CN101381203B - Component of molybdenum-containing sunalux glass and application - Google Patents
Component of molybdenum-containing sunalux glass and application Download PDFInfo
- Publication number
- CN101381203B CN101381203B CN2008102250580A CN200810225058A CN101381203B CN 101381203 B CN101381203 B CN 101381203B CN 2008102250580 A CN2008102250580 A CN 2008102250580A CN 200810225058 A CN200810225058 A CN 200810225058A CN 101381203 B CN101381203 B CN 101381203B
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- CN
- China
- Prior art keywords
- glass
- vitaglass
- molybdenum
- percent
- molybdenum group
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 3
- 239000011733 molybdenum Substances 0.000 title claims description 3
- 239000011521 glass Substances 0.000 title abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229910000833 kovar Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 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
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The invention relates to components and application of mlybdenum ultraviolet transmitting glass. The glass comprises the following components ( in percentage by weight of oxides): 62 to 65 percent of SiO2, 3 to 5 percent of Al2O3, 22 to 24 percent of B2O3, 5 to 7 percent of Na2O, 0.1 to 1 percent of Li2O, and 0.1 to 1 percent of ZnO. The glass has a coefficient of expansion close to that of metalmolybdenum or kovar alloy and belongs to electric-vacuum glass. The glass is suitable to be used as materials for tube shells and optical windows for photoelectric tubes and photomultiplier tubes.
Description
Technical field
The present invention relates to a kind of component and application of molybdenum group vitaglass, belong to electric-vacuum glass.
Background technology
Just there is the manufacturer production vitaglass in China as far back as the phase at the beginning of the seventies in last century, but gas line, striped, sand point are a lot, anti-water chemistry stability is low, when thickness of glass is 1mm, wavelength is that the ultraviolet ray transmissivity at 253.7nm place only has 60%～70%, and the decay of uv-exposure transmitance is big, anti-water chemistry less stable, so far basal conditions does not all have much changes, and oeverall quality does not still reach the requirement of making high-end vacuum device such as photomultiplier etc.
Summary of the invention
For overcoming defective of the prior art, the invention provides a kind of new molybdenum group vitaglass component that is applied in short-wave band, make at wavelength to be that ultraviolet ray transmissivity, uv-exposure transmitance and the anti-water chemistry stability at 253.7nm place all obviously is improved.Specifically, the present invention relates to a kind of molybdenum group vitaglass, comprise following component (by the weight percent of oxide compound): SiO
2Be 62%～65%, Al
2O
3Be 3%～5%, B
2O
3Be 22%～24%, Na
2O is 5%～7%, Li
2O is 0.1%～1%, and ZnO is 0.1%～1%.
The present invention is guaranteeing to have introduced a small amount of Li in the glass ingredient under the prerequisite that the transmitance and the coefficient of expansion and processing performance meet the demands
2O and ZnO are with its filling glass network gap, chilled glass structure, plug ion migrating channels, to improve anti-water chemistry stability and uvioresistant exposure transmitance fade performance, the Li of Yin Ruing simultaneously
2O also plays fluxing action, has improved processing performance.And when composition designs the corresponding Al that improved
2O
3Content, so both helped the chilled glass structure also to help to improve anti-water chemistry stability and the uvioresistant transmitance fade performance that exposes.In addition, the present invention has improved the coefficient of expansion 50 * 10
-7/ ℃ about the anti-water chemistry stability of molybdenum group vitaglass.
This molybdenum group vitaglass can be directly and metal molybdenum or kovar alloy sealing-in, is that the ultraviolet ray transmissivity at 253.7nm place is more than or equal to 85% at wavelength.
This glass is applicable to the shell or the optical window material of phototube, photomultiplier.
Embodiment
According to a kind of molybdenum group vitaglass of the present invention, the weight percent of its main ingredient is: SiO
2Be 62%～65%, Al
2O
3Be 3%～5%, B
2O
3Be 22%～24%, Na
2O is 5%～7%, Li
2O is 0.1%～1%, and ZnO is 0.1%～1%.Because it is very big that ultraviolet ray transmissivity is influenced by the purity of material, any defect and impurity is the ultraviolet ray transmissivity of grievous injury material all, so the purity grade of materials used should be excellent pure level at least, and in batching and charging technology, use the instrument of plastics or stainless steel, the impurity K that in the glass production process, produces like this
2O and Fe
2O
3Can be controlled in few content, its weight percent all is controlled at below 0.02%.In order not influence the transmitance of vitaglass, the weight percent summation of its all impurity should not surpass 0.03%.
