CN108773998A - A kind of radioresistance flexible glass and preparation method thereof - Google Patents
A kind of radioresistance flexible glass and preparation method thereof Download PDFInfo
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- CN108773998A CN108773998A CN201810648076.3A CN201810648076A CN108773998A CN 108773998 A CN108773998 A CN 108773998A CN 201810648076 A CN201810648076 A CN 201810648076A CN 108773998 A CN108773998 A CN 108773998A
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- 239000011521 glass Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 26
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000005855 radiation Effects 0.000 claims abstract description 17
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910011255 B2O3 Inorganic materials 0.000 claims abstract description 14
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims abstract description 14
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 12
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000005498 polishing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract 10
- 239000000203 mixture Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 8
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 8
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 8
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 7
- 239000006132 parent glass Substances 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 abstract description 19
- 238000002834 transmittance Methods 0.000 abstract description 16
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 9
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 11
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 10
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 239000006059 cover glass Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910019670 (NH4)H2PO4 Inorganic materials 0.000 description 1
- XDVMCVGTDUKDHL-UHFFFAOYSA-N [amino(2-azaniumylethylsulfanyl)methylidene]azanium;dibromide Chemical compound Br.Br.NCCSC(N)=N XDVMCVGTDUKDHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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
- C03C4/00—Compositions for glass with special properties
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
- C03B25/02—Annealing glass products in a discontinuous way
- C03B25/025—Glass sheets
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
-
- 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
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/29—Mixtures
Abstract
The present invention relates to a kind of radioresistance flexible glass and preparation method thereof, the glass includes the SiO matched according to mass percent2、Al2O3、P2O5、B2O3、SnO2、Y2O3、ZrO2、Ta2O5、Nb2O5、Li2O、CeO2、Na2O, MgO, CaO, BaO and ZnO, after being mixed to form raw material, successively by being melted, heat treatment, grinding and polishing, the techniques such as secondary heat treatment and handling flexibly prepare to form radioresistance flexible glass, the glass can be less than 0.3% in 330nm and following wave band optical transmittance, significantly improve the radiation resistance of glass, and it is more than 90% in 500-1000nm wave band optical transmittances, visible light transmittance is not reduced to greatest extent, ensure glass penetrates rate score, ensure space equipment solar absorptance and then reliable and stable power supply supply is provided, meet the performance requirement of space equipment confrontation radiation flexible special glass.
Description
Technical field
The invention belongs to glassmaking arts, are related to the ultra-thin radioresistance flexibility special glass of Aerospace Satellite, specifically
It is a kind of radioresistance flexible glass and preparation method thereof.
Background technology
In earth orbit space, there is the radiation zone of cosmic ray, the earth from the milky way galaxy and solar energy particles etc.
Radiation, is encroached on when artificial satellite is in space motion by Energetic particle and ray, in the sun of artificial satellite both wings
Energy solar panel can be breakdown, causes short circuit and fails, in order to protect solar cell, usually adds radioresistance on the solar cell
Cover glass cover plate.Use radiation resistance glass cover plate as the important component of space solar cell, the effective protection sun in space
Energy battery extends the service life of solar cell, does not reduce visible light transmittance from the bombardment of Energetic particle, filters
Fall ultraviolet light, artificial satellite is enable to obtain reliable and stable power supply supply.Existing Flouride-resistani acid phesphatase cover glass is in 330nm and following
Wave band optical transmittance≤0.8%, 400nm optical transmittance >=88%, 450nm optical transmittance >=89%, 500-
Average optical transmitance >=90% of 1000nm.
With the rapid development of Space Science and Technology, China starts development of new satellite, keeps the primary energy system of satellite more preferable
Adaptation space environment, reduce influence to solar cell, it is especially flexible less than the special type of 0.07mm with thickness to satellite
Flouride-resistani acid phesphatase cover glass demand is more and more extensive, and this glass needs small in wavelength 330nm and wave band optical transmittance below
In 0.3%, it is more than 90% in 500-1000nm wave band optics, ensure flexible Flouride-resistani acid phesphatase glass penetrates rate score, this is just needed
The composition and preparation process of flexible Flouride-resistani acid phesphatase glass are innovated, the performance for meeting artificial satellite confrontation radiation flexible glass is wanted
It asks.
