CN1613804A - Lead-free germanium bismuthate glass and preparation method thereof - Google Patents
Lead-free germanium bismuthate glass and preparation method thereof Download PDFInfo
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- CN1613804A CN1613804A CN 200410067698 CN200410067698A CN1613804A CN 1613804 A CN1613804 A CN 1613804A CN 200410067698 CN200410067698 CN 200410067698 CN 200410067698 A CN200410067698 A CN 200410067698A CN 1613804 A CN1613804 A CN 1613804A
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- glass
- raw material
- lead free
- mol
- bismuth germanate
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- 239000011521 glass Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052732 germanium Inorganic materials 0.000 title abstract 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title abstract 2
- 230000007704 transition Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 20
- 229910052797 bismuth Inorganic materials 0.000 claims description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 abstract description 9
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 abstract 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 238000000137 annealing Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004455 differential thermal analysis Methods 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000009738 saturating Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Classifications
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/253—Silica-free oxide glass compositions containing germanium
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
A lead-free germanium bismuthate glass and a preparation method thereof, the glass comprises the following components by mol percent: GeO2：62mol％；Bi2O3：30～38mol％；La2O3: 0 to 8 mol%. The test proves that: the glass has a transition temperature of 470-496 ℃, a glass stability parameter delta T of more than or equal to 80 ℃, and delta Tmax=145 ℃, infrared cut-off wavelength greater than 6 μm, up to 6.5 μm, indicating that the glass is suitable as a host material for upconversion and as an infrared-transmitting material.
Description
Technical field
The present invention relates to glass, especially a kind of lead free bismuth germanate glass and preparation method thereof.
Background technology
Bi
2O
3, PbO, GeO
2Equal size surpasses the heavy metal glass of 50mol%, because high refractive index, high-k and wide performances such as saturating infra-red range are arranged, is subjected to people's attention for many years always.Show by systematic research, phonon energy in this glass structure is low, be suitable for doing rare earth luminous fertile material, therefore this glass is considered to improve one of candidate's photonics functional materials of efficiency of conversion on the rare earth, referring to technology Daniel J.Coleman formerly, Stuart D.Jackson, Paul Golding, Terence A.King.Measurements of thespectroscopic and energy transfer parameters for Er
3+-doped andEr
3+, Pr
3+-codoped PbO-Bi
2O
3-Ga
2O
3Glasses, J.Opt.Soc.Am.B 19 (2002) 2927-2929.Simultaneously because the good saturating infrared property of this glass, might replace some crystal and become novel ir transmitting material, referring to technology A.Pan formerly, A.Ghosh.A newfamily of lead-bismuthate glass with a large transmitting window, J.Non-Cryst.Solids 271 (2000) 157-161.But consider that from the angle of environment protection and preparation safety unleaded heavy metal glass has more widely to be used.Thereby in order to satisfy current needs, it is necessary exploring the novel lead-free heavy metal glass that has good stability.
Summary of the invention
Weakness at containing toxic substance lead in the heavy metal glass the invention provides a kind of lead free bismuth germanate glass and preparation method thereof more, and this glass should have high transition temperature, high stability and good saturating infrared ability.This glass can be used as a kind of conversion substrate material and ir transmitting material gone up.
Technical solution of the present invention is as follows:
A kind of lead free bismuth germanate glass, it is composed as follows:
Glass ingredient molar percentage (mol%)
GeO
2 62
Bi
2O
3 30～38
La
2 O
3 0～8
Wherein: M is Li or Na.
The concrete preparation method of lead free bismuth germanate glass of the present invention comprises the steps:
1.: the molar percentage of forming by glass (mol%) calculates weight of glass per-cent, takes by weighing raw material then, mixes;
2.: compound is put into platinum crucible, place 1200～1250 ℃ silicon carbon rod electric furnace fusion, melting time is controlled at 20～30min;
3.: behind the glass melting, be cooled to 1150～1200 ℃, feed high purity oxygen gas and dewater, what of raw material aeration time be decided by;
4.: stop logical oxygen, glass metal is warmed up to 1200～1250 ℃ carries out clarification and homogenization, then glass metal is poured in the mould of preheating;
5.: glass is put into be warming up to transition temperature (T fast
g) retort furnace in, be incubated after 2 hours, be annealed to about 150 ℃ with 15 ℃/hour speed, and then after being annealed to 80 ℃ with 20 ℃/hour speed, close retort furnace, be cooled to room temperature, can obtain lead free bismuth germanate glass.
The experiment proved that: lead free bismuth germanate glass of the present invention has high transition temperature, high stability and good saturating infrared ability.This glass can be used as a kind of conversion substrate material and ir transmitting material gone up.
Description of drawings
Fig. 1 is the infrared permeation figure of lead free bismuth germanate glass of the present invention.
Embodiment
The invention will be further described below in conjunction with embodiment, but should not limit protection scope of the present invention with this.
