CN106242272A - A kind of doping Bi3+siO2caO MgO based laser glass and preparation method thereof - Google Patents
A kind of doping Bi3+siO2caO MgO based laser glass and preparation method thereof Download PDFInfo
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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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- 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+SiO2CaO MgO based laser glass, relates to fiber optic materials technical field, and this laser glass is made up of basis thing and alloy, and basis thing includes SiO2, CaO and MgO, alloy is containing Bi3+Compound, Bi3+Molal quantity account for basis thing total mole number 3% 8%.This laser glass is at SiO2Adulterate in CaO MgO system substrate Bi3+, under launching the exciting of wavelength 800nm～1100nm laser, generation is near-infrared luminous, and luminous efficiency bandwidth high, luminous is the widest.The present invention also provides for a kind of doping Bi3+SiO2The preparation method of CaO MgO based laser glass, is the heating of the raw material to specified raw material ratio, pours mould, molding into, then uses the annealing of specific process conditions, cooling, and this preparation method can give full play to the luminescent effect of Bi ion, and production efficiency is high, low cost.
Description
Technical field
The present invention relates to fiber optic materials technical field, in particular to one doping Bi3+SiO2-CaO-MgO system swashs
Light glass and preparation method thereof.
Background technology
Nobel Prize in physics winner Gao Kun professor proposed the (letter of low-loss optical fibers first as far back as 1966
Claim optical fiber) concept, he produced first optical fibers in the world later, make information superhighway the whole world fast development.
Window wave-length coverage based on low-loss optically fiber communication is 1200～1600nm, and fiber amplifier refers to apply to light
In fiber communication circuit, it is achieved signal amplify a kind of new all optical amplifier, fiber amplifier have Raman fiber amplifier and
The multiple rare-earth ion activated fiber amplifier such as Er, Tm, Pr.But, the near-infrared luminous source of rare earth ion is at 4f orbital energy level
Between transition can occur, this transition is shown narrow luminous bandwidth by the shielding of outer layer 6s, 5d orbital electron so that
The window wave-length coverage of rare earth ion doped optical fiber amplifier is narrow, such as, the wave-length coverage of conventional C-band be 1530～
The window wave-length coverage mixing Pr fiber amplifier of 1565nm, O wave band is 1280～1320nm, S-band mix Tm fiber amplifier
The window wave-length coverage of device TDFA is 1420～1520nm.
Therefore, even if by existing rare earth ion doped optical fiber amplifier in parallel or be together in series, can not realize whole
The light amplification of optical communicating waveband.If able to develop the fiber amplifier of ultra broadband, i.e. use optical fiber, a pumping source
Can be achieved with the light amplification of whole optical communicating waveband, this can bring a new revolution to optical communication field undoubtedly.
Calendar year 2001 Japanese Scientists Fujimoto is found that near-infrared ripple first in main group metal Bi ion-doped glass
The broad-band illumination of section, and its prospect being applied to broadband optical fiber amplifier is proposed.Russian scientist Dianov in 2005 etc. exist
The optical fiber of Bi ion doping achieves laser output that wavelength is 1150～1300nm first.Subsequently, other main group metals from
The broad-band illumination characteristic of son (s, p electronic configuration, including Bi, Te, Pb, Sn, Sb etc.) is gradually found.Scientist finds, main group
S, p valency electron of metal ion is in the outermost layer of electronic shell, interacts strong with ligand field, is easily formed and is similar to transition gold
Belong to the broad-band illumination of ion, and its emission wavelength extends near infrared region, has major application prospect.
But up to the present, the luminescent material of doping main group metal Bi ion is in near-infrared luminous luminous efficiency, luminescence
Bandwidth is the best, and main cause is that the Effective Doping concentration of Bi ion is the highest, and the Bi ionoluminescence quantum efficiency after doping is not
Enough ideals, therefore develop that new to mix Bi ion broad-band illumination material necessary.
Summary of the invention
It is an object of the invention to provide a kind of doping Bi3+SiO2-CaO-MgO based laser glass, is launching wavelength position
Under the exciting of 800nm～1100nm laser, generation is near-infrared luminous, and luminous efficiency bandwidth high, luminous is the widest.
