-MgO based laser glass, in launch wavelength position
Generated under the excitation of 800nm~1100nm laser near-infrared luminous, and luminous efficiency is high, the bandwidth that shines is very wide.
Another object of the present invention is to provide a kind of doping Bi3+SiO2The preparation side of-CaO-MgO based laser glass
Method, which can give full play to the luminescent effect of Bi ions, and production efficiency is high, at low cost.
What the embodiment of the present invention was realized in：
A kind of doping Bi3+SiO2- CaO-MgO based laser glass, is made of base and dopant, and base includes
SiO2, CaO and MgO, dopant is containing Bi3+Compound, Bi3+Molal quantity account for base total mole number 3%~8%.
In preferred embodiments of the present invention, above-mentioned dopant includes Bi2O3、BiCl3At least one of.
In preferred embodiments of the present invention, above-mentioned Bi3+Molal quantity account for base total mole number 4%~7.6%.
In preferred embodiments of the present invention, above-mentioned SiO2, CaO and MgO mole ratio be 40~60：40~25：20
~15.
A kind of doping Bi3+SiO2The preparation method of-CaO-MgO based laser glass comprising following steps：
It takes base and dopant to mix to obtain mixture, heats the mixture to the glass metal in molten state；
Glass metal is poured on and is preheated in 350 DEG C~400 DEG C of mold, glass is shaped to；
Annealing, cooling.
In preferred embodiments of the present invention, the method for above-mentioned heating is：By mixture with 5 DEG C/min~10 DEG C/min
Heating rate be warming up to 1280 DEG C~1340 DEG C, and keep the temperature 1h~1.5h.
In preferred embodiments of the present invention, above-mentioned heating is carried out in non-oxidising gas environment, the flow of non-oxidising gas
For 0.5L/min~0.6L/min.
In preferred embodiments of the present invention, the method for above-mentioned annealing is：By the mold equipped with glass be placed in 380 DEG C~
1h~2h is kept the temperature at 420 DEG C.
In preferred embodiments of the present invention, above-mentioned preparation method further includes being carried out to glass after cooling using X-ray
The step of radiation treatment.
In preferred embodiments of the present invention, the energy of above-mentioned X-ray is 20KeV~40KeV, and irradiation dose is ranging from
20KGy~30KGy, dosage rate are 100Gy/h~200Gy/h.
The advantageous effect of the embodiment of the present invention is：
The laser glass of the embodiment of the present invention is made of base and dopant, and base includes SiO2, CaO and
MgO, dopant are containing Bi3+Compound, Bi3+Molal quantity account for base total mole number 3%~8%.In SiO2-CaO-
Bi is adulterated in MgO systems matrix3+Later, generated under the excitation that launch wavelength is located at 800nm~1100nm laser it is near-infrared luminous,
And luminous efficiency is high, the bandwidth that shines is very wide, and luminescent lifetime extends.In addition, the laser glass of the embodiment of the present invention is to specific
Raw material than raw material heating, pour into mold, molding, then using specific process conditions annealing, cooling and formed, the preparation method
The luminescent effect of Bi ions can be given full play to, and production efficiency is high, at low cost.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is emission spectrum of the laser glass that provides of the embodiment of the present invention 1 under the laser diode excitation of 808nm；
Fig. 2 is fluorescence intensity attenuation curve at any time of the laser glass that provides of the embodiment of the present invention 1 at 1240nm.
Specific implementation mode
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to the doping Bi of the embodiment of the present invention3+SiO2- CaO-MgO based laser glass and preparation method thereof is had
Body explanation.
The embodiment of the present invention provides a kind of doping Bi3+SiO2- CaO-MgO based laser glass, by base and doping
Object is made, and base includes SiO2, CaO and MgO, dopant is containing Bi3+Compound, Bi3+Molal quantity account for the total of base
The 3%~8% of molal quantity.
