CN1618759A - Preparation method of low ultraviolet absorption porous and non-porous high silica glass - Google Patents
Preparation method of low ultraviolet absorption porous and non-porous high silica glass Download PDFInfo
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- CN1618759A CN1618759A CN 200410067899 CN200410067899A CN1618759A CN 1618759 A CN1618759 A CN 1618759A CN 200410067899 CN200410067899 CN 200410067899 CN 200410067899 A CN200410067899 A CN 200410067899A CN 1618759 A CN1618759 A CN 1618759A
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- borosilicate glass
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- 238000010521 absorption reaction Methods 0.000 title claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 45
- 238000002360 preparation method Methods 0.000 title claims description 37
- 239000011521 glass Substances 0.000 claims abstract description 167
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000010306 acid treatment Methods 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 8
- 239000005388 borosilicate glass Substances 0.000 claims description 119
- 238000010438 heat treatment Methods 0.000 claims description 51
- 239000011651 chromium Substances 0.000 claims description 37
- 230000004927 fusion Effects 0.000 claims description 37
- -1 iron ion Chemical class 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- 229910052742 iron Inorganic materials 0.000 claims description 33
- 229910052804 chromium Inorganic materials 0.000 claims description 29
- 238000005303 weighing Methods 0.000 claims description 24
- 229910052684 Cerium Inorganic materials 0.000 claims description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 20
- 239000005368 silicate glass Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 238000001778 solid-state sintering Methods 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 229910052810 boron oxide Inorganic materials 0.000 claims description 10
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 8
- 229910052728 basic metal Inorganic materials 0.000 claims description 8
- 150000003818 basic metals Chemical class 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000004567 concrete Substances 0.000 claims description 4
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910001430 chromium ion Inorganic materials 0.000 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 229940001516 sodium nitrate Drugs 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 3
- 238000003723 Smelting Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 42
- 239000012071 phase Substances 0.000 description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 24
- 239000003153 chemical reaction reagent Substances 0.000 description 21
- 229910052697 platinum Inorganic materials 0.000 description 21
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 15
- 238000007669 thermal treatment Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- CHCGWNQHGOGCNA-UHFFFAOYSA-N 2,3-dimethyl-4-nitrobenzoic acid Chemical compound CC1=C(C)C([N+]([O-])=O)=CC=C1C(O)=O CHCGWNQHGOGCNA-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 229910052593 corundum Inorganic materials 0.000 description 13
- 239000010431 corundum Substances 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 13
- 239000000428 dust Substances 0.000 description 13
- 229910002804 graphite Inorganic materials 0.000 description 13
- 239000010439 graphite Substances 0.000 description 13
- 238000009413 insulation Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 6
- 235000021384 green leafy vegetables Nutrition 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910001447 ferric ion Inorganic materials 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000005320 cranberry glass Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000005295 porous vycor glass Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
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
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
-
- 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
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
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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 process for preparing the porous and non-porous high-silica glass with low ultraviolet absorption includes adding oxidant, twice smelting, repeating acid treatment to obtain porous high-silica glass with low content of transition metal ions, and reduction sintering to obtain the non-porous high-silica glass with low ultraviolet absorption. The glass prepared by the method has low melting temperature and low production cost, can be prepared into various shapes such as blocks, tubes, rods, fibers and the like so as to meet the requirements of various applications, and has the characteristics of high optical quality, good thermo-optic stability and physicochemical properties, low ultraviolet absorption and the like.
Description
Technical field
The present invention is relevant with vagcor, the preparation method of particularly a kind of low ultraviolet absorption multipore and poreless high silica glass.
Background technology
Optical element and ultraviolet that the extreme ultraviolet permeable material is mainly used in ultraviolet photosensitive device, excimer laser now see through color filter etc.Present extreme ultraviolet permeable material mainly is silica glass and crystal of fluoride material.But making the bulky single crystal material has very big difficulty on technology, and cost of manufacture is also very high.Silica glass has good extreme ultraviolet light transmission, high chemical stability, high mechanical strength, can make different shape and is suitable for performances such as precision optics processing, if can in silica glass, add some functional materialss, for example light emitting ionics such as organic dye, organic photoelectrical material, rare earth and transition metal, photic catalytic material etc. just will be widened the range of application of silica glass greatly.But the preparation of silica glass needs the high temperature more than 2000 ℃, and organic materials is through can't stand such high temperature; And light emitting ionics such as rare earth and transition metal prepare in the glass process in high-temperature fusion, often are not homodisperse in glass structure, and often easy spontaneous formation is trooped and produced the concentration delustring; Photic catalytic material is iff being the surface that covers glass, and its specific surface is too little, and its catalytic activity is difficult to give full play to.Therefore, if silica glass is prepared into a kind of porous material, and maintain the good optical through performance of glass, the problems referred to above just might be resolved.
