CN102503123A - Preparation method of spaceborne anti-irradiation coverglass - Google Patents
Preparation method of spaceborne anti-irradiation coverglass Download PDFInfo
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- CN102503123A CN102503123A CN201110377843XA CN201110377843A CN102503123A CN 102503123 A CN102503123 A CN 102503123A CN 201110377843X A CN201110377843X A CN 201110377843XA CN 201110377843 A CN201110377843 A CN 201110377843A CN 102503123 A CN102503123 A CN 102503123A
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Abstract
The invention relates to a preparation method of special optical glass using both additional rare-earth elements and other oxides. The technology of the preparation method is as follows: the raw material formula of the glass contains silicon dioxide, sodium oxide, boron oxide, cerium oxide, aluminum oxide, titanium oxide and the like. The melting technology of the glass comprises the following steps of: heating an electric melting furnace to 1330-1400 DEG C, then slowly adding the proportioned material which is proportioned according to the designed components in a molten pool through an emptying hole while performing mechanical agitation, stopping charging at 1580-1600 DEG C, performing heat preservation to melt and clarify for 12hours, and then cooling and discharging. The annealing technology comprises the following steps of: placing the discharged material blocks in a resistance furnace, heating to 580 DEG C, and annealing according to a certain temperature schedule to obtain the product which is the spaceborne anti-irradiation coverglass.
Description
Technical field
The present invention relates to a kind of space and use the special glass technical field, is the preparation method of space with anti-irradiation cover glass.
Background technology
At earth orbit space; Exist the radiation such as radiation belt and sun power particle of Millikan's rays from the Via lastis, the earth; When space vehicle receives the infringement of space high energy particle and ray during at space motion, the solar panel of space vehicle both wings can be breakdown, causes short circuit and lost efficacy; In order to protect solar cell, on solar cell, add a cover cover glass usually.When common flint glass uses, generally can not change its visible light transmissive performance under home, but when space vehicle uses, can receive the radiation of high energy particle or ray when glass; And most of glass is under the radiation of various high energy particles or ray; To cause the variation of the color and luster and the ability of seeing through, and make glass rotten, transmitance significantly descends; Can not guarantee enough sunshine transmitances, make aerospacecraft lose reliable power supply supply.The space is with the important component part of anti-irradiation cover glass as space solar cell; Effectively the protection solar cell is avoided the bombardment of space high energy particle; Prolong the work-ing life of solar cell; Do not reduce or slightly reduce visible light transmissivity, and filter out ultraviolet ray, make spacecraft can obtain reliable power supply supply.
Summary of the invention
The objective of the invention is in order to solve since space high energy particle and ray to the infringement of space vehicle solar panel; Thereby the problem that causes solar cell failure; The preparation method of a kind of space with anti-irradiation cover glass is provided; Through in glass formula, adding a kind of rare earth oxide and the method that other oxide compounds use simultaneously, reach the performance requriements of national military standard cover glass.
The object of the invention is realized through following measure: the space comprises that with anti-irradiation cover glass prescription the one-tenth of following mass ratio is grouped into:
Silicon-dioxide (SiO
2) 60-68; Aluminum oxide (Al
2O
3) 4-5
Boron trioxide (B
2O
3) 8-12; Natural manganese dioxide (MgO) 0.8-1.2
Barium oxide (BaO) 1-4; Sodium oxide (Na
2O) 8-13
Potassium oxide (K
2O) 0.8-1.3; Cerium oxide (CeO
2) 4.8-5.3
Titanium oxide (TiO
2) 0.3-0.7; Weisspiessglanz (Sb
2O
3) 0.2-0.6
Select the requirement of mineral substance for use: because the transmitance of having relatively high expectations with anti-irradiation cover glass in the space, so higher to the purity requirement of raw mineral materials, the raw material index that test is adopted is following:
The employing electric melting furnace heats concrete technology and is: at first electric melting furnace is heated to 1330 ℃～1400 ℃; To add in the molten bath through tapping hole lentamente by the good admixtion of design mix proportioning then, carry out mechanical stirring simultaneously, and when temperature rises to 1580 ℃～1600 ℃, stop to feed in raw material; Insulation fusing 12 hours; Also played simultaneously the effect of clarification and homogenization, cooling discharge places fine annealing in the resistance furnace with institute's discharging piece then.Products obtained therefrom is the frit of space with anti-irradiation cover glass, and the space that the special optics cold machining process of process manufactures excellent property is with anti-irradiation cover glass.