The embodiment of the present invention selects SiO2, CaO and MgO SiO is made as basic object2- CaO-MgO systems matrix, it is one
Kind is particularly suitable for doping Bi3+Matrix, which can adulterate the Bi of high concentration3+, and will not generation concentration Quenching,
Wherein Bi3+A concentration of 3mol%~8mol% of Effective Doping, and adulterate after Bi3+Luminous quantum efficiency up to 80%
More than.Therefore, the laser glass of the embodiment of the present invention has higher Bi ion dopings concentration, and luminous efficiency is high, luminous
Bandwidth is very wide, and comprehensive performance is apparently higher than other Bi ion-doped glass；It is located at 800nm~1100nm in launch wavelength
It generates near-infrared luminous under the excitation of laser, can be applied to near-infrared communication, and to be located at optical transmission loss relatively low for the wavelength exported
Operation window wavelength, have important application prospect.
Under normal conditions, Bi is adulterated in matrix3+Doping chemical species there are many kinds of, as long as to the photism of laser glass
Can be without too big negative effect, in the present embodiment, dopant includes Bi2O3、BiCl3One or both of, it preferably includes
Bi2O3, this is because Bi2O3、 BiCl3It is smaller to the negative effect of laser glass luminescent properties, the Bi (Bi of oxidation state2O3) right
Laser glass luminescent properties almost have no adverse effect.
Under normal conditions, Bi3+There is different doping concentration ranges in different matrix, in the present embodiment, Bi3+Rub
Your number accounts for the 4%~7.6% of the total mole number of base, and preferably 5%~7%.Within the scope of this doping concentration, laser glass
The luminescent properties of glass are best, and the sexual valence being applied in industry is relatively high.
SiO2- CaO-MgO based laser glass is with SiO2, the SiO that is formed of CaO and MgO2- CaO-MgO systems matrix is base
Matter, SiO2, CaO and MgO molar ratio needs can play Bi3+Optical activity, in the present embodiment, SiO2, CaO and MgO rub
Your number ratio is 40~60：40~25：20~15, at this point, the emission lifetime of obtained laser glass is long, half at 1240nm
Phase of declining is 0.58 millisecond or more, and luminous intensity is big.
The embodiment of the present invention also provides a kind of doping Bi3+SiO2The preparation method of-CaO-MgO based laser glass, packet
Include following steps：
First, it takes base and dopant to mix to obtain mixture, heats the mixture to the glass metal in molten state, preferably
Heating means be：Mixture is warming up to 1280 DEG C~1340 DEG C with the heating rate of 5 DEG C/min~10 DEG C/min, and is kept the temperature
1h~1.5h.Further preferably, heating is carried out in the non-oxidising gas environment of flowing, and the flow of non-oxidising gas is 0.5L/
Min~0.6L/min, wherein heating can carry out in high-temperature atmosphere furnace, and non-oxidising gas environment is mostly nitrogen environment.
Secondly, glass metal is poured on and is preheated in 350 DEG C~400 DEG C of mold, glass is shaped to, the temperature of mold is preferred
Preheating is close or equal to subsequent annealing temperature.
Then, it anneals, is cooling to get laser glass.Preferably method for annealing is：Mold equipped with glass is placed in 380
DEG C~420 DEG C at keep the temperature 1.5h~2h, anneal, can fully eliminate in glass in 380 DEG C~420 DEG C of high-temperature atmosphere furnace
Residual stress, stable dimensions, reduce deformation and crackle tendency, make glass have evenly, stablize luminescent properties, Yi Jifa
The higher excellent luminance performance of the wide very wide while luminous efficiency of light belt.
Preferably, above-mentioned preparation method also needs to carry out radiation treatment to glass after cooling using X-ray.The energy of X-ray
Amount is 20KeV~40KeV, and irradiation dose ranging from 20KGy~30KGy, dosage rate is 100Gy/h~200Gy/h.X is added to penetrate
Line irradiation process can greatly improve the concentration of the laser glass centre of luminescence.