Invention content
The present invention makes up for the shortcomings of the prior art and provide a kind of radioresistance flexible glass and preparation method thereof, the glass
Glass can end in 330nm or less wave bands, and permeability is less than 0.3%, be more than 90% in 500-1000nm wave band optics.
The specific technical solution of the present invention is：
A kind of radioresistance flexible glass, key point are that the glass includes the 43.2%- matched according to mass percent
65.1% SiO2, 5.5%-13.5% Al2O3, 1.0%-5.5% P2O5, 1.5%-10.2% B2O3, 0.5%-
3.3% SnO2, 1.1%-2.9% Y2O3, 0.6%-3.7% ZrO2, 0.6%-3.5% Ta2O5, 0.8%-4.7%
Nb2O5, 1.5%-6% Li2O, the CeO of 3.5%-12.8%2, 0.9%-6.5% Na2O, the MgO of 0.2%-2.5%,
The BaO of CaO, 0.1%-2.3% of 0.2%-3.2% and
The ZnO of 1.1%-3.2%.
The glass includes the SiO of the 50%-60% matched according to mass percent2, 8%-10% Al2O3、
The P of 2.5%-4%2O5, 4%-7% B2O3, 1.5%-2.5% SnO2, 1.8%-2.2% Y2O3, 1.5%-2.5%
ZrO2, 1.5%-2.5% Ta2O5, 2%-3.5% Nb2O5, 3%-4.5% Li2O, the CeO of 7%-10%2, 3%-
4.5% Na2O, the ZnO of the BaO and 1.8%-2.3% of CaO, 1%-1.6% of MgO, 1%-2% of 1%-2%.
The glass includes 53% SiO matched according to mass percent2, 8% Al2O3, 3% P2O5, 5%
B2O3, 2% SnO2, 2% Y2O3, 2% ZrO2, 2% Ta2O5, 2.5% Nb2O5, 3% Li2O, 8% CeO2、
3.5% Na2O, the ZnO of 1.5% MgO, 1.5% CaO, 1% BaO and 2%.
The preparation method of radioresistance flexible glass based on said ratio, key point be, the preparation method include with
Lower step：
A, it is melted
By SiO2、Al2O3、P2O5、B2O3、SnO2、Y2O3、ZrO2、Ta2O5、Nb2O5、Li2O、CeO2、Na2O、MgO、CaO、
BaO and ZnO is weighed according to proportion relation and is mixed to form raw material, raw material is sent into the melting furnace after preheating, in advance
Heating temperature is 1670-1710 DEG C, and high temperature discharging forms melting charge；
B, it is heat-treated
It anneals to melting charge, temperature is 590-650 DEG C, time 1-2h, basis of formation glass, then again to basic glass
Glass carries out exact annealing process, and temperature is 600-640 DEG C, time 3-6h；
C, grinding and polishing
Grinding or polishing are carried out at the same time to the upper and lower surface of parent glass after heat treatment, thickness is machined to and is not more than
0.07mm；
D, secondary heat treatment
It send and is made annealing treatment into annealing furnace, temperature is 600-620 DEG C, time 5-9h, forms radiation resistance glass；
E, handling flexibly
One layer is coated by SnCl on radiation resistance glass surface2、SbCl3、CeCl3, KCl and TiCl4The mixture of composition,
And 0.5-3h is sintered at a temperature of 380-420 DEG C, it is cooled down with liquid nitrogen after sintering, is then rinsed with deionized water, most
Radiation-proof flexible glass is formed afterwards.