Said temperature is warming up to 1580 ℃～1600 ℃ by 1380 ℃～1400 ℃, and the TRT is 5 hours.
Above-mentioned institute's discharging piece is placed 580 ℃ of annealing in the resistance furnace.
Various glass ingredients are to the performance impact of space with anti-irradiation cover glass:
1. to the influence of transmitance: because the space is with the use under steric requirements for a long time of anti-irradiation cover glass, only guaranteed enough sunshine transmitances can make aerospacecraft obtain reliable power supply supply.Common flint glass can receive the radiation of energetic ray or particle when space vehicle uses; Cause the variation of color and luster and transmittancy; Its major cause is that various high-energy radiations all will cause the high energy unbound electron in glass; And these unbound electrons will make the positively charged ion in the glass change valence state, also can be formed colour center by vacant the catching of the negative ion in the network structure dot matrix in the glass, and this is that energetic ray causes the basic reason that the glass transmitance significantly descends.The effect of severe radiation also can make nucleus displacement in the glass, the network structure room occurs, and the formation of the fracture of original key and new key makes glass rotten.When existing the polyvalent ion of variable valence in the glass, radiation-induced unbound electron at first with ionic reaction, its valence state is changed, and does not cause the foundation of colour center, add proper C eO2 in the glass of the present invention, can prevent effectively that radiation is painted.The effect of the anti-irradiation of CeO2 is the effect at the hole capture center that Ce+3 is superpower, and Ce+4 plays the electron capture center, and electronics that radiation produced and hole are captured by glass network defective and Ce+3 and Ce+4.Because the ultraviolet ray in the sunshine has certain harm to cover plate glue, select for use CeO2 also can filter out the ultraviolet ray in the sunshine fully in addition.In anti-irradiation glass, the introducing amount aspect of CeO2 should consider that the radiation hardness ability is directly proportional with CeO2 content, will consider that also CeO2 introducing amount is too high, glass easy yellowly and cause phase-splitting, influence transmitance.Thereby TiO2-CeO2 unites use and can reduce ultraviolet ray transmissivity, increases irradiation stability, and TiO2 introduces and can reduce CeO2 content simultaneously, and TiO2 helps fusing and clarification, and can reduce the viscosity of glass; What experiment confirm, the Glassy Space charge ratio of introducing CeO2 were not introduced CeO2 wants many 2-4 doubly, thereby discharges, and for neutralize space charge, the content that increases sodium oxide in right amount conducts electricity to increase.
2. to the influence of density: the expense of spatial emission flyer is directly proportional with weight, and aircraft weight increases by one kilogram, and will to increase the launching costs hundreds of thousands of first, so the space should be as far as possible little with the density of anti-irradiation cover glass, I am defined in below 2.60 by national military standard.So select for use density at the borosilicate glass below 2.60.In this system, can know that through test aluminum oxide (Al2O3) too high levels has negatively influencing to glass density, thus last when confirming composition, suitably reducing the content of aluminum oxide (Al2O3), the ratio of adjusting other components is to satisfy the requirement of generation system.