Another object of the present invention is to provide a kind of doping Bi3+SiO2The preparation side of-CaO-MgO based laser glass
Method, this preparation method can give full play to the luminescent effect of Bi ion, and production efficiency is high, low cost.
Embodiments of the invention are achieved in that
A kind of doping Bi3+SiO2-CaO-MgO based laser glass, its by basis thing and alloy make, basis thing include
SiO2, CaO and MgO, alloy is containing Bi3+Compound, Bi3+Molal quantity account for basis thing total mole number 3%～8%.
In preferred embodiment of the present invention, above-mentioned alloy includes Bi2O3、BiCl3In at least one.
In preferred embodiment of the present invention, above-mentioned Bi3+Molal quantity account for basis thing total mole number 4%～7.6%.
In preferred embodiment of the present invention, above-mentioned SiO2, the mole ratio of CaO and MgO be 40～60:40～25:20
～15.
A kind of doping Bi3+SiO2The preparation method of-CaO-MgO based laser glass, it comprises the following steps:
Take basis thing and alloy mixes to obtain mixture, heat the mixture to the vitreous humour in molten state；
Vitreous humour is poured in the mould being preheated to 350 DEG C～400 DEG C, is shaped to glass；
Annealing, cooling.
In preferred embodiment of the present invention, the method for above-mentioned heating is: by mixture with 5 DEG C/min～10 DEG C/min
Heating rate is warming up to 1280 DEG C～1340 DEG C, and is incubated 1h～1.5h.
In preferred embodiment of the present invention, above-mentioned heating is to carry out in non-oxidising gas environment, the flow of non-oxidising gas
For 0.5L/min～0.6L/min.
In preferred embodiment of the present invention, the method for above-mentioned annealing is: will be equipped with the mould of glass be placed in 380 DEG C～
1h～2h it is incubated at 420 DEG C.
In preferred embodiment of the present invention, above-mentioned preparation method also includes using X-ray to carry out the glass after cooling
The step of radiation treatment.
In preferred embodiment of the present invention, the energy of above-mentioned X-ray is 20KeV～40KeV, and irradiation dose scope is
20KGy～30KGy, close rate is 100Gy/h～200Gy/h.
The embodiment of the present invention provides the benefit that:
The laser glass of the embodiment of the present invention is made up of basis thing and alloy, and basis thing includes SiO2, CaO and MgO,
Alloy is containing Bi3+Compound, Bi3+Molal quantity account for basis thing total mole number 3%～8%.At SiO2-CaO-MgO
It is doping Bi in substrate3+Afterwards, under launching the exciting that wavelength is positioned at 800nm～1100nm laser, generation is near-infrared luminous, and
And luminous efficiency bandwidth high, luminous is the widest, luminescent lifetime extends.It addition, the laser glass of the embodiment of the present invention is to specific former
The raw material of material ratio heats, pours mould, molding into, then uses the annealing of specific process conditions, cooling to be formed, this preparation method energy
Give full play to the luminescent effect of Bi ion, and production efficiency is high, low cost.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below by embodiment required use attached
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, and it is right to be therefore not construed as
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to this
A little accompanying drawings obtain other relevant accompanying drawings.
The laser glass that Fig. 1 provides for the embodiment of the present invention 1 emission spectrum under the laser diode of 808nm excites；
The laser glass that Fig. 2 provides for the embodiment of the present invention 1 fluorescence intensity at 1240nm attenuation curve in time.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below will be in the embodiment of the present invention
Technical scheme be clearly and completely described.In embodiment, unreceipted actual conditions person, builds according to normal condition or manufacturer
The condition of view is carried out.Agents useful for same or instrument unreceipted production firm person, being can be by the commercially available conventional product bought and obtain
Product.
Doping Bi to the embodiment of the present invention below3+SiO2-CaO-MgO based laser glass and preparation method thereof has
Body explanation.
The embodiment of the present invention provides one doping Bi3+SiO2-CaO-MgO based laser glass, it is by basis thing and doping
Thing is made, and basis thing includes SiO2, CaO and MgO, alloy is containing Bi3+Compound, Bi3+Molal quantity account for basis thing total
The 3%～8% of molal quantity.
