CN102358681B - Transparent oxyfluoride tellurate glass - Google Patents

Transparent oxyfluoride tellurate glass Download PDF

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CN102358681B
CN102358681B CN 201110213439 CN201110213439A CN102358681B CN 102358681 B CN102358681 B CN 102358681B CN 201110213439 CN201110213439 CN 201110213439 CN 201110213439 A CN201110213439 A CN 201110213439A CN 102358681 B CN102358681 B CN 102358681B
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glass
oxyfluoride tellurate
tellurate glass
transparent
raw material
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CN102358681A (en
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侯朝霞
薛召露
王少洪
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Shenyang University
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Abstract

A transparent oxyfluoride tellurate glass. A TeO2-AlF3 oxygen fluorine glass system is added with SiO2, MO and RF, wherein MO represents one or more compounds from CaO, BaO, MgO and SrO, and RF represents one or more compounds from NaF, LiF and KF. The transparent oxyfluoride tellurate glass comprises the following components: 20-55mol% of TeO2, 0-30mol% of SiO2, 10-40mol% of AlF3, 10-20mol% of MO and 5-15mol% of RF. The transparent oxyfluoride tellurate glass without toxic heavy metals of Pb and Cd of the invention has excellent glass forming performance, chemical stability and heat stability, and is a good matrix glass material for rare earth doped infrared laser fiber and optical fiber amplifier.