In order to reach the optical characteristics of this product, we have adopted is the multinomial component on basis with the borosilicate; Add an amount of cerium dioxide (CeO2) and titanium oxide (TiO2), the two has significantly improved the anti-radiation performance of cover glass through certain proportioning value; Add an amount of Antimony Trioxide: 99.5Min (Sb2O3), improved the visible light transmissivity that influences because of the adding Ce elements in the glass, reduced uv transmittance simultaneously, strengthened the anti-radiation performance of glass; Add an amount of zinc oxide (ZnO), thereby adjust the linear expansivity of this product effectively, physics and chemistry such as high temperature material property with found performance; Add appropriate amount of alumina (Al2O3), can improve the chemicalstability of product and effectively stop phase transformation; Utilize the way of elimination frit internal residual stress such as fine annealing, improved mechanical performance of products greatly.
The technical indicator of military standard of China
The spectral response curve of military standard of China
The technical parameter that this product has
The spectral response curve of this product
The innovative point of this product:
1. theory innovation: say that from point of theory (1) is more little good more in its transsmissivity of UV-light part, because substrate must guarantee the transmitance of other light; If ultraviolet permeability is high; Can cause the substrate variable color, influence the transmission of other light, can not normal power generation thereby influence solar cell.In addition, ultraviolet radiation can damage cover plate glue, causes the bonding of cover glass and solar cell to go wrong, and causes solar cell to damage even inefficacy.(2) through calculating, through a certain amount of doping of certain element, can strengthen the anti-radiation performance of this product, improve the work-ing life of substrate, effectively guaranteed the normal operation of aircraft simultaneously.(3) reduce substrate inner transverse stress and meridional stress simultaneously, reach the efficient that reduces the product practical application.(4) through certain element a certain amount of doping, can reduce the linear expansivity of substrate, reach the coupling of substrate and aircraft, work-ing life of raising substrate and to the provide protection of aircraft.
2. application innovation: main body is a borosilicate glass, through to a certain amount of doping of certain element, can make cover glass protect solar cell effectively, and makes it obtain the enough energy to generate electricity, and guarantees the normal operation of aircraft.
3. technological innovation: (1) anti-radiation performance, this product is through accumulative total flux 1 * 10
16E/cm
2Behind the irradiation, the transmitance of light is constant basically.(2) uv transmittance is very little, and is almost nil.
Embodiment
Embodiment 1: the space is with the preparation method of anti-irradiation cover glass
The space is grouped into the prescription of the anti-irradiation cover glass one-tenth by following mass ratio:
Silicon-dioxide (SiO
2) 67.0; Aluminum oxide (Al
2O
3) 4.0;
Boron trioxide (B
2O
3) 10.0; Natural manganese dioxide (MgO) 1.0;
Barium oxide (BaO) 1.0; Sodium oxide (Na
2O) 10.0;
Potassium oxide (K
2O) 1.2; Cerium oxide (CeO
2) 4.9;
Titanium oxide (TiO
2) 0.4; Weisspiessglanz (Sb
2O
3) 0.5;
Select raw mineral materials for use: because the transparency of having relatively high expectations with anti-irradiation cover glass in the space, so higher for the purity requirement of raw mineral materials, the raw materials quality index that test is adopted is following:
| Raw material | Purity % | Fe 2O 3％ | Cr％ | Cu％ | Cl％ | SO 4％ |
| SiO 2 | 99.99 | ≤0.0001 | ≤0.00001 | ≤0.00002 | ||
| Al(OH) 3 | 99.95 | ≤0.0002 | ≤0.6 | ≤0.04 | ||
| H 3BO 3 | 99.98 | ≤0.0001 | ≤0.01 | ≤0.003 | ||
| MgO | 99.00 | ≤0.05 | ≤0.035 | ≤0.2 | ||
| BaCO 3 | 99.00 | ≤0.0005 | ≤0.002 | ≤.005 | ||
| Na | 99.78 | ≤0.0017 |
| 2CO 3 | ||||||
| K 2CO 3 | 99.90 | ≤0.0005 | ≤0.0005 | ≤0.001 | ≤0.002 | |
| CeO 2 | 99.90 | ≤0.0003 | ||||
| TiO 2 | 99.00 | ≤0.0029 | ≤0.01 | |||
| Sb 2O 3 | 99.8 | ≤0.003 | ≤0.066 |
Frit is founded test:
The employing electric melting furnace heats concrete technology and is: at first electric melting furnace is heated to 1330 ℃～1400 ℃; To add in the molten bath through tapping hole lentamente by the good admixtion of design mix proportioning then, carry out mechanical stirring simultaneously, and when temperature rises to 1580 ℃～1600 ℃, stop to feed in raw material; Insulation fusing 12 hours; Also played simultaneously the effect of clarification and homogenization, cooling discharge places fine annealing in the resistance furnace with material piece of living in then.Products obtained therefrom is the frit of space with anti-irradiation cover glass, manufactures well behaved space with anti-irradiation cover glass through special optics cold machining process.