The embodiment of the present invention selects SiO2, thing makes SiO based on CaO and MgO2-CaO-MgO system substrate, it is a kind of
It is particularly suitable for the Bi that adulterates3+Substrate, this substrate can be with the Bi of doped with high concentration3+, and concentration quenching phenomena will not occur, its
Middle Bi3+Effective Doping concentration be 3mol%～8mol%, and adulterate after Bi3+Luminous quantum efficiency reach 80% with
On.Therefore, the laser glass of the embodiment of the present invention has higher Bi ion doping concentration, and luminous efficiency is high, luminous zone
Width is the widest, and its combination property is apparently higher than other Bi ion-doped glass；It is positioned at 800nm～1100nm laser at transmitting wavelength
Exciting under generation near-infrared luminous, can be applicable to near-infrared communication, and the wavelength of output be positioned at the work that optical transmission loss is relatively low
Make window wavelength, have important application prospect.
Under normal circumstances, adulterate in substrate Bi3+Doping chemical species have a variety of, if the photism to laser glass
Can the biggest negatively affect, in the present embodiment, alloy includes Bi2O3、BiCl3In one or both, preferably include
Bi2O3, this is because Bi2O3、BiCl3Negative effect to laser glass luminescent properties is less, the Bi (Bi of oxidation state2O3) to swashing
Light glass luminescent properties is almost without adverse effect.
Under normal circumstances, Bi3+Different doping content scopes, in the present embodiment, Bi is had in different substrate3+Rub
Your number accounts for the 4%～7.6% of the total mole number of basis thing, preferably 5%～7%.In the range of this doping content, laser glass
Luminescent properties best, the cost performance being applied in industry is higher.
SiO2-CaO-MgO based laser glass is with SiO2, CaO and MgO formed SiO2-CaO-MgO system substrate is substrate,
SiO2, CaO and MgO mol ratio need can play Bi3+Optical activity, in the present embodiment, SiO2, the molal quantity of CaO and MgO
Ratio is 40～60:40～25:20～15, and now, the emission lifetime of the laser glass obtained is long, and the half-life at 1240nm is
More than 0.58 millisecond, and luminous intensity is big.
The embodiment of the present invention also provides for a kind of doping Bi3+SiO2The preparation method of-CaO-MgO based laser glass, its bag
Include following steps:
First, take basis thing and alloy mixes to obtain mixture, heat the mixture to the vitreous humour 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 incubated
1h～1.5h.Further preferably, heating is to carry 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 be carried out in high-temperature atmosphere furnace, and non-oxidising gas environment mostly is nitrogen environment.
Secondly, being poured on by vitreous humour in the mould being preheated to 350 DEG C～400 DEG C, be shaped to glass, the temperature of mould is preferred
Preheating is close or equal to follow-up annealing temperature.
Then, anneal, cool down, obtain laser glass.Preferably method for annealing is: the mould that will be equipped with glass is placed in 380
DEG C～420 DEG C at be incubated 1.5h～2h, anneal in the high-temperature atmosphere furnace of 380 DEG C～420 DEG C, can fully eliminate in glass
Residual stress, stable dimensions, reduce deformation and be inclined to crackle, make glass have evenly, stable luminescent properties, Yi Jifa
Light bandwidth excellent luminance performance the widest, that luminous efficiency is higher simultaneously.
Preferably, above-mentioned preparation method also needs to use X-ray that the glass after cooling is carried out radiation treatment.The energy of X-ray
Amount is 20KeV～40KeV, and irradiation dose scope is 20KGy～30KGy, and close rate is 100Gy/h～200Gy/h.Set up X to penetrate
Line irradiation process can greatly improve the concentration of the laser glass centre of luminescence.
In the present embodiment, if using conventional glass object processing method, i.e. heating, melt, the working procedure processing such as cooling
Embodiment doping Bi3+SiO2-CaO-MgO based laser glass, prepared laser glass performance can be poor, this is because glass
The performance of glass can be had a major impact by the process conditions of processing.Only use the preparation method of the embodiment of the present invention, prepared
Doping Bi3+SiO2The combination property of-CaO-MgO based laser glass is better.
Below in conjunction with embodiment, inventive feature and performance are described in further detail.
