CN101182121B - Bismuth-nickel co-doped transparent silicate glass ceramics and preparation method thereof - Google Patents
Bismuth-nickel co-doped transparent silicate glass ceramics and preparation method thereof Download PDFInfo
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- CN101182121B CN101182121B CN2007100477608A CN200710047760A CN101182121B CN 101182121 B CN101182121 B CN 101182121B CN 2007100477608 A CN2007100477608 A CN 2007100477608A CN 200710047760 A CN200710047760 A CN 200710047760A CN 101182121 B CN101182121 B CN 101182121B
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- LGRDPUAPARTXMG-UHFFFAOYSA-N bismuth nickel Chemical compound [Ni].[Bi] LGRDPUAPARTXMG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000006017 silicate glass-ceramic Substances 0.000 title claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 74
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000156 glass melt Substances 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 44
- 230000003287 optical effect Effects 0.000 abstract description 12
- 229910052759 nickel Inorganic materials 0.000 abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 229910020068 MgAl Inorganic materials 0.000 description 13
- 238000004891 communication Methods 0.000 description 8
- 238000005086 pumping Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000013307 optical fiber Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- -1 rare earth ion Chemical class 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
A bismuth-nickel co-doped transparent silicate glass ceramics and a preparation method thereof, the glass comprises the following components by mol percent: SiO 22(45～55)、Al2O3(10～20)、Ga2O3(5～20)、MgO(15～25)、TiO2(5～10)、NiO(0.005～1)、Bi2O3(0.005-2), the near-infrared fluorescence intensity of nickel in the bismuth-nickel co-doped transparent silicate glass ceramics obtained by bismuth-nickel co-doping can be improved by about 4.4 times to the maximum, and the fluorescence life can be prolonged from 210 microseconds of single nickel doping to 350 microseconds of co-doping, so that the bismuth-nickel co-doped transparent glass ceramics is expected to be applied in the fields of broadband optical amplifiers, high-power lasers, tunable lasers and the like.
Description
Technical field
The present invention relates to opticglass, particularly a kind of bismuth-nickel co-doped transparent silicate glass-ceramics and preparation method thereof.This transparent glass-ceramics can produce the near infrared communication band fluorescence stronger than adulterated this transparent glass-ceramics of single nickel (abbreviating Ni as) under the pumping of 980nm light source, has long fluorescence lifetime, wide gain bandwidth is suitable as the gain media of wide-band optical amplifier and laser apparatus.
Background technology
In recent years, along with the develop rapidly of computer network and other new data transport service, fiber optic transmission system long haul sharply expands to the demand of message capacity.How further to improve the message capacity of existing fiber transmission system,, become the focus of optical communication field research to satisfy this demand of expansible day by day.Think extensively that at present increasing the gain bandwidth of fiber amplifier in the ferry optical transmission system and flatness is the effective means that increases the Optical Fiber Transmission capacity.Yet, practical now gain of EDFA bandwidth is difficult to be widened again, this is because the bandwidth of rare earth ion 4f-4f optical transition is narrow in essence, so by a kind of rare earth ion doped and the expansion optical amplifier bandwidth that causes is limited.Same problem also occurs in thulium, on one's body the praseodymium, rare earth ions such as samarium.Amplify in broadband in optical fiber Raman amplifier (FRAs) can be realized on a large scale, but its multiwave pumping of needs and gain efficiency are low, and the complex structure of wide band optical fiber Raman amplifier, needs extra heavy pump laser, and energy expenditure is big.Therefore, if can develop a kind of ultra-wideband-light amplifier that has high gain and cover whole communication window, so just might only realize that with an image intensifer optical signal of whole communication window obtains amplifying simultaneously, this will cause the progress that optical communication field is tremendous, promote that optical communication develops to all-optical communication network.