Description

Transparent oxyfluoride tellurate glass
Technical field
The present invention relates to a kind of oxyfluoride glass and preparation method thereof.
Background technology
In recent years, the up-conversion luminescence of rare earth ion doped material is subjected to paying close attention to widely, and value has a wide range of applications in fields such as color monitor, high density data storage, seabed optical communication, detection and laser medicines.Compare with rare-earth-doped crystal, glass is less to the restriction of the kind of the rare earth ion that mixes and quantity, have the manufacturing cycle short, be easy to processing, advantage such as output wavelength is many, tunable range is wide.Because the phonon energy of glass matrix is low more, the last efficiency of conversion of rare earth ion is strong more, and therefore up to the present, many investigators mainly concentrate on energy the research of fluoride glass.Oxide glass is owing to have better chemical stability, and thermostability and fibre-optical drawing characteristic have more advantage than fluoride glass in actual applications.The phonon energy of tellurate is minimum in the oxide glass, have that specific refractory power is big, IR transmittance is high and low-melting characteristics, compare with fluoride glass and to have stability preferably, so tellurate glass has higher excited state radiative transistion probability and lower nonradiative transition probability.Oxyfluoride glass not only has the good optical property of fluoride glass but also have good chemical stability of oxide glass and thermostability.Some researchs have been carried out though adjust the spectral quality of rare earth doped tellurate glass with fluorochemical, but the introducing of fluorochemical has aggravated the tellurate thermostability and has become the decline of glass properties, the introducing of Pb, Cd can enlarge tellurate glass and form the district, therefore the oxyfluoride tellurate glass of having reported at present nearly all contains human body and the deleterious toxic heavy metal Pb of environment, Cd, has limited its large-scale commercial applications.
Summary of the invention
The object of the present invention is to provide a kind of transparent oxyfluoride tellurate glass that does not contain poisonous heavy metal Pb, Cd, it becomes glass properties, chemical stability and good heat stability, is a kind of good rear-earth-doped infrared laser optical fiber and fiber amplifier host glass material.
Technical scheme of the present invention is:
A kind of transparent oxyfluoride tellurate glass constitutes: at TeO 2-AlF 3Add SiO in the oxygen fluorine glass system 2, MO and RF, wherein: MO is one or more compounds among CaO, BaO, MgO and the SrO, RF is one or more compounds among NaF, LiF and the KF, each component and content thereof are as follows in this transparent oxyfluoride tellurate glass: 20～55mol%TeO 2, 5～30mol%SiO 2, 10～40mol%AlF 3, 10～20mol%MO and 5～15mol%RF.
A kind of preparation method of transparent oxyfluoride tellurate glass is:
1, according to the component of above-mentioned transparent oxyfluoride tellurate glass, selected transparent oxyfluoride tellurate glass composition of raw materials is pressed each raw material of composition of raw materials weighing, wherein, and TeO 2Be high pure raw material, RF, SiO 2, MO and AlF 3Be the analytical pure raw material.
2, the even batch mixing in planetary ball mill of the raw material in the step 1 was poured into platinum crucible, and added a cover after 30 minutes.
3, put into the globars resistance furnace and found adding a cover platinum crucible in the step 2, glass melting temperature is 850～1100 ℃, through fusing, homogenizing, clarification, obtains oxyfluoride tellurate glass liquid.
4, the oxyfluoride tellurate glass liquid after will clarifying is cast on the stainless steel mould of preheating and carries out moulding, obtains transparent oxyfluoride tellurate glass.
5, the transparent oxyfluoride tellurate glass after the moulding is put near be warming up to the glass transformation temperature retort furnace annealing rapidly to eliminate stress, cycle of annealing is: insulation earlier 2 hours, reduce to room temperature with stove then.
The invention has the beneficial effects as follows: the invention provides a kind of transparent oxyfluoride tellurate glass that does not contain human body and the deleterious toxic heavy metal Pb of environment, Cd.The present invention introduces oxyfluoride tellurate glass system with SiO2 and other improved properties compounds, by each component, composition are rationally adjusted, greatly improve the oxyfluoride tellurate system that does not contain poisonous heavy metal Pb, Cd and become glass properties, obtained the glass of chemical stability and good thermal stability.The present invention can be used as the host glass material of rare earth ion doped infrared laser optical fiber and fiber amplifier, in the application of band optical fiber, possesses more wide practical application foreground.
Description of drawings
Fig. 1 is an XRD figure spectrum of the present invention.
Embodiment
The invention will be further described below in conjunction with specific embodiment.Table 1 provides the transparent oxyfluoride tellurate glass prescription of 10 specific embodiments of the present invention.Table 2 is that 10 specific embodiments become glass situation and glass transformation temperature.
Table 1
Figure GDA00002942062000021
Table 2
Numbering 1 2 3 4 5 6 7 8 9 10
Become the glass situation Transparent Transparent Transparent Transparent Transparent Transparent Transparent Transparent Transparent Transparent
Glass transformation temperature (℃) 402 394 396 393 398 401 410 407 405 409
Embodiment 1
A kind of transparent oxyfluoride tellurate glass is according to the 1st group of selected transparent oxyfluoride tellurate glass composition of raw materials, i.e. 30TeO in the table 1 2-15SiO 2-30AlF 3-15CaO-10NaF(mol%).Its preparation method is:
1, according to the component of above-mentioned transparent oxyfluoride tellurate glass, selected transparent oxyfluoride tellurate glass composition of raw materials is pressed each raw material of composition of raw materials weighing, wherein, and TeO 2Be high pure raw material, NaF, SiO 2, CaO and AlF 3Be the analytical pure raw material.
2, the even batch mixing in planetary ball mill of the raw material in the step 1 was poured into platinum crucible, and added a cover after 30 minutes.
3, put into the globars resistance furnace and found adding a cover crucible in the step 2,860 ℃ of glass melting temperatures, raw material melts fully, then in 1010 ℃ of homogenizing, clarification, obtains oxyfluoride tellurate glass liquid.