Utilize the phase-splitting of sodium borosilicate glass to prepare porous borosilicate glass, pass through sintering then, it is Corning Incorporated's patent of the forties (Patent U.S 2106774) that the elimination porous is prepared into poreless high silica glass, and the trade(brand)name of this glass is called Vycor glass (Vycor).This method is also extensively adopted by countries in the world till last century 70, the eighties, and the past mainly is to be used to replace silica glass, as fluorescent tube and the electrovacuum glass of sending out short wavelength ultraviolet.Because silica glass fusing point height, viscosity is big, is difficult to produce at that time.Along with the development of High Temperature Furnaces Heating Apparatus technology and CVD method, above-mentioned application is fewer and feweri.Still there are some glass companies to produce this porous Vycor glass (high silica) glass at present both at home and abroad, are mainly used in aspects such as the carrier of gas separation membrane, chromatograph, catalyzer and composite organic-inorganic material.Also have in the porous borosilicate glass with the preparation of the split-phase method of Corning Incorporated trace to transition metal ions such as the iron of extreme ultraviolet light strong absorption and nickel, make that this glass is that 250 nanometers just begin to occur the intensive photoabsorption at wavelength, in order to be prepared into the fluorescent tube that to send out short wavelength ultraviolet, this sintered glass of sintering under reducing atmosphere normally, ferric ion is reduced to the ferrous ion of low uv-absorbing, and making the uv-absorbing end of this glass move to wavelength is 230 nanometers.In order to reduce trace iron ionic content in the sintered glass, Osaka, JAPAN Industrial Technology Research Institute has developed this sintered glass has been carried out acid treatment once more with the acid solution of ethylenediamine tetraacetic acid (EDTA) (EDTA), with the iron ion stripping of trace, it is 220 nanometers (special permission discloses clear 57-205337) that this method can make the uv-absorbing end of the glass behind oversintering move to wavelength.But the present invention is not perfect, because the uv-absorbing end of silica glass is 155 nanometers at wavelength, illustrates that the iron ion that also has trace exists.
Summary of the invention
The objective of the invention is to overcome the defective of above-mentioned prior art, the preparation method of a kind of low ultraviolet absorption multipore and poreless high silica glass is provided, the glass melting temperature of the inventive method preparation is not high, production cost is low, can be prepared into multiple shapes such as bulk, tubulose, bar-shaped and fiber, adapting to the needs of various application, and characteristics such as it is good to have high optical quality, hot light stability and physics-chem characteristic, and uv-absorbing is low.
Technical scheme of the present invention is as follows:
The preparation method of a kind of low ultraviolet absorption multipore and poreless high silica glass, the main points that it is characterized in that this method are to add oxygenant, twice scorification, repeat acid treatment to prepare the porous borosilicate glass of low transition metal ion content, again, the reduction sintering, prepare the poreless high silica glass of low uv-absorbing.
The preparation method of described low ultraviolet absorption multipore and poreless high silica glass comprises following concrete steps:
1. press the proportioning of the selected glass of the following composition weight percent of glass:
Form: SiO
2Al
2O
3Na
2O CaO B
2O
2MO
2(M=Ce, Mn or Cr
2O
2)
Wt％：60.0-45.0 6.0-0 10.0-6.0 5.0-0 40.0-28.0 1.0-0.3
By selected each raw material of proportioning weighing, after mixing, high-temperature fusion obtains borosilicate glass;
2. this borosilicate glass is put into High Temperature Furnaces Heating Apparatus, near the phase separation temperature of glass, heat-treat, allow the glass phase-splitting;
3. the hot acid of this phase-splitting glass being put into 85-130 ℃ carries out acid treatment, molten boron, basic metal, alkaline-earth metal ions and other metal ion that goes in the glass, comprise the oxygenant ion and the trace iron ion that are added, to prepare the porous borosilicate glass of low uv-absorbing;
The porous borosilicate glass that 4. will hang down uv-absorbing is placed in the High Temperature Furnaces Heating Apparatus, through the solid state sintering of 1050-1200 ℃ of temperature, prepares the poreless high silica glass of low uv-absorbing in reducing atmosphere.
The boron ion of described boron oxide is to introduce with the form of boric acid, Sodium Tetraborate.
The sodium ion of described yellow soda ash is to introduce with the form of SODIUMNITRATE, sodium sulfate.
The calcium ion of described lime carbonate is to introduce with the form of nitrocalcite, calcium hydroxide.
The cerium ion of the aluminum ion of described aluminium hydroxide, the mn ion of manganese oxide or cerium oxide or the chromium ion corresponding compounds of chromium sesquioxide are that raw material is introduced.
The preparation method of described low ultraviolet absorption multipore and poreless high silica glass is characterized in that this method is the preparation method of second melting, that is:
1. prepare silicate glass earlier, its weight percent is as follows:
Form: SiO
2Na
2O CaO Al
2O
2MO
2(M=Ce, Mn or Cr
2O
2)
wt％：?83.0-74.5 14.0-8.4 7.0-0 8.4-0 1.65-0
2. after this silicate glass being pulverized, add boron oxide again according to following ratio
Form: the silicate glass boron oxide
Weight ratio: 100 65.0-39.0
Fusion more at high temperature is to obtain mixing the borosilicate glass of oxygenant;
3. this borosilicate glass is put into High Temperature Furnaces Heating Apparatus, near the phase separation temperature of glass, heat-treat, allow the glass phase-splitting;
4. this phase-splitting glass is put into 85-130 ℃ hot acid and is carried out acid treatment, to prepare the porous borosilicate glass of low uv-absorbing;
5. the porous borosilicate glass that will hang down uv-absorbing is put into High Temperature Furnaces Heating Apparatus, passes through 1050-1200 ℃ solid state sintering in reducing atmosphere, to prepare the poreless high silica glass of low uv-absorbing.