Transition metal nickel ion (Ni
2+) for a long time always as the active ions of crystalline material, it can realize covering the luminous of overall optical communication window near infrared region under the pumping of 980nm light source, and has high quantum yield and long life-span.For example, known Ni
2+: the MgO crystal, show broad-band illumination about 1.3 μ m places greatly, and realized laser output, but the nickel doped crystal is difficult to be drawn into optical fiber, limited its application aspect broadband light amplification and tunable laser.And Ni
2+Doped-glass at room temperature has only very weak infraluminescence, in addition in some glass, do not have luminous, this be because in the non-crystalline state environment Ni
2+Radiationless transition process dominate.Transparent glass-ceramics is expected to become the carrier of Ni, is easy to make different shape because it can resemble the glass, simultaneously the nanocrystalline Ni that can be used as in the devitrified glass
2+Ionic activates body, thereby realizes having high quantum yield in the Ni doped crystal and long-life broadband infrared is luminous.
But compare with crystal, the doping content of nickel in devitrified glass is very low, causes it a little less than the absorption of near-infrared region, and this greatly reduces its pumping efficiency and infraluminescence character.Based on the sensitized luminescence principle, if can find a kind of like this sensitized ions: its emission and Ni under the 980nm laser pumping
2+The near infrared absorption of ion in devitrified glass has spectra overlapping preferably, so just might shift by energy to strengthen Ni
2+Infraluminescence character.
Summary of the invention
The objective of the invention is in order to improve Ni in the transparent glass-ceramics
2+Ion spectra character proposes a kind of bismuth-nickel co-doped transparent silicate glass-ceramics and preparation method thereof, shifts luminosity with strongthener by bismuth to the energy of nickel.By mixing altogether of bismuth, the near-infrared fluorescent intensity of nickel is the highest to improve about 4.4 times, fluorescence lifetime can be brought up to 350 microseconds when mixing altogether from 210 microseconds of singly mixing nickel, makes this bismuth-nickel co-doped transparent glass-ceramics be expected to be applied in fields such as wide-band optical amplifier, superpower laser, tunable laser.
Technical solution of the present invention is as follows:
A kind of bismuth-nickel co-doped transparent silicate glass-ceramics, composition and molar percentage that this glass is raw materials used are as follows:
Ingredient m ol%
SiO
2 45～55
Al
2O
3 10～20
Ga
2O
3 5～20
TiO
2 5～10
NiO 0.005～1
Bi
2O
3 0.005～2
The preparation method of described bismuth-nickel co-doped transparent silicate glass-ceramics comprises the following steps:
(1) composition and the molar percentage of selected glass, each raw material by the certain total amount of this proportioning weighing ground in agate mortar 10～60 minutes;
(2) ground raw material is put into Platinum crucible, melt soaking time 1～10 hour in 1500～1650 ℃;
(3) glass melt is cast on the stainless-steel sheet, and gently flatten with another steel plate, change over to afterwards in the retort furnace and under 550～700 ℃, anneal soaking time 0.5～10 hour, close the retort furnace power supply then and reduce to room temperature with stove, take out and promptly get transparent glass by glass;
(4) according to the DTA on Glass result, be raised to 800～950 ℃ with 300 ℃/hour temperature rise rates from room temperature, be incubated 1～20 hour; Perhaps adopt two step thermal treatments: the temperature rise rate with 300 ℃/h is raised to 700～750 ℃ from room temperature earlier, be incubated 2～20 hours, be raised to 800～950 ℃ with same temperature rise rate again, be incubated 1～20 hour, close the retort furnace power supply then, allow the glass furnace cooling to room temperature, taking-up can obtain transparent glass-ceramics.