The specific embodiment of the invention is as follows:
Table one (embodiment 1 to embodiment 3) is for the invention provides the specific embodiment of glass ingredient.
Table one specific embodiment
| Following component be weight percentage (%) | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Silicon-dioxide (SiO 2) | 64.77 | 64.31 | 64.91 |
| Aluminum oxide (Al 2O 3) | 4.51 | 4.60 | 4.97 |
| Boron oxide (B 2O 3) | 22.66 | 23.54 | 22.18 |
| Sodium oxide (Na 2O) | 6.83 | 6.24 | 6.41 |
| Lithium Oxide 98min (Li 2O) | 0.41 | 0.51 | 0.64 |
| Zinc oxide (ZnO) | 0.81 | 0.79 | 0.87 |
| Potassium oxide (K 2O) | 0.0064 | 0.0053 | 0.0126 |
| Ferric oxide (Fe 2O 3) | 0.0036 | 0.0047 | 0.0074 |
Table two is the physical and chemical performance index of 3 embodiment correspondences in the table one
Table two embodiment physical and chemical performance index
| The physical and chemical performance index | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| The coefficient of expansion (* 10 -7/℃) | 50.49 | 50.12 | 50.40 |
| 253.7nm transmitance (%) (thickness of glass 1mm) | 87.13％ | 87.78％ | 87.08％ |
| Anti-water chemistry stability | The IV level | The IV level | The IV level |
| Softening temperature (℃) | 710 | 705 | 715 |
| Thermostability (℃) | 290 | 288 | 292 |
Table three is the uv-exposure transmitance index of 3 embodiment correspondences in the table one, this index is to be that the vitaglass sheet of 1mm places apart from the position of 500W ultraviolet lamp 20cm and shines with thickness, is the ultraviolet ray transmissivity at 253.7nm place at the same position place of sheet glass test wavelength.
Table three uv-exposure transmitance
Table four is the synopsis of table one, and it is for being different from molybdenum group vitaglass component of the present invention.
Table four comparative example
| Following component be weight percentage (%) | Comparative example |
| Silicon-dioxide (SiO 2) | 63.3 |
| Aluminum oxide (Al 2O 3) | 3.1 |
| Boron oxide (B 2O 3) | 26.18 |
| Sodium oxide (Na 2O) | 7.4 |
| Potassium oxide (K 2O) | 0.0106 |
| Ferric oxide (Fe 2O 3) | 0.0094 |
Table five is the physical and chemical performance index of table four comparative example
Table five comparative example physical and chemical performance index
| The coefficient of expansion (* 10 -7/℃) | 50.6 |
| 253.7nm transmitance (%) (thickness of glass 1mm) | 86.02％ |
| Anti-water chemistry stability | The V level |
| Softening temperature (℃) | 700 |
| Thermostability (℃) | 284.5 |
Table six is the uv-exposure transmitance index of table four comparative example, and the test of this index and table three method therefor are in full accord.
The uv-exposure transmitance of table six comparative example
Compare and can find with comparative example, the present invention is that the ultraviolet ray transmissivity at 253.7nm place is greater than 85%, because the present invention has introduced a certain amount of Lithium Oxide 98min (Li at wavelength
2O) and zinc oxide (ZnO), the anti-water chemistry stability of glass obviously improves, and uv-exposure transmitance performance also obviously improves simultaneously.
The glass sample of table one and table four, all be with following method manufacturing: each component composition is got the raw material of same batch of same producer, and the weight percent uniform mixing according to corresponding is blow molded into glass bulb after quartz crucible is founded, annealing, finished product warehouse-in.
Table two and table five relate to the physical and chemical performance index of glass, all are to test under the same conditions, and the testing method of concrete foundation is:
The coefficient of expansion: GB/T16920-1997 " mensuration of glass mean coefficient of linear thermal expansion ".
Ultraviolet ray transmissivity: GB/T7962.12-1987 " transmission measurement method in the colouless optical glass testing method spectrum ".
Anti-water chemistry stability: GB/T6582-1997 " glass is in 98 ℃ of water-proof particle test methods and classification ".