Described oxygenant both can add when the preparation silicate glass, also can add when the second time, fusion was prepared into borosilicate glass.
Technical foundation of the present invention:
Divide phase time to find at the research borosilicate glass, the distribution of transition metal ion is uneven in the borosilicate glass of phase-splitting, the ion of the different valence state of common element of the same race can be distributed in the different phase-splittings in the borosilicate glass, high valence ion often is distributed in the high boron-rich phase of basic metal and alkaline-earth metal ions content, and ion often is distributed in the low Si-rich phase of basic metal and alkaline-earth metal ions content at a low price.Therefore, by to carrying out oxidation-reduction reaction control in the glass melting process, just might realize the distribution of the transition metal ion in the borosilicate glass of phase-splitting is controlled.That is to say, iron ion exists with divalence and two kinds of forms of trivalent often in glass, ferric ion is distributed in the boron-rich phase, and ferrous ion is distributed in the Si-rich phase, borosilicate glass to phase-splitting carries out acid treatment, be boron, basic metal and the alkaline-earth metal ions that dissolves away in the boron-rich phase, stay Si-rich phase, just become porous borosilicate glass.Therefore, in order to eliminate the iron ion in the glass as much as possible, just should allow the low price iron ion in the borosilicate glass be oxidized to trivalent as much as possible, and it is distributed in the Si-rich phase, during acid treatment, by molten the going of hot acid, the Si-rich phase that stays so just becomes the porous borosilicate glass of low iron ion content with boron, basic metal and alkaline-earth metal ions.Concrete is exactly when the raw material of preparation borosilicate glass, adds oxygenants such as small amounts cerium, manganese oxide and chromic oxide in raw material, to reach the purpose that the low price iron ion in the glass is oxidized to ferric ion.
On the other hand, we also find the borosilicate glass with twice scorification preparation in experiment, and behind glass phase-splitting acid treatment and sintering, its uv-absorbing is starkly lower than the borosilicate glass of a common scorification preparation.The borosilicate glass of so-called twice scorification preparation is to prepare silicate glass earlier, then, after this glass pulverizing, adds boron oxide, and fusion more at high temperature just can obtain borosilicate glass.Curve 1 (dotted line) among Fig. 1 just be the prepared sintered glass of this disposable fusion reduce absorption curves behind the sintering through 1100 ℃ of degree, this glass just begins to absorb consumingly UV-light in 210 nanometers; Curve 2 (solid line) among Fig. 1 be exactly second melting method of the present invention preparation sintered glass through becoming the absorption curves of poreless high silica glass behind 1100 ℃ of degree reduction sintering, uv-absorbing in wavelength 185 nanometers is lower, shown second melting to removing the trace iron ion, reducing uv-absorbing has obvious effects.
Adopt interpolation oxygenant and twice scorification to eliminate iron ion even increase, but may also have the high price iron ion of denier to exist in the porous borosilicate glass, therefore, in reducing atmosphere, porous borosilicate glass is carried out solid state sintering, iron ion is reduced at a low price, the ultraviolet that improves the agglomerating vagcor is a requisite process procedure through ability, as shown in Figure 2, curve 1 (dotted line) is sintered glass absorption curves behind the sintering in air of twice fusion preparation, curve 2 (solid line) is sintered glass absorption curves behind the sintering in reducing atmosphere of twice fusion preparation, and the uv-absorbing of the resulting nonporous glass of sintering is starkly lower than the resulting glass of sintering in air in reducing atmosphere.
On the other hand, adopt and repeatedly to repeat acid-treated method and can further eliminate iron ion in the porous borosilicate glass.Concrete steps be with toply mix oxygenant, the resulting porous borosilicate glass of second melting method is put into electric furnace once more, in 250～900 ℃ of degree temperature ranges, thermal treatment 0.5～10 hour; Carry out hot acid treatmently afterwards once more, this technology can repeatedly repeat, and so just can further lower the uv-absorbing of vagcor.Curve 2 (solid line) shown in Figure 3 is exactly the absorption curves through the nonporous glass behind 1100 ℃ of degree reduction sintering of second melting method preparation of the present invention, the acid-treated sintered glass of secondary, at wavelength is that the uv-absorbing of 185 nanometers is very low, under the test of vacuum ultraviolet spectrometer, this uv-absorbing end reaches 155 nanometers, with the absorption limit basically identical of the silica glass of scorification preparation.Curve 1 (dotted line) shown in Figure 3 is the absorption curves of present external commercial atresia Vycor glass, this glass is that 230 nanometers just begin to absorb consumingly UV-light at wavelength, obvious poreless high silica glass of the present invention is substantially exceeding Vycor glass aspect the ultraviolet through performance, and this illustrates that also its high price iron ion content is far below dimension gram sintered glass in the high silica porous glass of the present invention.
