CN107640893B - Infrared tellurium germanate glass and preparation method in a kind of high er-doped - Google Patents
Infrared tellurium germanate glass and preparation method in a kind of high er-doped Download PDFInfo
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Abstract
The invention discloses infrared tellurium germanate glasses in a kind of high er-doped, and component includes: TeO2,GeO2,ZnCl2, BaO, denitrating catalyst waste material, Na2O,Er2O3.The glass as made from fusion method, middle infraluminescence intensity is strong, and rear-earth-doped concentration is high, has good thermal stability, is that one kind has promising high optical quality glass very much；Using the hardness and improvement thermal stability performance of discarded denitrating catalyst waste material reinforcing glass, preparation method is easy, short preparation period, is expected to be applied to national defense industry, military affairs and civil field.
Description
Technical field
The present invention relates to infrared tellurium germanate glass and preparation methods in a kind of high er-doped.
Background technique
The rear-earth-doped laser glass of infrared band and optical fiber are visited in national security and national defense construction, astrophysics in 2-3 μm
It surveys and the fields such as spectrum selective materials will all be with a wide range of applications.Currently, it is defeated only to obtain 3 μm of laser in fluoride glass
Out, but fluoride glass is because of its intrinsic defect, and chemical stability and mechanical strength are poor, preparation condition is harsh, easily by moisture
Erosion, devitrification resistance energy poor (Δ T≤85 DEG C) etc. limit the raising of its laser power.Erbium ion is can be swashed at 3 μm
The important rare earth ion of light, in 2 μm of less appear in the newspapers that shine.Lower (700~the 750cm of the phonon energy of tellurate glass-1), be conducive to improve rare earth radiative transistion probability, luminous efficiency is higher.And tellurate glass thermal stability, mechanical performance compared with
Difference adds GeO in tellurate glass2A part of tellurium oxide is substituted as glass former, forms tellurium germanate glass, it can be with
The thermal stability and mechanical performance of reinforcing glass.But after germanium dioxide introduces, glass refraction reduction will cause.
In conjunction with China's existing resource, makes full use of and solid waste resource recovery is promoted to recycle, the present invention selects denitration
Catalyst solid waste synthesizes tellurium germanate glass.Requirement with country to thermal power plant's ammonia-nitrogen atmos pollutant discharge amount
Be gradually increased, the usage amount of denitrating catalyst is gradually increased, the main component of denitrating catalyst be titanium dioxide, tungstic acid,
Vanadic anhydride etc., accounts for 95% of total amount or more.Denitrating catalyst after a large amount of uses becomes waste, does not only take up a large amount of
Space, the elements such as internal vanadium are harmful to body and environment.
Denitrating catalyst waste material of the present invention can be provided directly by power plant, refer to the catalysis generated in production process
The underproof denitrating catalyst product or intermediate products that effect reduces, utilize titanium dioxide remaining in denitrating catalyst waste material
Titanium, tungstic acid, vanadic anhydride etc. are utilized in conjunction with erbium and mix in the preparation of tellurium germanate glass, not only take full advantage of existing
Resource, while the pollution of solid waste bring is decreased, and effectively increase the middle infraluminescence performance of glass.
Summary of the invention
The purpose of the present invention is to provide infrared tellurium germanate glass tellurium germanate glass and its preparations in a kind of high er-doped
Method.Compared with previous glass host material, this kind of material overcomes tellurate glass (poor thermal stability), germanate
The intrinsic disadvantage of glass (higher glass melting temperature), tellurium germanate glass (refractive index reduction) is improving thermal stability
With, it can be achieved that rare earth ion is highly doped, and in the laser diode-pumped lower of 980nm wavelength while being obtained on the basis of mechanical strength
Very strong 2 μm and 3 μm of fluorescence provide a kind of suitable host material for infrared band laser device in 2-3 μm.
The specific technical solution of the present invention is as follows:
Infrared tellurium germanate glass in a kind of high er-doped: with TeO2、GeO2For main component, mass percentage composition includes:
TeO2: 55~75%, GeO2: 3~15%, ZnCl2: 3~10%, BaO:3~10%, denitrating catalyst waste material: 10~20%,
Na2O:2~10%, Er2O3: 0.1~17%.