Said temperature is warming up to 1580 ℃～1600 ℃ by 1380 ℃～1400 ℃, and the TRT is 12 hours.
The above-mentioned material piece with being gone out places 580 ℃ of annealing in the resistance furnace.
Embodiment 2: the space is with the preparation method of anti-irradiation cover glass
The space is grouped into the prescription of the anti-irradiation cover glass one-tenth by the following weight ratio:
Silicon-dioxide (SiO
2) 67.0; Aluminum oxide (Al
2O
3) 3.7;
Boron trioxide (B
2O
3) 10.1; Natural manganese dioxide (MgO) 1.0;
Barium oxide (BaO) 1.0; Sodium oxide (Na
2O) 10.0;
Potassium oxide (K
2O) 1.2; Cerium oxide (CeO
2) 5.1;
Titanium oxide (TiO
2) 0.4; Weisspiessglanz (Sb
2O
3) 0.5;
The raw materials quality index of raw mineral materials of selecting for use and frit is same as embodiment 1.
In this example, glass formula has increased the content of Ce elements, has reduced the content of aluminum oxide, anti-radiation performance that so not only can reinforcing glass, and reduced the density of glass itself, make these product performance perfect more, and develop towards the lightweight direction.
Claims (2)
1. a space comprises following proportion of masses with the preparation method of anti-irradiation cover glass:
Silicon-dioxide (SiO
2) 60-68; Aluminum oxide (Al
2O
3) 4-5
Boron trioxide (B
2O
3) 8-12; Natural manganese dioxide (MgO) 0.8-1.2
Barium oxide (BaO) 1-4; Sodium oxide (NaO) 8-13
Potassium oxide (K
2O) 0.8-1.3; Cerium oxide (CeO
2) 4.8-5.3
Titanium oxide (TiO
2) 0.3-0.7; Weisspiessglanz (Sb
2O) 0.2-0.6
The heating of employing electric melting furnace, concrete technology is: when melting furnaces are warming up to 1380～1400 ℃, will slowly add in the melting furnaces by the good admixtion of design mix proportioning; When furnace temperature reaches 1580～1600 ℃, stop to feed in raw material, this section TRT is 5 hours; Insulation fusing clarification 12 hours; Cooling discharge places smart annealing in the resistance furnace with the material piece that is gone out then, and the product of gained is the space with anti-irradiation cover glass.
2. space according to claim 1 is with the preparation method of anti-irradiation cover glass, described the material piece that is gone out placed 580 ℃ of smart annealing in the resistance furnace.