Specific implementation method of the present invention is to select silicon-dioxide, boron oxide (perhaps other boracic ionic compound, boric acid for example, Sodium Tetraborate etc.), (perhaps other contains composite and sodium ion composite to yellow soda ash, SODIUMNITRATE for example, sodium sulfate etc.), lime carbonate (the perhaps compound of other calcium ions, nitrocalcite for example, calcium hydroxide etc.), (perhaps other contains aluminum ions compound to aluminium hydroxide, aluminum nitrate for example, Tai-Ace S 150 etc.), (perhaps other contains manganese for manganese oxide or cerium oxide or chromium sesquioxide, cerium, the compound of chromium ion, nitrate for example, halogenide etc.) be raw material, by the prescription weighing, behind the mixing, high-temperature fusion obtains the glass of following composition:
SiO
2Al
2O
2Na
2O CaO B
2O
2MO
2(M=Ce, Mn or Cr
2O
2)
60.0～45.0 6.0～0 10.0～6.0 5.0～0 40.0～28.0 1.0～0.3
Then, this borosilicate glass that is added with oxygenant is put into high temperature aluminum, near the phase separation temperature of glass, heat-treat, allow the glass phase-splitting; Then the hot acid of this phase-splitting glass being put into 85 ~ 130 ℃ carries out acid treatment, molten boron, basic metal, alkaline-earth metal ions and other metal ion that goes in the glass, comprise the oxygenant ion and the trace iron ion that are added, so just can prepare the porous borosilicate glass of low uv-absorbing.The porous borosilicate glass of this low uv-absorbing is placed in the High Temperature Furnaces Heating Apparatus, in reducing atmosphere,, just can prepares the poreless high silica glass of low uv-absorbing through the solid state sintering of 1050-1200 ℃ of degree temperature.
As mentioned above, in order further to reduce uv-absorbing, we have developed more efficient methods again, and promptly second melting prepares borosilicate glass.Specifically be to prepare silicate glass earlier, and then be prepared into borosilicate glass that oxygenant promptly can add, and also can add when the second time, fusion was prepared into borosilicate glass when the preparation silicate glass.The silicate glass of preparation consists of earlier:
SiO
2Na
2O CaO Al
2O
2MO
2(M=Ce, Mn or with preparation technology's basically identical of common glass, the glass melting temperature is not high yet, production cost is low, and this glass can be prepared into different shapes such as bulk, tubulose, bar-shaped and fiber, to adapt to the needs of various application.This glass has high optical quality, hot light stability and physics-chem characteristic, and under the irradiation of UV-light, institute's intensity that fluoresces is low, person Cr
2O
2)
83.0-74.5 14.0-8.4 7.0-0 8.4-0 1.65-0
Then, after this glass pulverized, add boron oxide (perhaps other boracic ionic compound, for example boric acid, Sodium Tetraborate etc.) again according to following ratio, fusion more at high temperature just can obtain mixing the borosilicate glass of oxygenant.
The silicate glass boron oxide
100 65.0-39.0
Subsequently, this borosilicate glass is put into high temperature aluminum, near the phase separation temperature of glass, heat-treat, allow the glass phase-splitting; Then the hot acid of this phase-splitting glass being put into 85 ~ 130 ℃ carries out acid treatment, moltenly go boron, basic metal, alkaline-earth metal ions and other metal ion in the glass to comprise oxygenant ion and the trace iron ion that is added, so just can prepare the porous borosilicate glass of low uv-absorbing.The porous borosilicate glass of this low uv-absorbing is placed in the High Temperature Furnaces Heating Apparatus, in reducing atmosphere,, just can prepares the poreless high silica glass of low uv-absorbing through 1050-1200 ℃ of high temperature solid-phase sintering.
The composition of the resulting vagcor of the present invention is except that wherein micro-iron ion content difference, no matter be a scorification or the composition of the resulting porous borosilicate glass of second melting method is the same basically, compositing range (wt% by weight percentage) as follows:
SiO
2 B
2O
2 Al
2O
2
97.0～99.0 0.5～2.0 0.5～2.0
It is the key point of preparing the porous borosilicate glass of low transition metal ion content that interpolation oxygenant and twice scorification are added the repetition acid treatment, and the reduction sintering just can be prepared the poreless high silica glass of low uv-absorbing in the cooperation.
Glass preparation of the present invention is except twice fusion of needs, so other technology, glass of the present invention might become the porous borosilicate glass and the low uv-absorbing poreless high silica glass of new low transition metal ion content, is suitable for preparing the adulterated glass of functional ionic such as light emitting ionics such as organic dye, rare earth and transition metal, photic catalysis.Below be described with regard to embodiments of the invention:
Description of drawings
Fig. 1 is that the present invention reduces and becomes the spectral absorption curve of poreless high silica glass behind the sintering
Fig. 2 is the spectral absorption curve behind the sintered glass sintering of twice fusion preparation
Fig. 3 is the absorption curves through the nonporous glass behind 1100 ℃ of degree reduction sintering of second melting method preparation of the present invention, the acid-treated sintered glass of secondary
Embodiment
The invention will be further described below by embodiment, but should not limit protection scope of the present invention with this.