In the present embodiment, if using common glass object processing method, i.e. the processes such as heating, melting, cooling process this
Embodiment adulterates Bi3+SiO2- CaO-MgO based laser glass, laser glass performance obtained can be poor, this is because glass
The process conditions of processing can have a major impact the performance of glass.The preparation method of the embodiment of the present invention is only used, it is obtained
Adulterate Bi3+SiO2The comprehensive performance of-CaO-MgO based laser glass is better.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
Embodiment 1 provides a kind of doping Bi3+SiO2The group of-CaO-MgO based laser glass, the laser glass becomes
40SiO2-40CaO-20MgO-3Bi2O3, the laser glass according to following procedure be made：
Using SiO2、CaO、MgO、Bi2O3Make raw material (SiO2, CaO, MgO be basic object, Bi2O3For dopant), it presses
SiO2, CaO, MgO and Bi3+Mole ratio be 40：40：20：6 carry out dispensing, specifically weigh the SiO of 240g (4mol)2,
The Bi of the MgO and 139.8g (0.3mol) of the CaO of 224g (4mol), 80g (2mol)2O3, when being put into mortar one section of grinding
Between, so that it is sufficiently mixed uniformly, uniform raw material will be ground and poured into corundum crucible, the corundum crucible of sealing is then put into height
It is heated in warm atmosphere furnace, high-temperature atmosphere furnace (under argon gas atmosphere, protection gas argon flow amount is 0.6L/min) is heated up with 10 DEG C/min
Rate is warming up to 1280 DEG C, and in this temperature 1.5h, the sample in corundum crucible is the glass metal in molten state at this time.
Glass metal is poured into the mold for preheating 20min at 350 DEG C in advance, glass is shaped to, by the mold equipped with glass
It is put into heat preservation 1.5h in 380 DEG C of high-temperature atmosphere furnace to anneal, then cooled to room temperature, by glass sample by mold
It takes out.
It is cut into the glass blocks of 2cm × 1cm in glass sample, is milled to 2mm thickness, and surface is polished, then to the glass
Block carries out radiation treatment, and the X-ray energy that irradiation bomb uses is 20KeV, irradiation dose ranging from 20KGy, and dosage rate is
100Gy/h to get the present embodiment laser glass.
Product testing：Laser glass is tested into Room temperature emission spectra in Triax550 Fluorescence Spectrometer, using transmitted wave
The laser diode of a length of 808nm irradiates laser glass as pumping source, and test results are shown in figure 1：Laser glass emits light
The peak wavelength of spectrum is located at 1240nm, halfwidth about 300nm.
Using the attenuation curve of Tektronix TDS3052 digital oscilloscopes record 1240nm fluorescence intensities at any time, knot
Fruit is as shown in Fig. 2, it is 0.58ms to obtain 1240nm fluorescence lifetimes by first-order exponential decay equation model experimental data.
Embodiment 2
Embodiment 2 provides a kind of doping Bi3+SiO2The group of-CaO-MgO based laser glass, the laser glass becomes
60SiO2-25CaO-15MgO-1.5Bi2O3Glass, the laser glass are made according to following procedure：
By SiO2, CaO, MgO and Bi3+Mole ratio be 60：25：15：3, weigh the SiO of 6mol2, 2.5mol
The Bi of MgO, 0.15mol of CaO, 1.5mol2O3Make raw material, be put into grinding a period of time in mortar, it is made to be sufficiently mixed uniformly,
Raw material after grinding uniformly is poured into corundum crucible, then the corundum crucible after sealing is put into high-temperature atmosphere furnace and is heated,
High-temperature atmosphere furnace (under nitrogen atmosphere, protection gas nitrogen flow is 0.5L/min) is warming up to 1340 with 5 DEG C/min heating rates
DEG C, in this temperature 1.5h, the sample in corundum crucible is the glass metal in molten state at this time.
Glass metal is poured into the mold for preheating 20min at 350 DEG C in advance, glass is shaped to, by the mold equipped with glass
It is put into heat preservation 1.5h in 400 DEG C of high-temperature atmosphere furnace to anneal, then cooled to room temperature, by glass sample from mold
It takes out.
The glass blocks of 2cm × 1cm is cut into glass sample with cutting machine, is regrinded to 2mm thickness, and surface is polished,
Up to the laser glass of the present embodiment.
Product testing：The laser glass of the present embodiment is detected by the way of same as Example 1, the laser glass
The peak wavelength of the emission spectrum of glass is located at about 1245nm, halfwidth about 290nm.