4 concrete compositions of implementing of lead free bismuth germanate glass are as shown in table 1:
Table 1
Component (mol%) 1
#2
#3
#4
#
GeO
2 62 62 62 62
Bi
2O
3 38 36 33 30
La
2O
3 0 2 5 8
T
g(℃) 470 480 488 496
T
x(℃) 550 570 599 641
ΔT(℃) 80 90 111 145
Infrared by wavelength 6 6.1 6.2 6.5
(μm)
Annotate: T in the table
gBe glass transformation temperature, T
xBe the crystallization starting temperature, Δ T=T
x-T
g
Embodiment 1
#:
Form as in the table 11
#Shown in, concrete preparation method comprises the following steps:
1. the molar percentage of forming by selected glass (mol%) calculates weight of glass per-cent, takes by weighing each raw material then, mixes;
2. compound is put into corundum crucible, place 1200 ℃ silicon carbon rod electric furnace fusion, according to the length that how much determines melting time of raw material;
3. behind the glass melting, be cooled to 1150 ℃, feed high purity oxygen gas and dewater, what of raw material aeration time be decided by;
4. stop logical oxygen, glass metal is warmed up to 1200 ℃ carries out clarification and homogenization, what of raw material its time also depend on, then glass metal poured in the mould of preheating;
5. fast glass is put into the retort furnace that is warming up to 470 ℃, be incubated after 2 hours, be annealed to about 150 ℃ with 15 ℃/hour speed, and then after being annealed to 80 ℃ with 20 ℃/hour speed, close retort furnace, be cooled to room temperature, can obtain lead free bismuth germanate glass.
Test result to this glass is as follows:
Get 10 milligrams sample after the annealing, be ground into very thin powder, carry out differential thermal analysis with agate mortar.The T that records
gBe 470 ℃, T
xIt is 550 ℃.Can calculate Δ T according to above two characteristic temperatures is 80 ℃.
Sample after the annealing is processed into the sheet glass of 3 mm thick of six mirror polish, tests infrared property.Fig. 1 is the infrared permeation figure of glass of the present invention.Recording the IR-cut wavelength is 6 microns.
Embodiment 2
#:
Form as in the table 12
#Shown in, concrete preparation method comprises the following steps:
1.: the molar percentage of forming by selected glass (mol%) calculates weight of glass per-cent, takes by weighing each raw material then, mixes;
2.: compound is put into platinum crucible, place 1200 ℃ silicon carbon rod electric furnace fusion, according to the length that how much determines melting time of raw material;
3.: behind the glass melting, be cooled to 1150 ℃, feed high purity oxygen gas and dewater, what of raw material aeration time be decided by;
4.: stop logical oxygen, glass metal is warmed up to 1200 ℃ carries out clarification and homogenization, what of raw material its time also depend on, then glass metal poured in the mould of preheating;
5.: fast glass is put into the retort furnace that is warming up to 480 ℃, be incubated after 2 hours, be annealed to about 150 ℃ with 15 ℃/hour speed, and then after being annealed to 80 ℃ with 20 ℃/hour speed, close retort furnace, be cooled to room temperature, both can obtain lead free bismuth germanate glass.
Test result to this glass is as follows:
Get 10 milligrams sample after the annealing, be ground into very thin powder, carry out differential thermal analysis with agate mortar.The T that records
gBe 480 ℃, T
xIt is 570 ℃.Can calculate Δ T according to above two characteristic temperatures is 90 ℃.
Sample after the annealing is processed into the sheet glass of 3 mm thick of six mirror polish, tests infrared property.Recording the IR-cut wavelength is 6.1 microns.
Embodiment 3
#:
Form as in the table 13
#Shown in, concrete preparation method comprises the following steps:
1.: the molar percentage of forming by glass (mol%) calculates weight of glass per-cent, takes by weighing raw material then, mixes;
2.: compound is put into platinum crucible, place 1250 ℃ silicon carbon rod electric furnace fusion, according to the length that how much determines melting time of raw material;
3.: behind the glass melting, be cooled to 1200 ℃, feed high purity oxygen gas and dewater, what of raw material aeration time be decided by;
4.: stop logical oxygen, glass metal is warmed up to 1250 ℃ carries out clarification and homogenization, what of raw material its time also depend on, then glass metal poured in the mould of preheating;
5.: fast glass is put into the retort furnace that is warming up to 488 ℃, be incubated after 2 hours, be annealed to about 150 ℃, and then after being annealed to 80 ℃ with 20 ℃/hour speed, close retort furnace, be cooled to room temperature with 15 ℃/hour speed;
Test result to this glass is as follows:
Get 10 milligrams sample after the annealing, be ground into very thin powder, carry out differential thermal analysis with agate mortar.The T that records
gBe 488 ℃, T
xIt is 599 ℃.Can calculate Δ T according to above two characteristic temperatures is 111 ℃.