With analytical pure or chemical pure chemical reagent: SiO
2, H
3BO
3, Na
2CO
3, CaCO
3, Al (OH)
3And Cr
2O
3Press 51.7SiO
233.3B
2O
37.7Na
2O4.0CaO2.7Al
2O
30.6Cr
2O
3After the composition weighing of (weight percent), the mixing, put into platinum crucible, be prepared into green through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion and contain the chromium borosilicate glass; Then, with this green contain the chromium borosilicate glass put into High Temperature Furnaces Heating Apparatus through 560～630 ℃ after thermal treatment in 15～60 hours, the green that becomes the differential phase contains the chromium borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the green glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after the green completely dissolve of glass, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In High Temperature Furnaces Heating Apparatus with in the reducing atmosphere through 1050-1200 ℃ of high temperature solid-phase sintering, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.
With analytical pure or chemical pure chemical reagent: SiO
2, H
3BO
3, Na
2CO
3, CaCO
3, Al (OH)
3And MnO
2Press 60.0SiO
230.7B
2O
38.0Na
2O1.0Al
2O
30.3MnO
2After the composition weighing of (weight percent), the mixing, put into platinum crucible, be prepared into the dark brown manganese borosilicate glass that contains through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion; Then, with this dark brown contain the manganese borosilicate glass put into High Temperature Furnaces Heating Apparatus through 15～60 thermal treatments hour of 560～630 ℃ of degree after, the green that becomes the differential phase contains the manganese borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the cranberry glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after the dark brown completely dissolve of glass, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In High Temperature Furnaces Heating Apparatus with in the reducing atmosphere through the solid state sintering of 1050-1200 ℃ of degree temperature, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.
Embodiment 3
With analytical pure or chemical pure chemical reagent: SiO
2, H
3BO
3, Na
2CO
3, CaCO
3, Al (OH)
3And CeO
2Press 50.0SiO
228.0B
2O
310.0Na
2O5.0CaO6.0Al
2O
31.0CeO
3The composition weighing of (weight percent), mix after, put into platinum crucible, be prepared into through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion and contain the cerium borosilicate glass; Then, with this contain the cerium borosilicate glass put into High Temperature Furnaces Heating Apparatus through 15～60 thermal treatments hour of 560～630 ℃ of degree after, what become the differential phase contains the cerium borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after acid treatment finishes, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In High Temperature Furnaces Heating Apparatus with in the reducing atmosphere through the solid state sintering of 1050-1200 ℃ of degree temperature, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.
Embodiment 4
With analytical pure or chemical pure chemical reagent: SiO
2, H
3BO
3, Na
2CO
3, CaCO
3, Al (OH)
3And Cr
2O
3Press 50SiO
240B
2O
36.0Na
2O3.0CaO1.0Cr
2O
3After the composition weighing of (weight percent), the mixing, put into platinum crucible, be prepared into green through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion and contain the chromium borosilicate glass; Then, with this green contain the chromium borosilicate glass put into High Temperature Furnaces Heating Apparatus through 560～630 ℃ after 15～60 thermal treatments hour, the green that becomes the differential phase contains the chromium borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the green glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after the green completely dissolve of glass, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In High Temperature Furnaces Heating Apparatus with in the reducing atmosphere through the solid state sintering of 1050-1200 ℃ of temperature, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.
Embodiment 5
With analytical pure or chemical pure chemical reagent: SiO
2, H
3BO
3, Na
2CO
3, CaCO
3, Al (OH)
3And Cr
2O
3Press 45SiO
234.0B
2O
39.0Na
2O5.0CaO6.0Al
2O
31.0Cr
2O
3After the composition weighing of (weight percent), the mixing, put into platinum crucible, be prepared into green through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion and contain the chromium borosilicate glass; Then, with this green contain the chromium borosilicate glass put into High Temperature Furnaces Heating Apparatus through 560～630 ℃ after 15～60 thermal treatments hour, the green that becomes the differential phase contains the chromium borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the green glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after the green completely dissolve of glass, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In High Temperature Furnaces Heating Apparatus with in the reducing atmosphere through the solid state sintering of 1050-1200 ℃ of temperature, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.
Embodiment 6
With analytical pure or chemical pure chemical reagent: Na
2CO
3, SiO
2, Al (OH)
3, CaCO
3, Cr
2O
3, press 77.5SiO
211.5Na
2O6.0CaO4.0Al
2O
31.0Cr
2O
3The composition of (weight percent), weighing after the mixing, is put into platinum crucible, is prepared into green through 0.5～4 hour postcooling of 1500 ℃ high-temperature fusion and contains chromosilicates glass.Then, this glass is pulverized.Then contain chromosilicates glass: 50B by 100 greens
2O
3(use H
3BO
3Chemical reagent) ratio, weighing mixes, and puts into platinum crucible, is prepared into green through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion and contains the chromium borosilicate glass.Then, with this green contain the chromium borosilicate glass put into High Temperature Furnaces Heating Apparatus through 560～630 ℃ after 15～60 thermal treatments hour, the green that becomes the differential phase contains the chromium borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the green glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after the green completely dissolve of glass, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In the High Temperature Furnaces Heating Apparatus reducing atmosphere,, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing through the solid state sintering of 1050-1200 ℃ of temperature.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.Curve curve 2 (solid line) among Fig. 2 just be this glass absorption curves.