In the step E, each ingredient of mixture is 22-35 parts of SnCl according to mass fraction proportioning2, 14-23 parts of SbCl3、
8-16 parts of CeCl3, 35-50 parts of KCl and 6-12 parts of TiCl4。
In the step E, each ingredient of mixture is 26 parts of SnCl according to mass fraction proportioning2, 16 parts of SbCl3, 10 parts
CeCl3, 40 parts of KCl and 8 part of TiCl4。
The beneficial effects of the invention are as follows：The present invention provides a kind of space flight radioresistance flexibility special glasss, are meeting glass
On the basis of glass thickness, which can be less than 0.3% in 330nm and following wave band optical transmittance, significantly improve glass
The radiation resistance of glass, and it is more than 90% in 500-1000nm wave band optical transmittances, visible light-transmissive is not reduced to greatest extent
Rate, ensure glass penetrates rate score, ensures space equipment solar absorptance and then provides reliable and stable power supply supply, full
The performance requirement of sufficient space equipment confrontation radiation flexible special glass.
Specific implementation mode
The present invention relates to a kind of radioresistance flexible glass and preparation method thereof, and the glass includes matching according to mass percent
The SiO of the 43.2%-65.1% of ratio2, 5.5%-13.5% Al2O3, 1.0%-5.5% P2O5, 1.5%-10.2%
B2O3, 0.5%-3.3% SnO2, 1.1%-2.9% Y2O3, 0.6%-3.7% ZrO2, the Ta of 0.6%-3.5%2O5,
The Nb of 0.8%-4.7%2O5, the Li of 1.5%-6%2The CeO of O, 3.5%-12.8%2, the Na of 0.9%-6.5%2O, 0.2%-
The ZnO of the BaO of the CaO of 2.5% MgO, 0.2%-3.2%, 0.1%-2.3%, 1.1%-3.2%；Above-mentioned each component is mixed
Conjunction forms raw material, by being melted, heat treatment, grinding and polishing, secondary heat treatment and handling flexibly, obtain radioresistance flexible glass at
The detailed process of product, operation is illustrated by specific embodiment.
Specific embodiment, SiO2For the pure SiO of procurement analysis2, analytically pure SiO2Middle iron oxides impurities content is less than
20ppm ensures that the performance of glass is stablized, and Al2O3、P2O5、B2O3、SnO2、Y2O3、ZrO2、Ta2O5、Nb2O5、Li2O、CeO2、
Na2O, MgO, CaO, BaO and ZnO by with its corresponding analysis pure chemistry raw material A l2O3、(NH4)H2PO4、H3BO3、
SnO2、Y2O3、ZrO2、Ta2O5、Nb2O5、Li2CO3、CeO2、Na2CO3、Mg(OH)2、CaCO3、BaCO3It is introduced with ZnO, based on upper
The preparation method for stating the radioresistance flexible glass of component, includes the following steps：
A, it is melted
By various components in raw material according to the SiO of proportion relation 53%2, 8% Al2O3, 3% P2O5, 5% B2O3、
2% SnO2, 2% Y2O3, 2% ZrO2, 2% Ta2O5, 2.5% Nb2O5, 3% Li2O, 8% CeO2, 3.5%
Na2O, 1.5% MgO, 1.5% CaO, 1% BaO, 2% ZnO are weighed and are mixed to form raw material, raw material is sent
Enter and be preheated in 1700 DEG C of melting furnace, high temperature discharging forms melting charge；
CaO, Li are added in the glass formula2O、Na2O、B2O3, MgO, the addition of this five kinds of materials is conducive to radioresistance
Flexible glass is melted, wherein CaO, B2O3, MgO can adjust the material of its glass, including adjust the flexible foundation glass
Temperature-viscosity curve adjusts the relevant performance parameter of glass finished-product；Li2O and Na2The addition of O can improve glass chemistry toughening
Performance afterwards, to meet the requirement of space glass flexibility performance；
The present invention adds a small amount of ceria (CeO on the basis of conventional glass ingredient2) play the role of it is clear,
It may advantageously facilitate glass and exclude bubble in fusion process, reduce the generation of glass defect；Use ceria as empty simultaneously
Between anti-rad, enhance the intense radiation of the various high energy particles in glass finished-product reply space, electronics, proton of the composition etc.；?