4, the oxyfluoride tellurate glass liquid after will clarifying is cast on the stainless steel mould of preheating, obtains transparent oxyfluoride tellurate glass.
5, the transparent oxyfluoride tellurate glass after the moulding is put near be warming up to the glass transformation temperature retort furnace annealing rapidly to eliminate stress, cycle of annealing is: insulation earlier 2 hours, reduce to room temperature with stove then.
The XRD figure spectrum of the oxyfluoride tellurate glass sample for preparing under this Example formulations sees Fig. 1 for details, tangible as seen from Figure 1 glass steamed bun peak, and no crystallization diffraction peak exists, and no crystalline phase is separated out in the explanation system, and prepared material is a glass.
Embodiment 2
A kind of transparent oxyfluoride tellurate glass is according to the 2nd group of selected transparent oxyfluoride tellurate glass composition of raw materials, i.e. 25TeO in the table 1 2-15SiO 2-35AlF 3-15BaO-5LiF-5KF(mol%).Its preparation method is:
1, according to the component of above-mentioned transparent oxyfluoride tellurate glass, selected transparent oxyfluoride tellurate glass composition of raw materials is pressed each raw material of composition of raw materials weighing, wherein, and TeO 2Be high pure raw material, LiF, KF, SiO 2, BaO and AlF 3Be the analytical pure raw material.
2, the even batch mixing in planetary ball mill of the raw material in the step 1 was poured into platinum crucible, and added a cover after 30 minutes.
3, put into the globars resistance furnace and found adding a cover crucible in the step 2,850 ℃ of glass melting temperatures, raw material melts fully, then in 1000 ℃ of homogenizing, clarification, obtains oxyfluoride tellurate glass liquid.
4, the oxyfluoride tellurate glass liquid after will clarifying is cast on the stainless steel mould of preheating, obtains transparent oxyfluoride tellurate glass.
5, the transparent oxyfluoride tellurate glass after the moulding is put near be warming up to the glass transformation temperature retort furnace annealing rapidly to eliminate stress, cycle of annealing is: insulation earlier 2 hours, reduce to room temperature with stove then.
Embodiment 3
A kind of transparent oxyfluoride tellurate glass is according to the 5th group of selected transparent oxyfluoride tellurate glass composition of raw materials, i.e. 35TeO in the table 1 2-15SiO 2-25AlF 3-5CaO-10MgO-10LiF(mol%).Its preparation method is:
1, according to the component of above-mentioned transparent oxyfluoride tellurate glass, selected transparent oxyfluoride tellurate glass composition of raw materials is pressed each raw material of composition of raw materials weighing, wherein, and TeO 2Be high pure raw material, LiF, SiO 2, MgO, CaO and AlF 3Be the analytical pure raw material.
2, the even batch mixing in planetary ball mill of the raw material in the step 1 was poured into platinum crucible, and added a cover after 30 minutes.
3, put into the globars resistance furnace and found adding a cover crucible in the step 2,900 ℃ of glass melting temperatures, raw material melts fully, then in 1050 ℃ of homogenizing, clarification, obtains oxyfluoride tellurate glass liquid.
4, the oxyfluoride tellurate glass liquid after will clarifying is cast on the stainless steel mould of preheating, obtains transparent oxyfluoride tellurate glass.
5, the transparent oxyfluoride tellurate glass after the moulding is put near be warming up to the glass transformation temperature retort furnace annealing rapidly to eliminate stress, cycle of annealing is: insulation earlier 2 hours, reduce to room temperature with stove then.
Embodiment 4
A kind of transparent oxyfluoride tellurate glass is according to the 7th group of selected transparent oxyfluoride tellurate glass composition of raw materials, i.e. 35TeO in the table 1 2-25SiO 2-15AlF 3-15MgO-10NaF(mol%).Its preparation method is:
1, according to the component of above-mentioned transparent oxyfluoride tellurate glass, selected transparent oxyfluoride tellurate glass composition of raw materials is pressed each raw material of composition of raw materials weighing, wherein, and TeO 2Be high pure raw material, NaF, SiO 2, MgO and AlF 3Be the analytical pure raw material.
2, the even batch mixing in planetary ball mill of the raw material in the step 1 was poured into platinum crucible, and added a cover after 30 minutes.
3, put into the globars resistance furnace and found adding a cover crucible in the step 2,880 ℃ of glass melting temperatures, raw material melts fully, then in 1030 ℃ of homogenizing, clarification, obtains oxyfluoride tellurate glass liquid.
4, the oxyfluoride tellurate glass liquid after will clarifying is cast on the stainless steel mould of preheating, obtains transparent oxyfluoride tellurate glass.
5, the transparent oxyfluoride tellurate glass after the moulding is put near be warming up to the glass transformation temperature retort furnace annealing rapidly to eliminate stress, cycle of annealing is: insulation earlier 2 hours, reduce to room temperature with stove then.
Embodiment 5
A kind of transparent oxyfluoride tellurate glass is according to the 10th group of selected transparent oxyfluoride tellurate glass composition of raw materials, i.e. 35TeO in the table 1 2-25SiO 2-15AlF 3-10CaO-5MgO-5NaF-5LiF(mol%).Its preparation method is:
1, according to the component of above-mentioned transparent oxyfluoride tellurate glass, selected transparent oxyfluoride tellurate glass composition of raw materials is pressed each raw material of composition of raw materials weighing, wherein, and TeO 2Be high pure raw material, NaF, LiF, SiO 2, MgO, CaO and AlF 3Be the analytical pure raw material.
2, the even batch mixing in planetary ball mill of the raw material in the step 1 was poured into platinum crucible, and added a cover after 30 minutes.
3, put into the globars resistance furnace and found adding a cover crucible in the step 2,890 ℃ of glass melting temperatures, raw material melts fully, then in 1040 ℃ of homogenizing, clarification, obtains oxyfluoride tellurate glass liquid.
4, the oxyfluoride tellurate glass liquid after will clarifying is cast on the stainless steel mould of preheating, obtains transparent oxyfluoride tellurate glass.
5, the transparent oxyfluoride tellurate glass after the moulding is put near be warming up to the glass transformation temperature retort furnace annealing rapidly to eliminate stress, cycle of annealing is: insulation earlier 2 hours, reduce to room temperature with stove then.