Embodiment 7
With analytical pure or chemical pure chemical reagent: Na
2CO
3, SiO
2, Al (OH)
3, CaCO
3, MnO
2, press 83.0SiO
214.0Na
2O1.35CaO1.65MnO
2The composition of (weight percent), weighing after the mixing, is put into platinum crucible, is prepared into dark brown manganese and silicon containing silicate glass through 0.5～4 hour postcooling of 1500 ℃ high-temperature fusion.Then, this glass is pulverized.Then by 100 dark brown manganese and silicon containing silicate glass: 65B
2O
3(use H
3BO
3Chemical reagent) ratio, weighing mixes, and puts into platinum crucible, is prepared into the dark brown manganese borosilicate glass that contains through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion.Then, with this dark brown contain the manganese borosilicate glass put into High Temperature Furnaces Heating Apparatus through 560～630 ℃ after thermal treatment in 15～60 hours, become the dark brown manganese borosilicate glass that contains of differential phase; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the cranberry glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after the dark brown completely dissolve of glass, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In High Temperature Furnaces Heating Apparatus with in the reducing atmosphere through the solid state sintering of 1050-1200 ℃ of degree temperature, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.
Embodiment 8
With analytical pure or chemical pure chemical reagent: Na
2CO
3, SiO
2, Al (OH)
3, CaCO
3, press 74.5SiO
210.1Na
2O7.0CaO8.4Al
2O
3The composition of (weight percent), weighing after the mixing, is put into platinum crucible, is prepared into through 0.5～4 hour postcooling of 1500 ℃ high-temperature fusion to contain green chromosilicates glass.Then, this glass is pulverized.Then contain chromosilicates glass: 55B by 100 greens
2O
3(use H
3BO
3Chemical reagent) ratio, weighing mixes, and puts into platinum crucible, is prepared into green through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion and contains the chromium borosilicate glass.Then, with this green contain the chromium borosilicate glass put into High Temperature Furnaces Heating Apparatus through 560～630 ℃ after thermal treatment in 15～60 hours, the green that becomes the differential phase contains the chromium borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the green glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after the green completely dissolve of glass, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In High Temperature Furnaces Heating Apparatus with in the reducing atmosphere through the solid state sintering of 1050-1200 ℃ of degree temperature, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.
Embodiment 9
With analytical pure or chemical pure chemical reagent: Na
2CO
3, SiO
2, Al (OH)
3, CaCO
3, CeO
2, press 80.0SiO
214.0Na
2O5.0Al
2O
31.0CeO
2The composition of (weight percent), weighing after the mixing, is put into platinum crucible, is prepared into cerium-containing silicate glass through 0.5～4 hour postcooling of 1500 ℃ high-temperature fusion.Then, this glass is pulverized.Then by 100 cerium-containing silicate glass: 39 B
2O
3(use H
3BO
3Chemical reagent) ratio, weighing mixes, and puts into platinum crucible, is prepared into through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion to contain the cerium borosilicate glass.Then, with this contain the cerium borosilicate glass put into High Temperature Furnaces Heating Apparatus through 560～630 ℃ after thermal treatment in 15～60 hours, what become the differential phase contains the cerium borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after acid treatment is intact, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In High Temperature Furnaces Heating Apparatus with in the reducing atmosphere through the solid state sintering of 1050-1200 ℃ of degree temperature, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.
Embodiment 10
With analytical pure or chemical pure chemical reagent: Na
2CO
3, SiO
2, Al (OH)
3, CaCO
3, Cr
2O
3, press 83.0SiO
28.4Na
2O3.6CaO4.0.0Al
2O
31.0Cr
2O
3The composition of (weight percent), weighing after the mixing, is put into platinum crucible, is prepared into through 0.5～4 hour postcooling of 1500 ℃ high-temperature fusion to contain green chromosilicates glass.Then, this glass is pulverized.Then contain chromosilicates glass: 55B by 100 greens
2O
3(use H
3BO
3Chemical reagent) ratio, weighing mixes, and puts into platinum crucible, is prepared into green through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion and contains the chromium borosilicate glass.Then, this green is contained the chromium borosilicate glass put into High Temperature Furnaces Heating Apparatus through after 560～630 ℃ of 15～60 thermal treatment hour, the green that becomes the differential phase contains the chromium borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the green glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after the green completely dissolve of glass, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In the High Temperature Furnaces Heating Apparatus reducing atmosphere,, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing through the solid state sintering of 1050-1200 ℃ of temperature.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.