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|---|---|---|---|
| CN 201110377843 CN102503123B (en) | 2011-11-24 | 2011-11-24 | Preparation method of spaceborne anti-irradiation coverglass |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110377843 CN102503123B (en) | 2011-11-24 | 2011-11-24 | Preparation method of spaceborne anti-irradiation coverglass |
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| CN102503123B CN102503123B (en) | 2013-08-21 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833223A (en) * | 2014-01-20 | 2014-06-04 | 秦皇岛星箭特种玻璃有限公司 | Components of flexible base glass for spaceflight |
| CN104743877A (en) * | 2015-03-25 | 2015-07-01 | 秦皇岛星箭特种玻璃有限公司 | Continuous one-step preparation process of radiation-proof spatial glass cover plate |
| CN104909561A (en) * | 2015-06-01 | 2015-09-16 | 秦皇岛星箭特种玻璃有限公司 | Light-weight flexible irradiation-resistant cover glass and preparation method thereof |
| CN106116141A (en) * | 2016-06-23 | 2016-11-16 | 成都光明光电有限责任公司 | Glass composition |
| CN106477881A (en) * | 2016-09-21 | 2017-03-08 | 中国科学院西安光学精密机械研究所 | Weight crown ZK9 series space glass of resistance to illuminated optical and preparation method thereof |
| CN108773998A (en) * | 2018-06-22 | 2018-11-09 | 秦皇岛星箭特种玻璃有限公司 | A kind of radioresistance flexible glass and preparation method thereof |
| CN113582539A (en) * | 2021-08-30 | 2021-11-02 | 郑州大学 | Aluminosilicate glass and application |
| CN113660403A (en) * | 2021-08-23 | 2021-11-16 | 长春理工大学 | Satellite-borne ultra-miniature monitoring camera |
| CN114180832A (en) * | 2021-11-29 | 2022-03-15 | 中国建筑材料科学研究总院有限公司 | Ultraviolet radiation resistant and medium wave infrared glass and preparation method and application thereof |
| CN114538775A (en) * | 2022-02-17 | 2022-05-27 | 湖北省椿丰光电科技有限公司 | High-uniformity optical glass and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833223B (en) * | 2014-01-20 | 2016-01-06 | 秦皇岛星箭特种玻璃有限公司 | Space flight flexible foundation glass ingredient |
| CN103833223A (en) * | 2014-01-20 | 2014-06-04 | 秦皇岛星箭特种玻璃有限公司 | Components of flexible base glass for spaceflight |
| CN104743877B (en) * | 2015-03-25 | 2017-03-22 | 秦皇岛星箭特种玻璃有限公司 | Continuous one-step preparation process of radiation-proof spatial glass cover plate |
| CN104743877A (en) * | 2015-03-25 | 2015-07-01 | 秦皇岛星箭特种玻璃有限公司 | Continuous one-step preparation process of radiation-proof spatial glass cover plate |
| CN104909561A (en) * | 2015-06-01 | 2015-09-16 | 秦皇岛星箭特种玻璃有限公司 | Light-weight flexible irradiation-resistant cover glass and preparation method thereof |
| CN106116141A (en) * | 2016-06-23 | 2016-11-16 | 成都光明光电有限责任公司 | Glass composition |
| CN106477881A (en) * | 2016-09-21 | 2017-03-08 | 中国科学院西安光学精密机械研究所 | Weight crown ZK9 series space glass of resistance to illuminated optical and preparation method thereof |
| CN106477881B (en) * | 2016-09-21 | 2019-03-05 | 中国科学院西安光学精密机械研究所 | Weight crown ZK9 series space radiation resistance optical glass and preparation method thereof |
| CN108773998A (en) * | 2018-06-22 | 2018-11-09 | 秦皇岛星箭特种玻璃有限公司 | A kind of radioresistance flexible glass and preparation method thereof |
| CN113660403A (en) * | 2021-08-23 | 2021-11-16 | 长春理工大学 | Satellite-borne ultra-miniature monitoring camera |
| CN113582539A (en) * | 2021-08-30 | 2021-11-02 | 郑州大学 | Aluminosilicate glass and application |
| CN114180832A (en) * | 2021-11-29 | 2022-03-15 | 中国建筑材料科学研究总院有限公司 | Ultraviolet radiation resistant and medium wave infrared glass and preparation method and application thereof |
| CN114180832B (en) * | 2021-11-29 | 2023-09-29 | 中国建筑材料科学研究总院有限公司 | Ultraviolet radiation resistant intermediate wave transparent infrared glass and preparation method and application thereof |
| CN114538775A (en) * | 2022-02-17 | 2022-05-27 | 湖北省椿丰光电科技有限公司 | High-uniformity optical glass and preparation method thereof |
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