Infrared tellurium germanate glass in the high er-doped, including the following steps:
(1) raw material preparation: carrying out calcining 55~65 minutes at 120~200 DEG C for denitrating catalyst waste material, after grinding
The sieving of 325 mesh, screen over-size is less than 5%；
(2) technology of preparing: the mass percent formed according to glass calculates the weight accordingly respectively formed, weighs raw material；
After all raw material components grindings are formed uniformly mixture, it is put into gold crucible, is placed in 750-980 DEG C of Elema electric furnace
It is melted 20-30 minutes, obtains the glass metal of uniform bubble-free after homogenizing and clarification；
Further, purity is passed through into gold crucible in the form of bubbling in step (2) melting process to be greater than
99.95% high purity oxygen gas can prevent moisture in air from entering glass significantly, while be conducive to each in denitrating catalyst waste material
Further remaining raw material reacts component with glass ingredient；
(3) it is poured: on the glass metal Quick pouring to the mold for being pre-heated to 350-370 DEG C that step (2) is obtained；
(4) anneal: after place into and have warmed up into 360-380 DEG C of Muffle furnace, after heat preservation 2-3 hours, then with 9-11 DEG C/
The speed of hour is cooled to 100-110 DEG C, is then shut off Muffle furnace, is cooled to room temperature.
Beneficial effects of the present invention:
(1) tellurium germanate glass mainly introduces appropriate GeO in tellurate glass2。GeO2Addition glass can be improved
Hardness and thermal stability, but GeO2It is added excessively, glass melting temperature and glass transformation temperature is caused to improve, refractive index decline.
Therefore the additional amount of germanium oxide need to be less than 15%.The addition of denitrating catalyst waste material can be effectively improved GeO2Caused glass turns
The excessively high problem of temperature, moreover it is possible to increase thermal stability, while be capable of providing with low TgAnd the glass with high rigidity
Glass.The glass that the present invention designs is due to appropriate GeO2Addition with denitrating catalyst is, it can be achieved that Er2O3Highly doped, the Vickers of glass is hard
Degree improves, about 670-690kgf/mm2。
(2) the tellurium germanate glass glass melting temperature is low, and glass transformation temperature is low, has good thermal stability,
Manufacture craft is simple, environmentally protective, and production cost is relatively low, is easy to prepare high optical quality glass.
(3) under the pumping of 980nm semiconductor laser, erbium obtained by the embodiment of the present invention mixes tellurium germanate glass and exists
Can be obtained simultaneously within the scope of 1860-2860nm stronger central wavelength 2 μm and 2.7 μm shine.2 mu m wavebands hair is not obtained
The tellurium germanate glass for not mixing denitrating catalyst of light has substantial advance, does not mix the tellurium germanate glass of denitrating catalyst
2.7 mu m luminous intensity significantly improve.
Detailed description of the invention
Fig. 1 is 4 two kinds of er-doped tellurium germanate glasses of embodiment 3 and embodiment in the laser diode-pumped of 980nm wavelength
Luminous map down, embodiment 3 only obtain central wavelength about in the fluorescence of 2.7 mu m wavebands, and embodiment 4 obtains central wavelength about in 2 μ
The fluorescence spectrum of m and 2.7 mu m wavebands.
Specific embodiment
Following specific embodiments as exemplary and help to further understand the present invention, but case study on implementation to the present invention
Detail does not represent technical solution whole under present inventive concept, therefore should not be construed as merely to illustrate the present invention
Limited overall technical solution, it is some for the technician, without departing from present inventive concept unsubstantiality increase
And change, such as simply change or replace with the technical characteristic with same or similar technical effect, belong to protection of the present invention
Range.