Claims (2)

1. a transparent oxyfluoride tellurate glass is characterized in that: at TeO 2-AlF 3Add SiO in the oxygen fluorine glass system 2, MO and RF, wherein: MO is one or more compounds among CaO, BaO, MgO and the SrO, RF is one or more compounds among NaF, LiF and the KF, each component and content thereof are as follows in this transparent oxyfluoride tellurate glass: 20～55mol%TeO 2, 5～30mol%SiO 2, 10～40mol%AlF 3, 10～20mol%MO and 5～15mol%RF.
2. transparent oxyfluoride tellurate glass according to claim 1, it is characterized in that: its preparation method is: (1), according to the component of above-mentioned transparent oxyfluoride tellurate glass, and selected transparent oxyfluoride tellurate glass composition of raw materials is pressed each raw material of composition of raw materials weighing, wherein, TeO 2Be high pure raw material, RF, SiO 2, MO and AlF 3Be the analytical pure raw material; (2), the even batch mixing in planetary ball mill of the raw material in the step 1 was poured into platinum crucible, and added a cover after 30 minutes; (3), put into the globars resistance furnace and found, glass melting temperature is 850～1100 ℃, through fusing, homogenizing, clarification, obtains oxyfluoride tellurate glass liquid with adding a cover platinum crucible in the step 2; (4), the oxyfluoride tellurate glass liquid after will clarifying is cast on the stainless steel mould of preheating and carries out moulding, obtains transparent oxyfluoride tellurate glass; (5), the transparent oxyfluoride tellurate glass after the moulding is put near be warming up to the glass transformation temperature retort furnace annealing rapidly to eliminate stress, cycle of annealing is: insulation earlier 2 hours, reduce to room temperature with stove then.
CN 201110213439 2011-07-28 2011-07-28 Transparent oxyfluoride tellurate glass Expired - Fee Related CN102358681B (en)

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CN106430951B (en) * 2016-10-17 2019-06-04 西北工业大学 A kind of tellurium oxide and antimony fluoride system matrix glass and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001036353A1 (en) * 1999-11-19 2001-05-25 Corning Incorporated Fluorotellurite, amplifier glasses
CN1522979A (en) * 2003-09-05 2004-08-25 中国科学院上海光学精密机械研究所 Infrared permeating oxide fluoride glass

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001036353A1 (en) * 1999-11-19 2001-05-25 Corning Incorporated Fluorotellurite, amplifier glasses
CN1522979A (en) * 2003-09-05 2004-08-25 中国科学院上海光学精密机械研究所 Infrared permeating oxide fluoride glass

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《TeO2对氟铝酸盐玻璃性质和结构的影响》;范有余等;《无机材料学报》;20060331;第21卷(第2期);339-344页 *
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