Sample after the annealing is processed into the sheet glass of 3 mm thick of six mirror polish, tests infrared property.Recording the IR-cut wavelength is 6.2 microns.
Embodiment 4
#:
Form as in the table 14
#Shown in, concrete preparation method comprises the following steps:
1.: the molar percentage of forming by selected glass (mol%) calculates weight of glass per-cent, takes by weighing raw material then, mixes;
2.: compound is put into platinum crucible, place 1250 ℃ silicon carbon rod electric furnace fusion, according to the length that how much determines melting time of raw material;
3.: behind the glass melting, be cooled to 1200 ℃, feed high purity oxygen gas and dewater, what of raw material aeration time be decided by;
4.: stop logical oxygen, glass metal is warmed up to 1250 ℃ carries out clarification and homogenization, what of raw material its time also depend on, then glass metal poured in the mould of preheating;
5.: fast glass is put into the retort furnace that is warming up to 496 ℃, be incubated after 2 hours, be annealed to about 150 ℃, and then after being annealed to 80 ℃ with 20 ℃/hour speed, close retort furnace, be cooled to room temperature with 15 ℃/hour speed;
Test result to this glass is as follows:
Get 10 milligrams sample after the annealing, be ground into very thin powder, carry out differential thermal analysis with agate mortar.The T that records
gBe 496 ℃, T
xIt is 641 ℃.Can calculate Δ T according to above two characteristic temperatures is 145 ℃.
Sample after the annealing is processed into the sheet glass of 3 mm thick of six mirror polish, tests infrared property.Recording the IR-cut wavelength is 6.5 microns.
In the process of founding, melting technology is controlled improper meeting and is caused the small devitrification of glass edge.The transition temperature of this glass that we obtain in the experiment is at 470～496 ℃, stability, glass parameter Δ T 〉=80 ℃, Δ T
Max=145 ℃, the IR-cut wavelength reaches as high as 6.5 μ m greater than 6 μ m, illustrates that this glass is fit to do to go up the substrate material and the ir transmitting material of conversion.
Claims (2)
1, a kind of lead free bismuth germanate glass is characterized in that the composed as follows of this glass:
Glass ingredient molar percentage (mol%)
GeO
2 62
Bi
2O
3 30～38
La
2O
3 0～8
Wherein: M is Li or Na.
2, the concrete preparation method of lead free bismuth germanate glass according to claim 1 is characterized in that comprising the steps:
1. the molar percentage of forming by selected glass (mol%) calculates weight of glass per-cent, takes by weighing each raw material then, mixes;
2.: compound is put into platinum crucible, place 1200～1250 ℃ silicon carbon rod electric furnace fusion, melting time is controlled at 20～30min;
3.: behind the glass melting, be cooled to 1150～1200 ℃, feed high purity oxygen gas and dewater, what of raw material aeration time be decided by;
4.: stop logical oxygen, glass metal is warmed up to 1200～1250 ℃ carries out clarification and homogenization, then glass metal is poured in the mould of preheating;
5.: fast glass is put into the retort furnace that is warming up to transition temperature (Tg), be incubated after 2 hours, be annealed to about 150 ℃ with 15 ℃/hour speed, and then after being annealed to 80 ℃ with 20 ℃/hour speed, close retort furnace, be cooled to room temperature, can obtain lead free bismuth germanate glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410067698 CN1242947C (en) | 2004-11-02 | 2004-11-02 | Lead-free germanium bismuthate glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410067698 CN1242947C (en) | 2004-11-02 | 2004-11-02 | Lead-free germanium bismuthate glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1613804A true CN1613804A (en) | 2005-05-11 |
| CN1242947C CN1242947C (en) | 2006-02-22 |
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|---|---|---|---|
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674690A (en) * | 2012-05-31 | 2012-09-19 | 中国科学院上海光学精密机械研究所 | 3 mu m rare earth ion doped bismuth-germinate laser glass and preparation method thereof |
| CN103848570A (en) * | 2014-03-26 | 2014-06-11 | 南京信息工程大学 | Intermediate infrared optical glass with high refractive index and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100563447C (en) * | 2005-03-28 | 2009-12-02 | 北京华京五方实用纳米科技开发有限公司 | A kind of aqueous pesticide and preparation method thereof |
-
2004
- 2004-11-02 CN CN 200410067698 patent/CN1242947C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674690A (en) * | 2012-05-31 | 2012-09-19 | 中国科学院上海光学精密机械研究所 | 3 mu m rare earth ion doped bismuth-germinate laser glass and preparation method thereof |
| CN103848570A (en) * | 2014-03-26 | 2014-06-11 | 南京信息工程大学 | Intermediate infrared optical glass with high refractive index and preparation method thereof |
| CN103848570B (en) * | 2014-03-26 | 2016-04-20 | 南京信息工程大学 | A kind of high refractive index mid-infrared light glass and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1242947C (en) | 2006-02-22 |
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Granted publication date: 20060222 Termination date: 20111102 |