Table 1:
| Component (%) | 1# | 2# | 3# | 4# | 5# | 6# | 7# | 8# |
| TeO2 | 80 | 60 | 60 | 60 | 55 | 55 | 75 | 55 |
| GeO2 | 0 | 20 | 20 | 5 | 4 | 3 | 3 | 15 |
| ZnCl2 | 5 | 5 | 5 | 5 | 3 | 10 | 3 | 3 |
| BaO | 5 | 5 | 5 | 5 | 10 | 3 | 5 | 3 |
| Denitrating catalyst waste material | 0 | 0 | 0 | 15 | 20 | 10 | 10 | 10 |
| Na2O | 10 | 10 | 4 | 4 | 4 | 2 | 3.9 | 10 |
| Er2O3 | 0 | 0 | 6 | 6 | 4 | 17 | 0.1 | 4 |
A kind of embodiment 1: tellurate glass；
A kind of tellurate glass, raw material are formed as shown in 1# in table 1；
According to the mass percent that 1# glass in table 1 forms, the weight respectively formed accordingly is calculated, and weighs each raw material
Component；
It after raw material grinding is formed uniformly mixture, is put into gold crucible, is placed in 980 DEG C of Elema electric furnace and melts
30 minutes glass metals melted are made, high purity oxygen gas is passed through always in glass melting process and carries out atmosphere protection to remove glass
Moisture in glass liquid.The dewatered homogenized clarification of glass metal, then on Quick pouring to the mold for being pre-heated to 370 DEG C,
It places into and is had warmed up into 370 DEG C of the glass metal of Muffle furnace afterwards, after heat preservation 3 hours, then with 11 DEG C/h of speed drop
Temperature is then shut off Muffle furnace, is cooled to room temperature to 110 DEG C.
To glass, test result is as follows:
1. sheet glass and polishing by the glass processing after annealing at 10 × 20 × 1 millimeter.It is measured by prism-coupled instrument
The refractive index of glass is 2.23.
2. taking a little sample or particle after annealing, fine powdered is worn into agate mortar, carries out differential thermal analysis calorifics
Matter, glass start the difference of crystallization temperature and glass transformation temperature frequently as thermal stability parameter.Measure the glass of the present embodiment
Transition temperature Tg=351 DEG C, glass starts crystallization temperature Tx=451 DEG C, their difference DELTA T (Tx-Tg)=100 DEG C.
It is 645kgf/mm 3. measuring the Vickers hardness of the glass2。
A kind of embodiment 2: tellurium germanate glass；
A kind of tellurium germanate glass, raw material are formed as shown in 2# in table 1；
According to the mass percent that 2# glass in table 1 forms, the weight respectively formed accordingly is calculated, and weighs each raw material
Component；
It after raw material grinding is formed uniformly mixture, is put into gold crucible, is placed in 900 DEG C of Elema electric furnace and melts
30 minutes glass metals melted are made, high purity oxygen gas is passed through always in glass melting process and carries out atmosphere protection to remove glass
Moisture in glass liquid.The dewatered homogenized clarification of glass metal, then on Quick pouring to the mold for being pre-heated to 450 DEG C,
It places into and is had warmed up into 460 DEG C of Muffle furnace afterwards, after heat preservation 3 hours, then with 11 DEG C/h of speed be cooled to 110 DEG C, so
After close Muffle furnace, be cooled to room temperature.
To glass, test result is as follows:
1. the tellurium germanate compound glass that the present embodiment is prepared is transparent, by the glass processing after annealing at 10 × 20 ×
1 millimeter of sheet glass and polishing.The refractive index of glass is measured by prism-coupled instrument.It is compared with embodiment 1, refractive index is from 2.24
2.00 are reduced to, illustrates GeO2Addition can cause the refractive index of glass to decline.
2. taking a little sample or particle after annealing, fine powdered is worn into agate mortar, carries out differential thermal analysis calorifics
Matter.It is compared with embodiment 1, glass transformation temperature increases to 451 DEG C from 351 DEG C, and thermal stability parameter increases to Δ T from 100 DEG C
=127 DEG C, illustrate GeO2Glass transformation temperature caused by the thermal stability of energy reinforcing glass but meeting is added to increase.
3. measuring the Vickers hardness of the glass.It is compared with embodiment 1, the Vickers hardness of glass is from 654kgf/mm2Increase to
654kgf/mm2, illustrate GeO2Be added can reinforcing glass hardness.
Embodiment 3: a kind of erbium mixes tellurium germanate glass；
A kind of erbium mixes tellurium germanate glass, and raw material is formed as shown in 3# in table 1；
According to the mass percent that 3# glass in table 1 forms, the weight respectively formed accordingly is calculated, and weighs each raw material
Component；
It after raw material grinding is formed uniformly mixture, is put into gold crucible, is placed in 900 DEG C of Elema electric furnace and melts
30 minutes glass metals melted are made, high purity oxygen gas is passed through always in glass melting process and carries out atmosphere protection to remove glass
Moisture in glass liquid.The dewatered homogenized clarification of glass metal, then on Quick pouring to the mold for being pre-heated to 460 DEG C,
It places into and is had warmed up into 460 DEG C of Muffle furnace afterwards, after heat preservation 3 hours, then with 11 DEG C/h of speed be cooled to 110 DEG C, so
After close Muffle furnace, be cooled to room temperature.