Embodiment 1
Embodiment 1 provides a kind of doping Bi3+SiO2-CaO-MgO based laser glass, consisting of of this laser glass
40SiO2-40CaO-20MgO-3Bi2O3, this laser glass prepares according to procedure below:
Use SiO2、CaO、MgO、Bi2O3Make raw material (SiO2, thing based on CaO, MgO, Bi2O3For alloy), press
SiO2, CaO, MgO and Bi3+Mole ratio be that 40:40:20:6 carries out dispensing, specifically weigh the SiO of 240g (4mol)2,
The MgO of the CaO, 80g (2mol) of 224g (4mol), and the Bi of 139.8g (0.3mol)2O3, put into mortar and grind a period of time,
Make it be sufficiently mixed uniformly, uniform for grinding raw material is poured in corundum crucible, then the corundum crucible of sealing is put into high temperature
Heating in atmosphere furnace, high-temperature atmosphere furnace (under argon gas atmosphere, protection gas argon flow amount be 0.6L/min) heats up speed with 10 DEG C/min
Rate is warming up to 1280 DEG C, and at this temperature 1.5h, now the sample in corundum crucible is the vitreous humour in molten state.
Vitreous humour is poured in advance in the mould of 350 DEG C of preheating 20min, be shaped to glass, will be equipped with the mould of glass
Put into insulation 1.5h in the high-temperature atmosphere furnace of 380 DEG C to anneal, then naturally cool to room temperature, by glass sample by mould
Take out.
In glass sample, cut out the glass blocks of 2cm × 1cm, be milled to 2mm thick, and by surface finish, then to this glass
Block carries out radiation treatment, and the X-ray energy that irradiation bomb uses is 20KeV, and irradiation dose scope is 20KGy, and close rate is
100Gy/h, obtains the laser glass of the present embodiment.
Product checking: laser glass is tested in Triax550 fluorescence spectrophotometer Room temperature emission spectra, uses transmitted wave
The laser diode of a length of 808nm as pumping source irradiating laser glass, test result as shown in Figure 1: laser glass launch light
The peak wavelength of spectrum is positioned at 1240nm, halfwidth about 300nm.
Use Tektronix TDS3052 digital oscilloscope record 1240nm fluorescence intensity attenuation curve in time, knot
Fruit is as in figure 2 it is shown, obtaining 1240nm fluorescence lifetime by first-order exponential decay equation model experimental data is 0.58ms.
Embodiment 2
Embodiment 2 provides a kind of doping Bi3+SiO2-CaO-MgO based laser glass, consisting of of this laser glass
60SiO2-25CaO-15MgO-1.5Bi2O3Glass, this laser glass prepares according to procedure below:
By SiO2, CaO, MgO and Bi3+Mole ratio be 60:25:15:3, weigh the SiO of 6mol2, the CaO of 2.5mol,
The Bi of MgO, 0.15mol of 1.5mol2O3Make raw material, put into mortar and grind a period of time so that it is be sufficiently mixed uniformly, will grind
Raw material after mill is uniform is poured in corundum crucible, and the corundum crucible after then sealing is put in high-temperature atmosphere furnace and heated, high temperature
Atmosphere furnace (under nitrogen atmosphere, protection gas nitrogen flow is 0.5L/min) is warming up to 1340 DEG C, at this with 5 DEG C/min heating rate
Temperature 1.5h, now the sample in corundum crucible is the vitreous humour in molten state.
Vitreous humour is poured in advance in the mould of 350 DEG C of preheating 20min, be shaped to glass, will be equipped with the mould of glass
Put into insulation 1.5h in the high-temperature atmosphere furnace of 400 DEG C to anneal, then naturally cool to room temperature, by glass sample from mould
Take out.
In glass sample, cut out the glass blocks of 2cm × 1cm with cutting machine, regrind thick to 2mm, and by surface finish,
Obtain the laser glass of the present embodiment.
Product checking: use mode same as in Example 1 that the laser glass of the present embodiment is detected, this laser glass
The peak wavelength of the emission spectrum of glass is positioned at about 1245nm, halfwidth about 290nm.