Experiment shows: the color of glass of the present invention and devitrified glass is with NiO and Bi
2O
3Doping content and present different colours (seeing Table 1); All glass and devitrified glass sample be homogeneous transparent all.The crystallite of separating out in the devitrified glass is MgAl mutually
2O
4Spinel solid solution, below 7nm, and with the prolongation of heat treatment time, size does not have considerable change 950 ℃ of sizes after handling 2 hours.MgAl
2O
4Spinel has tetrahedron and octahedra two kinds of rooms, wherein Mg
2+Ion occupies eighth tetrahedral vacancy, Al
3+Ion occupies the octahedral voids of half.Ni in this transparent glass-ceramics that Bi, Ni mix altogether
2+Ion enters the Al in remaining octahedral voids and/or the alternative octahedron of part
3+Ion forms spinel solid solution, and the Bi ion resides in the glassy phase, and this is much bigger because of the size of tetrahedron in the Bi ionic radius ratio spinel and octahedral voids, can't enter in the spinel.Spectrum test is found, Ni in the devitrified glass
2+Ion
3A
2(
3F) →
3T
2(
3F) the near infrared emission under the 980nm pumping of absorption and Bi ion has spectra overlapping (as shown in Figure 1) preferably, according to the sensitized luminescence principle Bi might take place and shift to the useful energy of Ni.Our result proves that also the Bi ion is really to Ni
2+The useful energy transfer has taken place in ion, has improved Ni greatly
2+The near-infrared luminous character of ionic.
Experiment shows: by mixing altogether of bismuth nickel, the near-infrared fluorescent intensity of nickel is the highest to improve about 4.4 times, fluorescence lifetime can be brought up to 350 microseconds when mixing altogether from 210 microseconds of singly mixing nickel, makes this bismuth-nickel co-doped transparent glass-ceramics be expected to be applied in fields such as wide-band optical amplifier, superpower laser, tunable laser.
Description of drawings
Fig. 1 is the emmission spectrum (curve 1, the 980nm laser diode excites) of comparative example's 2 devitrified glasses of the present invention and the absorption spectrum (curve 2) of Comparative Examples 3 devitrified glasses.
Fig. 2 is the emmission spectrum (the 980nm laser diode excites) of Comparative Examples 3 of the present invention and embodiment 4-7 devitrified glass.
Embodiment
The present invention is further illustrated below in conjunction with embodiment and accompanying drawing, but should not limit protection scope of the present invention with this.
Table 1 has been listed composition and the molar percentage thereof of 11 embodiment of glass of the present invention, the color of the color of corresponding glass, heat treating regime, devitrified glass, fluorescence peak position, halfwidth, the test result in life-span of devitrified glass under the 980nm pump light excites also listed in wherein, and wherein embodiment 2 and 3 is Comparative Examples.
Embodiment 1
This embodiment's micro-NiO and Bi has only mixed
2O
3The preparation method of transparent glass-ceramics is as follows: press the raw material of the about 50g of composition proportioning weighing of embodiment 1, ground 30 minutes in agate mortar, place the inherent 1550 ℃ of fusions of Platinum crucible 2 hours then; Glass melt is cast on the stainless-steel sheet fast, and gently flattens with another block plate, changes over to afterwards in the retort furnace to anneal 2 hours down at 650 ℃, closes the retort furnace power supply then and reduces to room temperature by glass with stove, takes out promptly to get to be similar to colourless transparent glass.The transparent glass sample is put into retort furnace be raised to 950 ℃ with the speed of 300 ℃/h from room temperature, be incubated 2 hours, close the retort furnace power supply then and drop to room temperature by glass sample with stove, taking-up can obtain transparent glass-ceramics, is approximate colourless.The devitrified glass sample is processed into 7 * 7 * 2mm
3, the polishing back is for the usefulness of test.Because of doping content is very low, 980nm is laser diode-pumped have only down very weak from Ni
2+Ionic is near-infrared luminous, the about 124nm of halfwidth, and the life-span under the room temperature is about 62 microseconds.