Embodiment 3
Embodiment 3 provides a kind of doping Bi3+SiO2The group of-CaO-MgO based laser glass, the laser glass becomes
40SiO2-40CaO-20MgO-1.5Bi2O3, the laser glass according to following procedure be made：
By SiO2, CaO, MgO and Bi3+Mole ratio be 40：40：20：3, weigh the SiO of 4mol2, 4mol CaO,
The Bi of the MgO and 0.15mol of 2mol2O3As raw material, be put into grinding in mortar makes it be sufficiently mixed uniformly for a period of time, will grind
It grinds uniform raw material to pour into corundum crucible, then the corundum crucible of sealing is put into high-temperature atmosphere furnace and is heated, high-temperature atmosphere
Stove (under nitrogen atmosphere, protection gas nitrogen flow is 0.6L/min) is warming up to 1300 DEG C with 10 DEG C/min heating rates, warm herein
Degree heat preservation 1h, the sample in corundum crucible is the glass metal in molten state at this time.
Glass metal is poured into the mold for preheating 15min at 400 DEG C in advance, glass is shaped to, mold is put into togerther 420
DEG C high-temperature atmosphere furnace in heat preservation 1h anneal, then cooled to room temperature, glass sample is removed from the molds.
The glass blocks of 2cm × 1cm is cut into glass sample with cutting machine, is milled to 2mm thickness, and surface is polished, i.e.,
Obtain the laser glass of the present embodiment.
Product testing：The laser glass of the present embodiment is detected using detection method same as Example 1, this swashs
The peak wavelength of the emission spectrum of light glass is located at about 1230nm, halfwidth about 300nm.
Embodiment 4
Embodiment 4 provides a kind of doping Bi3+SiO2The group of-CaO-MgO based laser glass, the laser glass becomes
60SiO2-20CaO-20MgO-3Bi2O3, the laser glass according to following procedure be made：
By SiO2, CaO, MgO and Bi3+Mole ratio be 60：20：20：6, weigh the SiO of 6mol2, 2mol CaO,
The Bi of the MgO and 0.3mol of 2mol2O3Make raw material, be put into grinding in mortar makes it be sufficiently mixed uniformly for a period of time, will grind equal
Even raw material pours into corundum crucible, and then the corundum crucible of sealing is put into high-temperature atmosphere furnace and is heated, high-temperature atmosphere furnace (argon
Under gas atmosphere, protection air-flow amount is 0.5L/min) with 10 DEG C/min heating rates 1340 DEG C are warming up to, in this temperature 1h,
The sample in corundum crucible is the glass metal in molten condition at this time.
Glass metal is poured into the mold for preheating 15min at 400 DEG C in advance, glass is shaped to, by the mold equipped with glass
It is put into heat preservation 1.5h in 400 DEG C of high-temperature atmosphere furnace to anneal, then cooled to room temperature, by glass sample after cooling
It is removed from the molds.
The glass blocks of 2cm × 1cm is cut into glass sample with cutting machine, is milled to 2mm thickness, and surface is polished, i.e.,
Obtain the laser glass of the present embodiment.
Product testing：The laser glass of the present embodiment is detected using detection method same as Example 1, this swashs
The peak wavelength of the emission spectrum of light glass is located at about 1235nm, halfwidth about 290nm.
Embodiment 5
Embodiment 5 provides a kind of doping Bi3+SiO2The group of-CaO-MgO based laser glass, the laser glass becomes
50SiO2-30CaO-20MgO-4Bi2O3, the laser glass according to following procedure be made：
By SiO2, CaO, MgO and Bi3+Mole ratio be 50：30：20：8, weigh the SiO using 5mol2, 3mol
The Bi of MgO, 0.4mol of CaO, 2mol2O3Make raw material, is put into grinding a period of time in mortar, so that it is sufficiently mixed uniformly, will grind
It grinds uniform raw material to pour into corundum crucible, then the corundum crucible of sealing is put into high-temperature atmosphere furnace and is heated, high-temperature atmosphere
Stove (under nitrogen atmosphere, protection air-flow amount 0.5L/min) is warming up to 1320 DEG C with 10 DEG C/min heating rates, in this temperature
1.5h, the sample in corundum crucible is the glass metal in molten condition at this time.
Glass metal is poured into the mold for preheating 20min at 390 DEG C in advance, glass is shaped to, by the mold equipped with glass
It is put into heat preservation 2h in 410 DEG C of high-temperature atmosphere furnace to anneal, then cooled to room temperature is to get glass sample.