Embodiment 3
Embodiment 3 provides a kind of doping Bi3+SiO2-CaO-MgO based laser glass, consisting of of this laser glass
40SiO2-40CaO-20MgO-1.5Bi2O3, this laser glass prepares according to procedure below:
By SiO2, CaO, MgO and Bi3+Mole ratio be 40:40:20:3, weigh the SiO of 4mol2, the CaO of 4mol,
The Bi of MgO and 0.15mol of 2mol2O3As raw material, put into mortar grind a period of time make it be sufficiently mixed uniformly, will grind
Grind uniform raw material and pour in corundum crucible, then the corundum crucible of sealing is put in high-temperature atmosphere furnace and heat, 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 rate, temperature at this
Degree insulation 1h, now the sample in corundum crucible is the vitreous humour in molten state.
Vitreous humour is poured in advance in the mould of 400 DEG C of preheating 15min, be shaped to glass, mould is put into together 420
DEG C high-temperature atmosphere furnace in be incubated 1h anneal, then naturally cool to room temperature, glass sample be removed from the molds.
In glass sample, cut out the glass blocks of 2cm × 1cm with cutting machine, be milled to 2mm thick, and by surface finish, i.e.
Obtain the laser glass of the present embodiment.
Product checking: use detection method same as in Example 1 to detect the laser glass of the present embodiment, this swashs
The peak wavelength of the emission spectrum of light glass is positioned at about 1230nm, halfwidth about 300nm.
Embodiment 4
Embodiment 4 provides a kind of doping Bi3+SiO2-CaO-MgO based laser glass, consisting of of this laser glass
60SiO2-20CaO-20MgO-3Bi2O3, this laser glass prepares according to procedure below:
By SiO2, CaO, MgO and Bi3+Mole ratio be 60:20:20:6, weigh the SiO of 6mol2, the CaO of 2mol,
The Bi of MgO and 0.3mol of 2mol2O3Make raw material, put into mortar and grind a period of time and make it be sufficiently mixed uniformly, will grind equal
Even raw material is poured in corundum crucible, is then put into by the corundum crucible of sealing in high-temperature atmosphere furnace and heats, high-temperature atmosphere furnace (argon
Under gas atmosphere, protection throughput is 0.5L/min) it is warming up to 1340 DEG C with 10 DEG C/min heating rate, at this temperature 1h,
Now the sample in corundum crucible is the vitreous humour in molten condition.
Vitreous humour is poured in advance in the mould of 400 DEG C of preheating 15min, be shaped to glass, will be equipped with the mould of glass
Put into insulation 1.5h in the high-temperature atmosphere furnace of 400 DEG C to anneal, then naturally cool to room temperature, the glass sample after cooling down
It is removed from the molds.
In glass sample, cut out the glass blocks of 2cm × 1cm with cutting machine, be milled to 2mm thick, and by surface finish, i.e.
Obtain the laser glass of the present embodiment.
Product checking: use detection method same as in Example 1 to detect the laser glass of the present embodiment, this swashs
The peak wavelength of the emission spectrum of light glass is positioned at about 1235nm, halfwidth about 290nm.
Embodiment 5
Embodiment 5 provides a kind of doping Bi3+SiO2-CaO-MgO based laser glass, consisting of of this laser glass
50SiO2-30CaO-20MgO-4Bi2O3, this laser glass prepares according to procedure below:
By SiO2, CaO, MgO and Bi3+Mole ratio be 50:30:20:8, weigh use 5mol SiO2, 3mol
The Bi of MgO, 0.4mol of CaO, 2mol2O3Make raw material, put into mortar and grind a period of time so that it is be sufficiently mixed uniformly, will grind
Grind uniform raw material and pour in corundum crucible, then the corundum crucible of sealing is put in high-temperature atmosphere furnace and heat, high-temperature atmosphere
Stove (under nitrogen atmosphere, protecting throughput 0.5L/min) is warming up to 1320 DEG C with 10 DEG C/min heating rate, at this temperature
1.5h, now the sample in corundum crucible is the vitreous humour in molten condition.
Vitreous humour is poured in advance in the mould of 390 DEG C of preheating 20min, be shaped to glass, will be equipped with the mould of glass
Put into insulation 2h in the high-temperature atmosphere furnace of 410 DEG C to anneal, then naturally cool to room temperature, obtain glass sample.