To glass, test result is as follows:
1. the erbium that the present embodiment is prepared is mixed, tellurium germanate glass is transparent, by the glass processing after annealing at 10 × 20 ×
1 millimeter of sheet glass and polishing.The refractive index of glass is measured by prism-coupled instrument.It is compared with embodiment 1, the refractive index of glass
It is 2.01.
2. taking a little sample or particle after annealing, fine powdered is worn into agate mortar, carries out differential thermal analysis calorifics
Matter.Glass transformation temperature is 463 DEG C, and thermal stability parameter is 143 DEG C.
It is 660kgf/mm 3. measuring the Vickers hardness of the glass2。
4. erbium obtained by the present embodiment mixes tellurium germanate glass in 1860- under the pumping of 980nm semiconductor laser
Only obtained within the scope of 2860nm central wavelength 2.7 μm shine, as shown in Figure 1.
A kind of embodiment 4: infrared tellurium germanate glass in high er-doped；
Infrared tellurium germanate glass in a kind of high er-doped, raw material are formed as shown in 4# in table 1；
Denitrating catalyst waste material is carried out to calcining 55 minutes at 120 DEG C, is sieved after grinding in 325 mesh, screen over-size 3%.
According to the mass percent that 4# glass in table 1 forms, the weight respectively formed accordingly is calculated, and weighs each raw material component, is ground
It after mill is formed uniformly mixture, is put into gold crucible, is placed in 980 DEG C of Elema electric furnace melted 30 minutes and is melted
Glass metal, be passed through always in glass melting process high purity oxygen gas carry out atmosphere protection to remove the moisture and rush in glass metal
It is sufficiently reacted into each raw material.The dewatered homogenized clarification of glass metal, then Quick pouring to the mold for being pre-heated to 370 DEG C
On, after place into and have warmed up into 380 DEG C of Muffle furnace, after heat preservation 3 hours, then with 11 DEG C/h of speed be cooled to 110
DEG C, it is then shut off Muffle furnace, is cooled to room temperature.
To glass, test result is as follows:
1. the erbium that the present embodiment is prepared is mixed, tellurium germanate glass is transparent, by the glass processing after annealing at 10 × 20 ×
1 millimeter of sheet glass and polishing.The refractive index of glass is measured by prism-coupled instrument.It is compared with embodiment 1, the refractive index of glass
Increase to 2.32 from 2.23, illustrates that the introducing of denitrating catalyst waste material effectively improves GeO2The decline of refractive index caused by being added is asked
Topic.
2. taking a little sample or particle after annealing, fine powdered is worn into agate mortar, carries out differential thermal analysis calorifics
Matter.It is compared with embodiment 3, glass transformation temperature is reduced to 370 DEG C from 460 DEG C, and thermal stability parameter increases to from 143 DEG C
154 DEG C, illustrate that the addition of denitrating catalyst waste material can effectively improve GeO2The problem of glass transformation temperature caused by being added increases,
And keep the good thermal stability of glass.
3. measuring the Vickers hardness of the glass.It is compared with embodiment 3, glass hard (HRC65Yi Shang) is from 660kgf/mm2Increase to
670kgf/mm2, illustrate the hardness that energy reinforcing glass is added of denitrating catalyst waste material.
4. erbium obtained by the present embodiment mixes tellurium germanate glass in 1860- under the pumping of 980nm semiconductor laser
Within the scope of 2860nm obtain central wavelength 2 μm and 2.7 μm shine, as shown in Figure 1.And with embodiment 3 in same spectra
Test condition compares, and luminous strength ratio embodiment 3 of the present embodiment central wavelength near 2.7 μm improves 5 times.
A kind of embodiment 5: infrared tellurium germanate glass in high er-doped；
Infrared tellurium germanate glass in a kind of high er-doped, raw material are formed as shown in 5# in table 1；
Denitrating catalyst waste material is carried out to calcining 55 minutes at 120 DEG C, is sieved after grinding in 325 mesh, screen over-size 3%.