Embodiment 11
With analytical pure or chemical pure chemical reagent: Na
2CO
3, SiO
2, Al (OH)
3, CaCO
3, CeO
2, press 78.0SiO
211.5Na
2O5.5CaO4.0Al
2O
31.0CeO
2The composition of (weight percent), weighing after the mixing, is put into platinum crucible, is prepared into cerium-containing silicate glass through 0.5～4 hour postcooling of 1500 ℃ high-temperature fusion.Then, this glass is pulverized.Then by 100 cerium-containing silicate glass: 50 B
2O
3(use H
3BO
3Chemical reagent) ratio, weighing mixes, and puts into platinum crucible, is prepared into through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion to contain the cerium borosilicate glass.Then, with this contain the cerium borosilicate glass put into High Temperature Furnaces Heating Apparatus through 560～630 ℃ of thermal treatments in 15～60 hours after, what become the differential phase contains the cerium borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after acid treatment is finished, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.Subsequently, the porous borosilicate glass that obtains is put into electric furnace once more, in 250～900 ℃ of degree temperature ranges, thermal treatment 0.5～10 hour; Carry out hot acid treatmently afterwards once more, heating and acid-treated technology repetition are more than twice once more.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In High Temperature Furnaces Heating Apparatus with in the reducing atmosphere through the solid state sintering of 1050-1200 ℃ of degree temperature, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the minimum uv-absorbing of agglomerating with the speed of per minute below 5 ℃.Curve 2 (solid line) shown in Figure 3 is exactly the absorption curves behind this glass reduction sintering.
Embodiment 12
With analytical pure or chemical pure chemical reagent: Na
2CO
3, SiO
2, Al (OH)
3, CaCO
3, Cr
2O
3, press 82SiO
210.5Na
2O4.0CaO3.0Al
2O
30.5Cr
2O
3The composition of (weight percent), weighing after the mixing, is put into platinum crucible, is prepared into through 0.5～4 hour postcooling of 1500 ℃ high-temperature fusion to contain green chromosilicates glass.Then, this glass is pulverized.Then contain chromosilicates glass: 60B by 100 greens
2O
3(use H
3BO
3Chemical reagent) ratio, weighing mixes, and puts into platinum crucible, is prepared into green through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion and contains the chromium borosilicate glass.Then, with this green contain the chromium borosilicate glass put into High Temperature Furnaces Heating Apparatus through 560～630 ℃ of thermal treatments in 15～60 hours after, the green that becomes the differential phase contains the chromium borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the green glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after the green completely dissolve of glass, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In the High Temperature Furnaces Heating Apparatus reducing atmosphere,, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing through the solid state sintering of 1050-1200 ℃ of temperature.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.
Embodiment 13
With analytical pure or chemical pure chemical reagent: Na
2CO
3, SiO
2, Al (OH)
3, CaCO
3, Cr
2O
3, press 78.5SiO
212.5Na
2O4.0CaO4.0Al
2O
31.0Cr
2O
3The composition of (weight percent), weighing after the mixing, is put into platinum crucible, is prepared into through 0.5～4 hour postcooling of 1500 ℃ high-temperature fusion to contain green chromosilicates glass.Then, this glass is pulverized.Then contain chromosilicates glass: 46B by 100 greens
2O
3(use H
3BO
3Chemical reagent) ratio, weighing mixes, and puts into platinum crucible, is prepared into green through 0.5～4 hour postcooling of 1400 ℃ high-temperature fusion and contains the chromium borosilicate glass.Then, with this green contain the chromium borosilicate glass put into High Temperature Furnaces Heating Apparatus through 560～630 ℃ of thermal treatments in 15～60 hours after, the green that becomes the differential phase contains the chromium borosilicate glass; With the ratio of every gram glass to 10～50 milliliters of normal salpeter solutions, the green glass of this differential phase is put into simultaneously the container of airtight acidproof, heatproof, carrying capacity with salpeter solution, carry out 12-72 hour acid treatment 900～140 ℃ temperature, in the acid treatment process, to change 2～3 nitroxylic acid solution, after the green completely dissolve of glass, this glass is taken out from container, use the distilled water wash clean, just can obtain the porous borosilicate glass of low iron ion content.This porous borosilicate glass is put into 50cc corundum crucible with cover, and around glass, put 5-10g graphite or carbon dust; In the High Temperature Furnaces Heating Apparatus reducing atmosphere,, eliminate the vagcor that micropore becomes closely knit transparent low uv-absorbing through the solid state sintering of 1050-1200 ℃ of temperature.In sintering process,, heat up with the speed of per minute below 5 ℃ from room temperature to 400 ℃; Afterwards, be warmed up to 950 ℃ of front and back with the speed of per minute below 10 ℃; Then be raised to 1100-1200 ℃ and after this temperature insulation is more than 30 minutes from this temperature, turn off the power supply of High Temperature Furnaces Heating Apparatus, allow the glass furnace cooling, just obtain the vagcor of the low uv-absorbing of agglomerating with the speed of per minute below 5 ℃.
Claims (8)
1, the preparation method of a kind of low ultraviolet absorption multipore and poreless high silica glass, the main points that it is characterized in that this method are to add oxygenant, twice scorification, add the porous borosilicate glass that low transition metal ion content is prepared in the repetition acid treatment, cooperate the reduction sintering to prepare the poreless high silica glass of low uv-absorbing again.