Increase yttria (Y in glass composition2O3) stabilized glass structure can be played the role of, the chemical stability of glass is improved,
And it can reduce due to Fe2+And Fe3+Caused glass coloration problem；
Barium monoxide (BaO), tantalum pentoxide (Ta have been additionally added in the glass ingredient2O5), niobium pentaoxide (Nb2O5), this
Three kinds of oxides can effectively improve the optical property of glass, conducive to the effect that solar cell is generated electricity using luminous energy is improved
Rate, while tantalum pentoxide (Ta2O5), niobium pentaoxide (Nb2O5) also there is compact structure, the reinforcing glass network for making glass
Effect, improve the stability of glass, improve the performances such as intensity of glass itself.
B, it is heat-treated
Anneal to melting charge, temperature be 620 DEG C, time 1.5h, basis of formation glass, then again to parent glass into
Row exact annealing process, temperature are 620 DEG C, and time 4.5h eliminates the stress of parent glass；
Stringent control is using Fe in the parent glass of instant component preparation2O3Content≤25ppm, it is molten to solve glass
Fe during system2+And Fe3+Coloring is also easy to produce to formed glass, reduces Glass optical transmitance, reduction solar cell in space
The double linear problems of difficulty for solving of middle generating efficiency；
C, grinding and polishing
It is carried out at the same time the surface treatment of grinding or polishing to the upper and lower surface of the parent glass after heat treatment, shortens processing
Time improves the yield rate of radiation resistance glass, by every dimensioned of glass to requirement is met, is machined to thickness not
More than 0.07mm；
D, secondary heat treatment
It send and is made annealing treatment into annealing furnace, temperature is 610 DEG C, time 5-9h, eliminates the remnants generated due to processing
Stress forms radiation resistance glass；
E, handling flexibly
One layer is coated by SnCl on radiation resistance glass surface2、SbCl3、CeCl3, KCl and TiCl4The mixture of composition,
Each ingredient of mixture is 26 parts of SnCl according to mass fraction proportioning2, 16 parts of SbCl3, 10 parts of CeCl3, 40 parts KCl and 8 part
TiCl4, and it is sintered 0.5-3h at a temperature of 380-420 DEG C, it is cooled down, is prevented in cooling procedure with liquid nitrogen after sintering
Air enters, and surface will not be oxidized, again be rinsed glass with deionized water after cooling, remove the impurity etc. on surface, profit
Liquid nitrogen enhancing processing is carried out with the temperature of coating, sintering, increases glass flexibility, improves the compression of glass surface, increases glass
Transmitance, and make glass surface that there is certain self-cleaning property.
Existing Flouride-resistani acid phesphatase glass is in 330nm and the optical transmittance of wave band optical transmittance≤0.8%, 400nm below
Average optical transmitance >=90% of optical transmittance >=89%, 500-1000nm of >=88%, 450nm.
Component involved in through the invention and preparation method ensure the radioresistance flexible glass prepared using the present invention,
Meet space application requirement, ensure the safety of spacecraft, reduces the cutoff value of radiation resistance glass cover plate 330nm.Pass through
The formula and technical matters of the present invention realizes existing Flouride-resistani acid phesphatase glass in 330nm and wave band optical transmittance≤0.3% below,
The average optical transmitance of optical transmittance >=90%, 500-1000nm of optical transmittance >=89%, 450nm of 400nm >=
90.5%.The performance requirements that disclosure satisfy that radioresistance flexible glass is beneficial to the promotion and implementation of the present invention.
Claims (6)
1. a kind of radioresistance flexible glass, it is characterised in that：The glass includes the 43.2%- matched according to mass percent
65.1% SiO2, 5.5%-13.5% Al2O3, 1.0%-5.5% P2O5, 1.5%-10.2% B2O3, 0.5%-
3.3% SnO2, 1.1%-2.9% Y2O3, 0.6%-3.7% ZrO2, 0.6%-3.5% Ta2O5, 0.8%-4.7%
Nb2O5, 1.5%-6% Li2O, the CeO of 3.5%-12.8%2, 0.9%-6.5% Na2O, the MgO of 0.2%-2.5%,
The ZnO of the BaO and 1.1%-3.2% of CaO, 0.1%-2.3% of 0.2%-3.2%.