According to the mass percent that 5# glass in table 1 forms, the weight respectively formed accordingly is calculated, and weighs each raw material component, is ground
It after mill is formed uniformly mixture, is put into gold crucible, is placed in 980 DEG C of Elema electric furnace melted 30 minutes and is melted
Glass metal, high purity oxygen gas is passed through in glass melting process always and carries out atmosphere protection to remove moisture and the promotion in glass metal
Each raw material sufficiently reacts.By the homogenized clarification of dewatered glass metal, then Quick pouring to the mold for being pre-heated to 370 DEG C
On, after place into and have warmed up into 380 DEG C of Muffle furnace, after heat preservation 3 hours, then with 11 DEG C/h of speed be cooled to 110
DEG C, it is then shut off Muffle furnace, is cooled to room temperature.
To glass, test result is as follows:
1. the erbium that the present embodiment is prepared is mixed, tellurium germanate glass is transparent, by the glass processing after annealing at 10 × 20 ×
1 millimeter of sheet glass and polishing.It is 2.33 by the refractive index that prism-coupled instrument measures glass.
2. taking a little sample or particle after annealing, fine powdered is worn into agate mortar, carries out differential thermal analysis calorifics
Matter obtains glass transformation temperature TgIt is 382 DEG C, thermal stability parameter, Δ T is 150 DEG C.
It is 690kgf/mm 3. measuring the Vickers hardness of the glass2。
4. under the pumping of 980nm semiconductor laser, with not waste material containing denitrating catalyst, remaining raw material and preparation method
Blank example all identical with the present embodiment compares, and blank example only obtains central wavelength about in 2.7 μm of luminous, the present embodiment gained
Erbium mixes tellurium germanate glass and obtains central wavelength within the scope of 1860-2860nm to shine at 2 μm and 2.7 μm, and this implementation
Fluorescence intensity of the example at 2.7 μm is remarkably reinforced, and about enhances 4 times compared with blank example.
A kind of embodiment 6: infrared tellurium germanate glass in high er-doped；
Infrared tellurium germanate glass in a kind of high er-doped, raw material are formed as shown in 6# in table 1；
Denitrating catalyst waste material is carried out to calcining 60 minutes at 150 DEG C, is sieved after grinding in 325 mesh, screen over-size 4%.
According to the mass percent that 6# glass in table 1 forms, the weight respectively formed accordingly is calculated, and weighs each raw material component, is ground
It after mill is formed uniformly mixture, is put into gold crucible, is placed in 780 DEG C of Elema electric furnace melted 25 minutes and is melted
Glass metal, high purity oxygen gas is passed through in glass melting process always and carries out atmosphere protection to remove moisture and the promotion in glass metal
Each raw material sufficiently reacts.By the homogenized clarification of dewatered glass metal, then Quick pouring to the mold for being pre-heated to 360 DEG C
On, after place into and have warmed up into 370 DEG C of Muffle furnace, after heat preservation 2.5 hours, then with 10 DEG C/h of speed be cooled to 105
DEG C, it is then shut off Muffle furnace, is cooled to room temperature.
To glass, test result is as follows:
1. the erbium that the present embodiment is prepared is mixed, tellurium germanate glass is transparent, by the glass processing after annealing at 10 × 20 ×
1 millimeter of sheet glass and polishing.It is 2.30 by the refractive index that prism-coupled instrument measures glass.
2. taking a little sample or particle after annealing, fine powdered is worn into agate mortar, carries out differential thermal analysis calorifics
Matter obtains glass transformation temperature TgIt is 372 DEG C, thermal stability parameter, Δ T is 151 DEG C.
It is 685kgf/mm 3. measuring the Vickers hardness of the glass2
4. under the pumping of 980nm semiconductor laser, with not waste material containing denitrating catalyst, remaining raw material and preparation method
Blank example all identical with the present embodiment compares, and blank example only obtains central wavelength about in 2.7 μm of luminous, the present embodiment gained
Erbium mixes tellurium germanate glass and obtains central wavelength within the scope of 1860-2860nm to shine at 2 μm and 2.7 μm, and this implementation
Fluorescence intensity of the example at 2.7 μm is remarkably reinforced, and about enhances 2 times compared with blank example.