In glass sample, cut out the glass blocks of 2cm × 1cm, be milled to 2mm thick, and by surface finish, then to this glass
Block carries out radiation treatment, and the X-ray energy that irradiation bomb uses is 40KeV, and irradiation dose is 30KGy, and close rate is 200Gy/h,
Obtain the laser glass of the present embodiment.
Product checking: use detection method same as in Example 1 to detect the laser glass of the present embodiment, this swashs
The peak wavelength of light glass emission spectrum is positioned at about 1245nm, halfwidth about 290nm.
Embodiment 6
Embodiment 6 provides a kind of doping Bi3+SiO2-CaO-MgO based laser glass, consisting of of this laser glass
50SiO2-35CaO-15MgO-3Bi2O3, this laser glass prepares according to procedure below:
By SiO2, CaO, MgO and Bi3+Mole ratio be 50:35:15:6, weigh use 5mol SiO2, 3.5mol
The Bi of MgO, 0.3mol of CaO, 1.5mol2O3Make raw material, put into mortar and grind a period of time so that it is be sufficiently mixed uniformly, will
Grind uniform raw material and pour in corundum crucible, then the corundum crucible of sealing is put in high-temperature atmosphere furnace and heat, High Temperature Gas
Atmosphere stove (under nitrogen atmosphere, protecting throughput 0.55L/min) is warming up to 1310 DEG C with 7 DEG C/min heating rate, protects in this temperature
Temperature 1.5h, now the sample in corundum crucible is the vitreous humour in molten condition.
Vitreous humour is poured in advance in the mould of 370 DEG C of preheating 20min, be shaped to glass, will be equipped with the mould of glass
Put into insulation 1.5h in the high-temperature atmosphere furnace of 400 DEG C to anneal, then naturally cool to room temperature, obtain glass sample.
In glass sample, cut out the glass blocks of 2cm × 1cm, be milled to 2mm thick, and by surface finish, then to this glass
Block carries out radiation treatment, and the X-ray energy that irradiation bomb uses is 30KeV, and irradiation dose is 25KGy, and close rate is 150Gy/h,
Obtain the laser glass of the present embodiment.
Product checking: use detection method same as in Example 1 to detect the laser glass of the present embodiment, this swashs
The peak wavelength of light glass emission spectrum is positioned at about 1250nm, halfwidth about 300nm.
Embodiment 7
Embodiment 7 provides a kind of doping Bi3+SiO2-CaO-MgO based laser glass, consisting of of this laser glass
50SiO2-35CaO-15MgO-6BiCl3, this laser glass prepares according to procedure below:
By SiO2, CaO, MgO and Bi3+Mole ratio be 50:35:15:6, weigh use 5mol SiO2, 3.5mol
The BiCl of MgO, 0.6mol of CaO, 1.5mol3Making raw material, remaining preparation process is identical with the preparation process of embodiment 6, obtains
The laser glass of the present embodiment.
Product checking: use detection method same as in Example 1 to detect the laser glass of the present embodiment, this swashs
The peak wavelength of light glass emission spectrum is positioned at about 1240nm, halfwidth about 290nm.
Embodiment 8
Embodiment 8 provides a kind of doping Bi3+SiO2-CaO-MgO based laser glass, consisting of of this laser glass
50SiO2-35CaO-15MgO-4BiCl3, this laser glass prepares according to procedure below:
By SiO2, CaO, MgO and Bi3+Mole ratio be 50:35:15:4, weigh use 5mol SiO2, 3.5mol
The BiCl of MgO, 0.4mol of CaO, 1.5mol3Make raw material, remaining preparation process and its preparation process and the preparation of embodiment 6
Journey is roughly the same, obtains the laser glass of the present embodiment.
Product checking: use detection method same as in Example 1 to detect the laser glass of the present embodiment, this swashs
The peak wavelength of light glass emission spectrum is positioned at about 1235nm, halfwidth about 280nm.