It is cut into the glass blocks of 2cm × 1cm in glass sample, is milled to 2mm thickness, and surface is polished, then to the glass
Block carries out radiation treatment, and the X-ray energy that irradiation bomb uses is 40KeV, irradiation dose 30KGy, dosage rate 200Gy/h,
Up to the laser glass of the present embodiment.
Product testing：The laser glass of the present embodiment is detected using detection method same as Example 1, this swashs
The peak wavelength of light glass emission spectrum is located at about 1245nm, halfwidth about 290nm.
Embodiment 6
Embodiment 6 provides a kind of doping Bi3+SiO2The group of-CaO-MgO based laser glass, the laser glass becomes
50SiO2-35CaO-15MgO-3Bi2O3, the laser glass according to following procedure be made：
By SiO2, CaO, MgO and Bi3+Mole ratio be 50：35：15：6, weigh the SiO using 5mol2, 3.5mol
The Bi of MgO, 0.3mol of CaO, 1.5mol2O3Make raw material, is put into grinding a period of time in mortar, it is made to be sufficiently mixed uniformly, it will
It grinds uniform raw material to pour into corundum crucible, then the corundum crucible of sealing is put into high-temperature atmosphere furnace and is heated, High Temperature Gas
Atmosphere stove (under nitrogen atmosphere, protection air-flow amount 0.55L/min) is warming up to 1310 DEG C with 7 DEG C/min heating rates, is protected in this temperature
Warm 1.5h, the sample in corundum crucible is the glass metal in molten condition at this time.
Glass metal is poured into the mold for preheating 20min at 370 DEG C in advance, glass is shaped to, by the mold equipped with glass
It is put into heat preservation 1.5h in 400 DEG C of high-temperature atmosphere furnace to anneal, then cooled to room temperature is to get glass sample.
It is cut into the glass blocks of 2cm × 1cm in glass sample, is milled to 2mm thickness, and surface is polished, then to the glass
Block carries out radiation treatment, and the X-ray energy that irradiation bomb uses is 30KeV, irradiation dose 25KGy, dosage rate 150Gy/h,
Up to the laser glass of the present embodiment.
Product testing：The laser glass of the present embodiment is detected using detection method same as Example 1, this swashs
The peak wavelength of light glass emission spectrum is located at about 1250nm, halfwidth about 300nm.
Embodiment 7
Embodiment 7 provides a kind of doping Bi3+SiO2The group of-CaO-MgO based laser glass, the laser glass becomes
50SiO2-35CaO-15MgO-6BiCl3, the laser glass according to following procedure be made：
By SiO2, CaO, MgO and Bi3+Mole ratio be 50：35：15：6, weigh the SiO using 5mol2, 3.5mol
The BiCl of MgO, 0.6mol of CaO, 1.5mol3Make raw material, remaining preparation process is identical as the preparation process of embodiment 6, obtains
The laser glass of the present embodiment.
Product testing：The laser glass of the present embodiment is detected using detection method same as Example 1, this swashs
The peak wavelength of light glass emission spectrum is located at about 1240nm, halfwidth about 290nm.
Embodiment 8
Embodiment 8 provides a kind of doping Bi3+SiO2The group of-CaO-MgO based laser glass, the laser glass becomes
50SiO2-35CaO-15MgO-4BiCl3, the laser glass according to following procedure be made：
By SiO2, CaO, MgO and Bi3+Mole ratio be 50：35：15：4, weigh the SiO using 5mol2, 3.5mol
The BiCl of MgO, 0.4mol of CaO, 1.5mol3Make raw material, the preparation of remaining preparation process and its preparation process and embodiment 6
Journey is roughly the same, obtains the laser glass of the present embodiment.
Product testing：The laser glass of the present embodiment is detected using detection method same as Example 1, this swashs
The peak wavelength of light glass emission spectrum is located at about 1235nm, halfwidth about 280nm.