Comparative Examples 2 and 3
Comparative example 2 and 3 has singly mixed Bi respectively
2O
3And NiO.The preparation method of transparent glass-ceramics is as follows: press the raw material of the about 50g of composition proportioning difference weighing of comparative example 2 and 3, ground 30 minutes in agate mortar, place the inherent 1550 ℃ of fusions of Platinum crucible 2 hours then; Glass melt is cast on the stainless-steel sheet fast, and gently flattens with another block plate, changes over to afterwards in the retort furnace to anneal 2 hours down at 650 ℃, closes the retort furnace power supply then and reduces to room temperature by glass with stove, takes out and promptly gets transparent glass.Comparative example's 2 glass pinkiness, comparative example's 3 glass are pale brown look.The transparent glass sample is put into retort furnace be raised to 950 ℃ with the speed of 300 ℃/h from room temperature, be incubated 2 hours, close the retort furnace power supply then and drop to room temperature by glass sample with stove, taking-up can obtain transparent glass-ceramics.Comparative example's 2 devitrified glasses are reddish brown, and comparative example's 3 devitrified glasses are light sea blue look.The devitrified glass sample is processed into 7 * 7 * 2mm
3, the polishing back is for the usefulness of test.Fig. 1 is the emission (980nm excites) of comparative example's 2 devitrified glasses and the absorption spectrum of comparative example's 3 devitrified glasses, can see that Bi ion center is at emmission spectrum and the Ni of 1137nm in the devitrified glass
2+Overlapping at the absorption spectrum of 1000nm in the ion center, therefore the Bi ion might take place to Ni
2+Energy of ions shifts.Fluorescence spectrum under comparative example's 3 devitrified glass 980nm pumpings as shown in Figure 2, the fluorescence peak position is at 1240nm, the fluorescence halfwidth is about 262nm, the life-span under the room temperature is about 210 microseconds.
Embodiment 4-7
These four embodiment have similar composition, the Bi of the different content that mixed
2O
3, and the content of NiO is fixed as 0.3mol%.The preparation method of transparent glass-ceramics is as follows: press the raw material of the about 50g of composition proportioning difference weighing of four embodiment, ground 30 minutes in agate mortar, place the inherent 1550 ℃ of fusions of Platinum crucible 2 hours then; Glass melt is cast on the stainless-steel sheet fast, and gently flattens with another block plate, changes over to afterwards in the retort furnace to anneal 2 hours down at 650 ℃, closes the retort furnace power supply then and reduces to room temperature by glass with stove, takes out and promptly gets transparent glass, all is pale brown look.The transparent glass sample is put into retort furnace be raised to 950 ℃ from room temperature with the speed of 300 ℃/h, be incubated 2 hours, close the retort furnace power supply then and drop to room temperature by glass sample with stove, taking-up can obtain transparent glass-ceramics, embodiment 4 devitrified glasses are shallow reddish brown, the individual reddish brown that all is of its excess-three.The devitrified glass sample is processed into 7 * 7 * 2mm
3, the polishing back is for the usefulness of test.The fluorescence spectrum of devitrified glass can be seen along with Bi as shown in Figure 2
2O
3The increase Ni of concentration
2+The ionic fluorescence intensity constantly strengthens, and at Bi
2O
3Fluorescence intensity began to descend when concentration surpassed 0.75mol%.Singly mix the fluorescence intensity of NiO devitrified glass with comparative example 3 and compare, embodiment 4,5, and 6 and 7 fluorescence intensity has strengthened about 2.2,3.4,4.4 and 3.1 times respectively, and the fluorescence halfwidth changes little, and fluorescence lifetime has improved about 40～140 microseconds.
Embodiment 8-11
These four embodiment's NiO and Bi of high level have mixed
2O
3The preparation method of transparent glass-ceramics is as follows: press the raw material of the about 50g of composition proportioning difference weighing of above-mentioned four embodiment, ground 30 minutes in agate mortar, place the inherent 1580 ℃ of fusions of Platinum crucible 2 hours then; Glass melt is cast on the stainless-steel sheet fast, and gently flattens with another block plate, changes over to afterwards in the retort furnace to anneal 2 hours down at 650 ℃, closes the retort furnace power supply then and reduces to room temperature by glass with stove, takes out and promptly gets transparent glass; The glass of embodiment 8 is pale brown look, and its excess-three is individual to be brown.The transparent glass sample is put into retort furnace be raised to 950 ℃ with the speed of 300 ℃/h from room temperature, be incubated 2 hours, close the retort furnace power supply then and drop to room temperature by glass sample with stove, taking-up can obtain transparent glass-ceramics.The devitrified glass of embodiment 8 is reddish brown, and the devitrified glass of its excess-three embodiment is dark reddish brown.The devitrified glass sample is processed into 7 * 7 * 2mm
3, the polishing back is for the usefulness of test.Because NiO and Bi
2O
3Doping content higher, Ni
2+Concentration quenching between the ion and Ni
2+Cross relaxation between ion and the Bi ion greatly reduces Ni
2+The ionic fluorescence intensity, fluorescence lifetime also shortens greatly simultaneously, and the fluorescence peak position is then with NiO concentration increase red shift gradually, and the fluorescence halfwidth also increases gradually with NiO concentration, sees Table 1.