A kind of embodiment 7: infrared tellurium germanate glass in high er-doped；
Infrared tellurium germanate glass in a kind of high er-doped, raw material are formed as shown in 7# in table 1；
Denitrating catalyst waste material is carried out to calcining 65 minutes at 200 DEG C, is sieved after grinding in 325 mesh, screen over-size 3%.
According to the mass percent that 7# glass in table 1 forms, the weight respectively formed accordingly is calculated, and weighs each raw material component；It grinds
It after mill is formed uniformly mixture, is put into gold crucible, is placed in 750 DEG C of Elema electric furnace melted 20 minutes and is melted
Glass metal, high purity oxygen gas is passed through in glass melting process always and carries out atmosphere protection to remove moisture and the promotion in glass metal
Each raw material sufficiently reacts.By the homogenized clarification of glass metal, then on Quick pouring to the mold for being pre-heated to 350 DEG C, after put again
Enter and have warmed up into 360 DEG C of Muffle furnace, after heat preservation 2 hours, then with 9 DEG C/h of speed is cooled to 100 DEG C, is then shut off
Muffle furnace is cooled to room temperature.
To glass, test result is as follows:
1. the erbium that the present embodiment is prepared is mixed, tellurium germanate glass is transparent, by the glass processing after annealing at 10 × 20 ×
1 millimeter of sheet glass and polishing.It is 2.34 by the refractive index that prism-coupled instrument measures glass.
2. taking a little sample or particle after annealing, fine powdered is worn into agate mortar, carries out differential thermal analysis calorifics
Matter obtains glass transformation temperature TgIt is 342 DEG C, thermal stability parameter, Δ T is 159 DEG C.
It is 688kgf/mm 3. measuring the Vickers hardness of the glass2。
4. under the pumping of 980nm semiconductor laser, with not waste material containing denitrating catalyst, remaining raw material and preparation method
Blank example all identical with the present embodiment compares, and blank example only obtains central wavelength about in 2.7 μm of luminous, the present embodiment gained
Erbium mixes tellurium germanate glass and obtains central wavelength within the scope of 1860-2860nm to shine at 2 μm and 2.7 μm, and this implementation
Fluorescence intensity of the example at 2.7 μm is remarkably reinforced, and about enhances 1 times compared with blank example.
A kind of embodiment 8: infrared tellurium germanate glass in high er-doped；
Infrared tellurium germanate glass in a kind of high er-doped, raw material are formed as shown in 8# in table 1；
Denitrating catalyst waste material is carried out to calcining 65 minutes at 200 DEG C, is sieved after grinding in 325 mesh, screen over-size 3%.
According to the mass percent that 8# glass in table 1 forms, the weight respectively formed accordingly is calculated, and weighs each raw material component；It grinds
It after mill is formed uniformly mixture, is put into gold crucible, is placed in 780 DEG C of Elema electric furnace melted 25 minutes and is melted
Glass metal, high purity oxygen gas is passed through in glass melting process always and carries out atmosphere protection to remove moisture and the promotion in glass metal
Each raw material sufficiently reacts.By the homogenized clarification of glass metal, then on Quick pouring to the mold for being pre-heated to 360 DEG C, after put again
Enter and have warmed up into 370 DEG C of Muffle furnace, after heat preservation 2.5 hours, then with 10 DEG C/h of speed is cooled to 105 DEG C, then closes
Muffle furnace is closed, room temperature is cooled to.
To glass, test result is as follows:
1. the erbium that the present embodiment is prepared mixes tellurium germanate glass, by the glass processing after annealing at 10 × 20 × 1 milli
Rice sheet glass and polishing.It is 2.31 by the refractive index that prism-coupled instrument measures glass.
2. taking a little sample or particle after annealing, fine powdered is worn into agate mortar, carries out differential thermal analysis calorifics
Matter obtains glass transformation temperature TgIt is 351 DEG C, thermal stability parameter, Δ T is 151 DEG C.
It is 683kgf/mm 3. measuring the Vickers hardness of the glass2。
4. under the pumping of 980nm semiconductor laser, with not waste material containing denitrating catalyst, remaining raw material and preparation method
Blank example all identical with the present embodiment compares, and blank example only obtains central wavelength about in 2.7 μm of luminous, the present embodiment gained
Erbium mixes tellurium germanate glass and obtains central wavelength within the scope of 1860-2860nm to shine at 2 μm and 2.7 μm, and this implementation
Fluorescence intensity of the example at 2.7 μm is remarkably reinforced, and about enhances 3 times compared with blank example.