Embodiment 9
Embodiment 9 provides a kind of doping Bi3+SiO2The group of-CaO-MgO based laser glass, the laser glass becomes
50SiO2-35CaO-15MgO-7BiCl3, the laser glass according to following procedure be made：
By SiO2, CaO, MgO and Bi3+Mole ratio be 50：35：15：7, weigh the SiO using 5mol2, 3.5mol
The BiCl of MgO, 0.7mol of CaO, 1.5mol3Make raw material, the preparation of remaining preparation process and its preparation process and embodiment 6
Journey is roughly the same, obtains the laser glass of the present embodiment.
Product testing：The laser glass of the present embodiment is detected using detection method same as Example 1, this swashs
The peak wavelength of light glass emission spectrum is located at about 1245nm, halfwidth about 295nm.
Through statistics, the peak wavelength of the laser glass emission spectrum in embodiment 1 to 9 is located at 1230~1250nm ranges,
Halfwidth about 280~300nm ranges, fluorescence lifetime is 0.5ms or more.
To sum up, the doping Bi of the embodiment of the present invention3+SiO2- CaO-MgO based laser glass launch wavelength be located at 800~
Generate near-infrared luminous under the excitation of 1100nm laser, and luminous efficiency is high, the bandwidth that shines is very wide.Doping Bi3+SiO2-
The preparation method of CaO-MgO based laser glass can give full play to the luminescent effect of Bi ions, and production efficiency is high, at low cost.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (9)
1. a kind of doping Bi3+SiO2- CaO-MgO based laser glass, which is characterized in that it is made of base and dopant,
The base includes SiO2, CaO and MgO, the SiO2, the CaO and the MgO mole ratio be 40~60：40~
25：20~15, the dopant is containing Bi3+Compound, the Bi3+Molal quantity account for the total mole number of the base
3%~8%.
2. doping Bi according to claim 13+SiO2- CaO-MgO based laser glass, which is characterized in that the doping
Object includes Bi2O3、BiCl3At least one of.
3. doping Bi according to claim 13+SiO2- CaO-MgO based laser glass, which is characterized in that the Bi3+'s
Molal quantity accounts for the 4%~7.6% of the total mole number of the base.
4. a kind of doping Bi described in claim 13+SiO2The preparation method of-CaO-MgO based laser glass, feature exist
In comprising following steps：
It takes the base and the dopant to mix to obtain mixture, the mixture is heated to the glass metal in molten state；
The glass metal is poured on and is preheated in 350 DEG C~400 DEG C of mold, glass is shaped to；
Annealing, cooling.
5. doping Bi according to claim 43+SiO2The preparation method of-CaO-MgO based laser glass, feature exist
In the method for the heating is：By the mixture with the heating rate of 5 DEG C/min~10 DEG C/min be warming up to 1280 DEG C~
1340 DEG C, and keep the temperature 1h~1.5h.
6. doping Bi according to claim 4 or 53+SiO2The preparation method of-CaO-MgO based laser glass, feature
It is, the heating is carried out in non-oxidising gas environment, and the flow of the non-oxidising gas is 0.5L/min~0.6L/min.
7. doping Bi according to claim 43+SiO2The preparation method of-CaO-MgO based laser glass, feature exist
In the method for the annealing is：The mold equipped with the glass is placed in heat preservation 1h~2h at 380 DEG C~420 DEG C.
8. doping Bi according to claim 43+SiO2The preparation method of-CaO-MgO based laser glass, feature exist
In the preparation method further includes the steps that carrying out radiation treatment to glass after cooling using X-ray.
9. doping Bi according to claim 83+SiO2The preparation method of-CaO-MgO based laser glass, feature exist
In the energy of, the X-ray be 20KeV~40KeV, irradiation dose ranging from 20KGy~30KGy, dosage rate be 100Gy/h~
200Gy/h。
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| CN101817636A (en) * | 2009-11-17 | 2010-09-01 | 昆明理工大学 | Bismuth-doped silicon-aluminum-calcium optical glass and preparation method thereof |
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| CN101182121A (en) * | 2007-11-02 | 2008-05-21 | 中国科学院上海光学精密机械研究所 | Bismuth-nickel co-doped transparent silicate glass ceramics and preparation method thereof |
| CN101817636A (en) * | 2009-11-17 | 2010-09-01 | 昆明理工大学 | Bismuth-doped silicon-aluminum-calcium optical glass and preparation method thereof |
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