Table 1
| The embodiment sequence number | 1 | 2 | 3 | 4 | 5 |
| SiO 2Al 2O 3Ga 2O 3MgOTiO 2NiOBi 2O 3The glass colour heat treating regime (℃-h) devitrified glass color crystallite phase fluorescence peak position (nm) fluorescence halfwidth (nm) fluorescence lifetime *(μs) | The approximate colourless MgAl of 45 10 20 20 5 0.005 0.005 approximate colourless 950-2 2O 4 1190 124 62 | 48 15 11 25 10 0 0.75 pink 950-2 reddish brown MgAl 2O 4 1137 191 285 | The light sea blue look MgAl of 50 16.5 8.3 16.6 8.3 0.3 0 pale brown 950-2 2O 4 1240 262 210 | The shallow reddish brown MgAl of 50 16.5 8.3 16.5 8.15 0.3 0.25 pale brown look 950-2 2 O 4 1240 270 250 | 50 16.4 8.3 16.4 8.1 0.3 0.5 pale brown look 950-2 reddish brown MgAl 2 O 4 1240 271 312 |
*The semiconductor diode pump of 980nm
Continuous table 1
| 6 | 7 | 8 | 9 | 10 | 11 |
| 50 16.3 8.15 16.3 8.2 0.3 0.75 pale brown look 950-2 reddish brown MgAl 2O 4 1240 264 350 | 50 16.2 8.1 16.2 8.2 0.3 1 pale brown look 950-2 reddish brown MgAl 2O 4 1240 272 313 | 52 20 5 15 6.25 0.5 1.25 pale brown look 950-2 reddish brown MgAl 2O 4 1260 286 235 | The dark reddish brown MgAl of 53 18 7 14.5 5.3 0.7 1.5 brown 950-2 2O 4 1296 302 168 | The dark reddish brown MgAl of 54 12 10 16 5.25 1 1.75 brown 950-2 2O 4 1328 315 110 | The dark reddish brown MgAl of 55 12 8 15 712 brown 950-2 2O 4 1328 320 94 |
Claims (2)
1. bismuth-nickel co-doped transparent silicate glass-ceramics is characterized in that composition and molar percentage that this glass is raw materials used are as follows:
Ingredient m ol%
SiO
2 45～55
Al
2O
3 10～20
Ga
2O
3 5～20
MgO 15～25
TiO
2 5～10
NiO 0.005～1
Bi
2O
30.005～2, the preparation method of this glass is as follows:
(1) composition and the molar percentage of selected glass, each raw material by the certain total amount of this proportioning weighing ground in agate mortar 10～60 minutes;
(2) ground raw material is put into Platinum crucible, melt soaking time 1～10 hour in 1500～1650 ℃;
(3) glass melt is cast on the stainless-steel sheet, and gently flattens, change over to afterwards in the retort furnace and under 550～700 ℃, anneal with another steel plate, soaking time 0.5～10 hour, close the retort furnace power supply then, allow glass reduce to room temperature, take out and promptly get transparent glass with stove;
(4) according to the DTA on Glass result, be raised to 800～950 ℃ with 300 ℃/hour temperature rise rates from room temperature, be incubated 1～20 hour; Perhaps adopt two step thermal treatments: the temperature rise rate with 300 ℃/h is raised to 700～750 ℃ from room temperature earlier, be incubated 2～20 hours, be raised to 800～950 ℃ with same temperature rise rate again, be incubated 1～20 hour, close the retort furnace power supply then, allow the glass furnace cooling to room temperature, taking-up can obtain transparent glass-ceramics.