2. a kind of radioresistance flexible glass according to claim 1, it is characterised in that：The glass includes according to quality
The SiO of the 50%-60% of percentage proportioning2, 8%-10% Al2O3, 2.5%-4% P2O5, 4%-7% B2O3、
The SnO of 1.5%-2.5%2, 1.8%-2.2% Y2O3, 1.5%-2.5% ZrO2, 1.5%-2.5% Ta2O5, 2%-
3.5% Nb2O5, 3%-4.5% Li2O, the CeO of 7%-10%2, 3%-4.5% Na2O, MgO, 1%- of 1%-2%
The ZnO of the BaO and 1.8%-2.3% of 2% CaO, 1%-1.6%.
3. a kind of radioresistance flexible glass according to claim 1, it is characterised in that：The glass includes according to quality
53% SiO of percentage proportioning2, 8% Al2O3, 3% P2O5, 5% B2O3, 2% SnO2, 2% Y2O3, 2%
ZrO2, 2% Ta2O5, 2.5% Nb2O5, 3% Li2O, 8% CeO2, 3.5% Na2O, 1.5% MgO, 1.5%
CaO, 1% BaO and 2% ZnO.
4. the preparation method based on radioresistance flexible glass described in claim 1, it is characterised in that：The preparation method includes
Following steps：
A, it is melted
By SiO2、Al2O3、P2O5、B2O3、SnO2、Y2O3、ZrO2、Ta2O5、Nb2O5、Li2O、CeO2、Na2O, MgO, CaO, BaO with
And ZnO is weighed according to proportion relation and is mixed to form raw material, raw material is sent into the melting furnace after preheating, preheating temperature
Degree is 1670-1710 DEG C, and high temperature discharging forms melting charge；
B, it is heat-treated
Anneal to melting charge, temperature be 590-650 DEG C, time 1-2h, basis of formation glass, then again to parent glass into
Row exact annealing process, temperature are 600-640 DEG C, time 3-6h；
C, grinding and polishing
Grinding or polishing are carried out at the same time to the upper and lower surface of parent glass after heat treatment, thickness is machined to and is not more than 0.07mm；
D, secondary heat treatment
It send and is made annealing treatment into annealing furnace, temperature is 600-620 DEG C, time 5-9h, forms radiation resistance glass；
E, handling flexibly
One layer is coated by SnCl on radiation resistance glass surface2、SbCl3、CeCl3, KCl and TiCl4The mixture of composition, and
It is sintered 0.5-3h at a temperature of 380-420 DEG C, is cooled down with liquid nitrogen after sintering, is then rinsed with deionized water, last shape
At radiation-proof flexible glass.
5. the preparation method of radioresistance flexible glass according to claim 4, it is characterised in that：In the step E, mix
It is 22-35 parts of SnCl that each ingredient of object, which is closed, according to mass fraction proportioning2, 14-23 parts of SbCl3, 8-16 parts of CeCl3, 35-50 parts of KCl with
And 6-12 parts of TiCl4。
6. the preparation method of radioresistance flexible glass according to claim 5, it is characterised in that：In the step E, mix
It is 26 parts of SnCl that each ingredient of object, which is closed, according to mass fraction proportioning2, 16 parts of SbCl3, 10 parts of CeCl3, 40 parts of KCl and 8 part of TiCl4。
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Cited By (3)
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| CN112919802A (en) * | 2021-02-24 | 2021-06-08 | 河北省沙河玻璃技术研究院 | High-strength flexible radiation-resistant glass and preparation method thereof |
| CN113072300A (en) * | 2021-04-06 | 2021-07-06 | 浙江大学 | Organic solar cell ultraviolet radiation resistant layer glass and preparation method thereof |
| CN116177902A (en) * | 2023-04-26 | 2023-05-30 | 秦皇岛星箭特种玻璃有限公司 | Preparation method of flexible glass |
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Application publication date: 20181109 |