Softening temperature: SJ/T11038-96 " testing method of electronic glass softening temperature ".
Thermostability: GB/T15727-1995 " Laboratory Instruments glass heat impact test method (bar-shaped method) ".
Claims (9)
1. a molybdenum group vitaglass is characterized in that comprising component by weight percentage: SiO
2Be 62%～65%, Al
2O
3Be 3%～5%, B
2O
3Be 22%～24%, Na
2O is 5%～7%, Li
2O is 0.1%～1%, and ZnO is 0.1%～1%; And the weight percent summation of impurities is no more than 0.03% in its component.
2. molybdenum group vitaglass as claimed in claim 1 is characterized in that at wavelength being that the ultraviolet ray transmissivity at 253.7nm place is more than 85%.
3. molybdenum group vitaglass as claimed in claim 1 is characterized in that anti-water chemistry stability reaches the IV level.
4. molybdenum group vitaglass as claimed in claim 1 or 2 is characterized in that impurity K
2O and Fe
2O
3Weight percent all be controlled at below 0.02%.
5. molybdenum group vitaglass as claimed in claim 1 or 2, it is pure to it is characterized in that the material purity that uses is at least top grade.
6. molybdenum group vitaglass as claimed in claim 1 or 2, it is characterized in that can be directly and the metal molybdenum sealing-in.
7. molybdenum group vitaglass as claimed in claim 1 or 2, it is characterized in that can be directly and the kovar alloy sealing-in.
8. molybdenum group vitaglass as claimed in claim 1 or 2 is characterized in that using in making photomultiplier.
9. molybdenum group vitaglass as claimed in claim 1 or 2 is characterized in that using in making phototube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102250580A CN101381203B (en) | 2008-10-27 | 2008-10-27 | Component of molybdenum-containing sunalux glass and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102250580A CN101381203B (en) | 2008-10-27 | 2008-10-27 | Component of molybdenum-containing sunalux glass and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101381203A CN101381203A (en) | 2009-03-11 |
| CN101381203B true CN101381203B (en) | 2011-02-09 |
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ID=40461287
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102250580A Active CN101381203B (en) | 2008-10-27 | 2008-10-27 | Component of molybdenum-containing sunalux glass and application |
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| Country | Link |
|---|---|
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102135631B (en) * | 2010-12-15 | 2013-02-06 | 安徽华东光电技术研究所 | Miniature high-sensitivity ultraviolet detector |
| JP7134396B2 (en) * | 2017-02-24 | 2022-09-12 | 日本電気硝子株式会社 | optical glass |
| CN108341594A (en) * | 2018-04-27 | 2018-07-31 | 海南中航特玻科技有限公司 | A kind of effective high borosilicate glass material of photomultiplier transit |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1118596B1 (en) * | 2000-01-12 | 2003-10-15 | Schott Glas | Alkali-free aluminoborosilicate glass and its use |
| CN1583624A (en) * | 2003-06-06 | 2005-02-23 | 肖特玻璃制造厂 | UV-absorbing glass with low absorption in the visible range, method for the production thereof and use thereof |
| 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 |
| CN1938238A (en) * | 2004-04-05 | 2007-03-28 | 日本电气硝子株式会社 | Illuminating glass |
-
2008
- 2008-10-27 CN CN2008102250580A patent/CN101381203B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1118596B1 (en) * | 2000-01-12 | 2003-10-15 | Schott Glas | Alkali-free aluminoborosilicate glass and its use |
| CN1583624A (en) * | 2003-06-06 | 2005-02-23 | 肖特玻璃制造厂 | UV-absorbing glass with low absorption in the visible range, method for the production thereof and use thereof |
| CN1938238A (en) * | 2004-04-05 | 2007-03-28 | 日本电气硝子株式会社 | Illuminating 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 |
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| Publication number | Publication date |
|---|---|
| CN101381203A (en) | 2009-03-11 |
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Address after: 100070, room 3, building 128, No. 903 South Fourth Ring Road, Beijing, Fengtai District Patentee after: Beijing Hamamatsu Photonics Technology Co., Ltd. Address before: 100070, No. 18, No. 11, No. 188, South Fourth Ring Road, Fengtai District, Beijing Patentee before: Beijing Hamamatsu Photonics Technology Co., Ltd. |