2. the concrete preparation method of the described bismuth-nickel co-doped transparent silicate glass-ceramics of claim 1 is characterised in that to comprise the following steps:
(1) composition and the molar percentage of selected glass, each raw material by the certain total amount of this proportioning weighing ground in agate mortar 10～60 minutes;
(2) ground raw material is put into Platinum crucible, melt soaking time 1～10 hour in 1500～1650 ℃;
(3) glass melt is cast on the stainless-steel sheet, and gently flattens, change over to afterwards in the retort furnace and under 550～700 ℃, anneal with another steel plate, soaking time 0.5～10 hour, close the retort furnace power supply then, allow glass reduce to room temperature, take out and promptly get transparent glass with stove;
(4) according to the DTA on Glass result, be raised to 800～950 ℃ with 300 ℃/hour temperature rise rates from room temperature, be incubated 1～20 hour; Perhaps adopt two step thermal treatments: the temperature rise rate with 300 ℃/h is raised to 700～750 ℃ from room temperature earlier, be incubated 2～20 hours, be raised to 800～950 ℃ with same temperature rise rate again, be incubated 1～20 hour, close the retort furnace power supply then, allow the glass furnace cooling to room temperature, taking-up can obtain transparent glass-ceramics.
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| CN104163572A (en) * | 2014-07-15 | 2014-11-26 | 南昌大学 | Transparent glass ceramic having high efficiency white light emission and preparation method thereof |
| CN105712633B (en) * | 2016-01-13 | 2018-01-12 | 武汉理工大学 | Devitrified glass for lasing safety and preparation method thereof |
| CN106242272B (en) * | 2016-08-08 | 2018-10-30 | 盐城工学院 | A kind of doping Bi3+SiO2- CaO-MgO based laser glass and preparation method thereof |
| CN110407472B (en) * | 2019-07-30 | 2022-05-24 | 华南理工大学 | Nickel-doped ultra-wideband luminescent glass ceramic and preparation method and application thereof |
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| CN1587136A (en) * | 2004-09-02 | 2005-03-02 | 中国科学院上海光学精密机械研究所 | Preparation method of bismuth-doped high-silica near-infrared broadband luminescent glass |
| CN1676483A (en) * | 2005-03-18 | 2005-10-05 | 中国科学院上海光学精密机械研究所 | Nanometer bismuth cluster doped silicon dioxide-based optical glass and preparation method thereof |
| CN1807310A (en) * | 2006-02-10 | 2006-07-26 | 华南理工大学 | Rare earth doped gallium germanium bismuth lead luminous glass material and its preparation method and uses |
| EP1736452A1 (en) * | 2005-06-21 | 2006-12-27 | Elop Electro-Optics Industries Ltd. | Glass-ceramics for laser systems |
-
2007
- 2007-11-02 CN CN2007100477608A patent/CN101182121B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4470922A (en) * | 1982-11-12 | 1984-09-11 | Denker Boris I | Phosphate neodymium glass for laser use |
| CN1587136A (en) * | 2004-09-02 | 2005-03-02 | 中国科学院上海光学精密机械研究所 | Preparation method of bismuth-doped high-silica near-infrared broadband luminescent glass |
| CN1676483A (en) * | 2005-03-18 | 2005-10-05 | 中国科学院上海光学精密机械研究所 | Nanometer bismuth cluster doped silicon dioxide-based optical glass and preparation method thereof |
| EP1736452A1 (en) * | 2005-06-21 | 2006-12-27 | Elop Electro-Optics Industries Ltd. | Glass-ceramics for laser systems |
| CN1807310A (en) * | 2006-02-10 | 2006-07-26 | 华南理工大学 | Rare earth doped gallium germanium bismuth lead luminous glass material and its preparation method and uses |
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