Embodiment 9
Embodiment 9 provides a kind of doping Bi3+SiO2-CaO-MgO based laser glass, consisting of of this laser glass
50SiO2-35CaO-15MgO-7BiCl3, this laser glass prepares according to procedure below:
By SiO2, CaO, MgO and Bi3+Mole ratio be 50:35:15:7, weigh use 5mol SiO2, 3.5mol
The BiCl of MgO, 0.7mol of CaO, 1.5mol3Make raw material, remaining preparation process and its preparation process and the preparation of embodiment 6
Journey is roughly the same, obtains the laser glass of the present embodiment.
Product checking: use detection method same as in Example 1 to detect the laser glass of the present embodiment, this swashs
The peak wavelength of light glass emission spectrum is positioned at about 1245nm, halfwidth about 295nm.
Through statistics, the peak wavelength of the laser glass emission spectrum in embodiment 1 to 9 is positioned at 1230～1250nm scopes,
Halfwidth about 280～300nm scope, fluorescence lifetime is more than 0.5ms.
To sum up, the doping Bi of the embodiment of the present invention3+SiO2-CaO-MgO based laser glass launch wavelength be positioned at 800～
Under the exciting of 1100nm laser, generation is near-infrared luminous, and luminous efficiency bandwidth high, luminous is the widest.This doping Bi3+SiO2-
The preparation method of CaO-MgO based laser glass can give full play to the luminescent effect of Bi ion, and production efficiency is high, low cost.
Embodiments described above is a part of embodiment of the present invention rather than whole embodiments.The reality of the present invention
The detailed description executing example is not intended to limit the scope of claimed invention, but is merely representative of the selected enforcement of the present invention
Example.Based on the embodiment in the present invention, those of ordinary skill in the art are obtained under not making creative work premise
Every other embodiment, broadly falls into the scope of protection of the invention.
Claims (10)
1. a doping Bi3+SiO2-CaO-MgO based laser glass, it is characterised in that it is made up of basis thing and alloy,
Described basis thing includes SiO2, CaO and MgO, described alloy is containing Bi3+Compound, described Bi3+Molal quantity account for described base
The 3%～8% of the total mole number of plinth thing.
Doping Bi the most according to claim 13+SiO2-CaO-MgO based laser glass, it is characterised in that described doping
Thing includes Bi2O3、BiCl3In at least one.
Doping Bi the most according to claim 13+SiO2-CaO-MgO based laser glass, it is characterised in that described Bi3+'s
Molal quantity accounts for the 4%～7.6% of the total mole number of described basis thing.
Doping Bi the most according to claim 13+SiO2-CaO-MgO based laser glass, it is characterised in that described SiO2、
The mole ratio of described CaO and described MgO is 40～60:40～25:20～15.
5. the doping Bi described in a claim 13+SiO2The preparation method of-CaO-MgO based laser glass, its feature exists
In, it comprises the following steps:
Take described basis thing and described alloy mixes to obtain mixture, described mixture is heated to the vitreous humour in molten state；
Described vitreous humour is poured in the mould being preheated to 350 DEG C～400 DEG C, is shaped to glass；
Annealing, cooling.
Doping Bi the most according to claim 53+SiO2The preparation method of-CaO-MgO based laser glass, its feature exists
In, the method for described heating is: by described 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 it is incubated 1h～1.5h.
7. according to the doping Bi described in claim 5 or 63+SiO2The preparation method of-CaO-MgO based laser glass, its feature
Being, described heating is to carry out in non-oxidising gas environment, and the flow of described non-oxidising gas is 0.5L/min～0.6L/min.
Doping Bi the most according to claim 53+SiO2The preparation method of-CaO-MgO based laser glass, its feature exists
In, the method for described annealing is: the described mould that will be equipped with described glass is placed at 380 DEG C～420 DEG C insulation 1h～2h.
Doping Bi the most according to claim 53+SiO2The preparation method of-CaO-MgO based laser glass, its feature exists
In, described preparation method also includes using X-ray that the glass after cooling is carried out the step of radiation treatment.
Doping Bi the most according to claim 93+SiO2The preparation method of-CaO-MgO based laser glass, its feature exists
In, the energy of described X-ray is 20KeV～40KeV, and irradiation dose scope is 20KGy～30KGy, close rate be 100Gy/h～
200Gy/h。
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