Infrared tellurium germanate glass in the high er-doped prepared through the invention, glass smelting temperature is low, glass transformation temperature
It is low, there is good thermal stability, the refractive index of glass is high, and rear-earth-doped concentration is high, good mechanical performance, in 980nm half
Under the pumping of conductor laser, obtain central wavelength about 2 μm and 2.7 μm it is stronger shine, preparation method is easy, is suitable for
The preparation and application of 2-3 μm of laser glass and fiber optic materials.
Claims (3)
1. infrared tellurium germanate glass in a kind of high er-doped, which is characterized in that by mass percentage, including the following raw material:
It include titanium dioxide, tungstic acid and vanadic anhydride in the denitrating catalyst waste material.
2. the preparation method of infrared tellurium germanate glass in high er-doped as described in claim 1, which is characterized in that this method packet
Include the following steps:
(1) raw material preparation: denitrating catalyst waste material is subjected to calcining 55~65 minutes at 120~200 DEG C, in 325 mesh after grinding
Sieving, screen over-size is less than 5%；According to the mass percent that glass forms, the weight accordingly respectively formed is calculated, raw material is weighed；
(2) it technology of preparing: after all raw material components grindings are formed uniformly mixture, are put into gold crucible, are placed in 750-980
DEG C Elema electric furnace in be melted 20-30 minute, homogenizing and clarify after obtain the glass metal of uniform bubble-free；
(3) it is poured: the glass metal that step (2) obtains is poured on the mold for being pre-heated to 350-370 DEG C；
(4) anneal: after place into and have warmed up into 360-380 DEG C of Muffle furnace, after heat preservation 2-3 hours, then with 9-11 DEG C/h
Speed be cooled to 100-110 DEG C, be then shut off Muffle furnace, be cooled to room temperature.
3. the preparation method of infrared tellurium germanate glass in high er-doped according to claim 2, which is characterized in that in step
(2) constantly it is passed through the high purity oxygen gas that purity is greater than 99.95% in melting process into gold crucible in the form of bubbling.
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| CN112110649A (en) * | 2020-09-23 | 2020-12-22 | 中国计量大学 | Tellurium bismuthate mid-infrared 2.7 micron luminescent glass and preparation method thereof |
| CN112342621B (en) * | 2020-10-15 | 2023-01-06 | 江苏师范大学 | Tellurium-doped bismuth germanate crystal material and preparation method and application thereof |
| CN112321154A (en) * | 2020-12-16 | 2021-02-05 | 中国计量大学 | Low-phonon-energy high-erbium-doped intermediate infrared laser glass and preparation method thereof |
| CN113754279B (en) * | 2021-10-21 | 2023-02-03 | 中国计量大学 | High erbium-doped mid-infrared 3.5-micron laser glass and preparation method thereof |
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| CN101224947A (en) * | 2008-02-04 | 2008-07-23 | 中国科学院上海光学精密机械研究所 | 2 mu m waveband luminescent oxyhalide tellurate glass |
| CN103241948A (en) * | 2013-04-27 | 2013-08-14 | 中国电子科技集团公司第二十三研究所 | Method for preparing oxygen fluorine chlorine tellurate glass with intermediate infrared fluorescence output at 4 mu m |
| CN103771717A (en) * | 2014-01-23 | 2014-05-07 | 中国科学院上海光学精密机械研究所 | Preparation method for tellurate glass compound optical fibers |
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| CN101224947A (en) * | 2008-02-04 | 2008-07-23 | 中国科学院上海光学精密机械研究所 | 2 mu m waveband luminescent oxyhalide tellurate glass |
| CN103241948A (en) * | 2013-04-27 | 2013-08-14 | 中国电子科技集团公司第二十三研究所 | Method for preparing oxygen fluorine chlorine tellurate glass with intermediate infrared fluorescence output at 4 mu m |
| CN103771717A (en) * | 2014-01-23 | 2014-05-07 | 中国科学院上海光学精密机械研究所 | Preparation method for tellurate glass compound optical fibers |
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