2, the preparation method of low ultraviolet absorption multipore according to claim 1 and poreless high silica glass is characterized in that this method comprises following concrete steps:
1. press the proportioning of the selected glass of the following composition weight percent of glass:
Form: SiO
2Al
2O
2Na
2O CaO B
2O
2MO
2(M=Ce, Mn or Cr
2O
2)
Wt％：60.0-45.0 6.0-0 10.0-6.0 5.0-0 40.0-28.0 1.0-0.3
By selected each raw material of proportioning weighing, after mixing, high-temperature fusion obtains borosilicate glass;
2. this borosilicate glass is put into High Temperature Furnaces Heating Apparatus, near the phase separation temperature of glass, heat-treat, allow the glass phase-splitting;
3. the hot acid of this phase-splitting glass being put into 85-130 ℃ carries out acid treatment, molten boron, basic metal, alkaline-earth metal ions and other metal ion that goes in the glass, comprise the oxygenant ion and the trace iron ion that are added, to prepare the porous borosilicate glass of low uv-absorbing;
The porous borosilicate glass that 4. will hang down uv-absorbing is placed in the High Temperature Furnaces Heating Apparatus, through the solid state sintering of 1050-1200 ℃ of temperature, prepares the poreless high silica glass of low uv-absorbing in reducing atmosphere.
3, the preparation method of low ultraviolet absorption multipore according to claim 2 and poreless high silica glass is characterized in that the boron ion of described boron oxide, is to introduce with the form of boric acid, Sodium Tetraborate.
4, the preparation method of low ultraviolet absorption multipore according to claim 2 and poreless high silica glass is characterized in that the sodium ion of described yellow soda ash, is to introduce with the form of SODIUMNITRATE, sodium sulfate.
5, the preparation method of low ultraviolet absorption multipore according to claim 2 and poreless high silica glass is characterized in that the calcium ion of described lime carbonate, is to introduce with the form of nitrocalcite, calcium hydroxide.
6, the preparation method of low ultraviolet absorption multipore according to claim 2 and poreless high silica glass is characterized in that the aluminum ion of described aluminium hydroxide, the mn ion of manganese oxide or the cerium ion of cerium oxide or the chromium ion corresponding compounds of chromium sesquioxide are that raw material is introduced.
7, the preparation method of low ultraviolet absorption multipore according to claim 1 and poreless high silica glass is characterized in that this method is the preparation method of second melting, that is:
1. prepare silicate glass earlier, its weight percent is as follows:
Form: SiO
2Na
2O CaO Al
2O
2MO
2(M=Ce, Mn or Cr
2O
3)
wt％：83.0-74.5 14.0-8.4 7.0-0 8.4-0 1.65-0
2. after this silicate glass being pulverized, add boron oxide again according to following ratio
Form: the silicate glass boron oxide
Weight ratio: 100 65.0-39.0
Fusion more at high temperature obtains mixing the borosilicate glass of oxygenant;
3. this borosilicate glass is put into High Temperature Furnaces Heating Apparatus, near the phase separation temperature of glass, heat-treat, allow the glass phase-splitting;
4. the hot acid of then this phase-splitting glass being put into 85-130 ℃ carries out acid treatment, prepares the porous borosilicate glass of low uv-absorbing;
5. the porous borosilicate glass that will hang down uv-absorbing is put into High Temperature Furnaces Heating Apparatus, passes through 1050-1200 ℃ solid state sintering in reducing atmosphere, to prepare the poreless high silica glass of low uv-absorbing.
8, the preparation method of low ultraviolet absorption multipore according to claim 7 and poreless high silica glass is characterized in that described oxygenant both can add, and also can add when the second time, fusion was prepared into borosilicate glass when the preparation silicate glass.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701590A (en) * | 2012-06-29 | 2012-10-03 | 中国科学院上海光学精密机械研究所 | Preparation method of near ultraviolet-excited high silica blue-light-emitting glass |
| CN103508667B (en) * | 2012-06-26 | 2016-01-06 | 广东华兴玻璃股份有限公司 | A kind of glass and preparation method thereof |
| CN108484095A (en) * | 2018-04-09 | 2018-09-04 | 翟琳 | A kind of preparation method of high-strength heat-insulating type aerogel material |
| CN114249531A (en) * | 2021-12-17 | 2022-03-29 | 陕西华特新材料股份有限公司 | Preparation method of high silica glass solution capable of improving liquid level melting capacity |
-
2004
- 2004-11-05 CN CN 200410067899 patent/CN1259268C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508667B (en) * | 2012-06-26 | 2016-01-06 | 广东华兴玻璃股份有限公司 | A kind of glass and preparation method thereof |
| CN102701590A (en) * | 2012-06-29 | 2012-10-03 | 中国科学院上海光学精密机械研究所 | Preparation method of near ultraviolet-excited high silica blue-light-emitting glass |
| CN102701590B (en) * | 2012-06-29 | 2015-07-29 | 中国科学院上海光学精密机械研究所 | The preparation method of near ultraviolet excitated high silica blue light emitting glass |
| CN108484095A (en) * | 2018-04-09 | 2018-09-04 | 翟琳 | A kind of preparation method of high-strength heat-insulating type aerogel material |
| CN114249531A (en) * | 2021-12-17 | 2022-03-29 | 陕西华特新材料股份有限公司 | Preparation method of high silica glass solution capable of improving liquid level melting capacity |
| CN114249531B (en) * | 2021-12-17 | 2024-01-19 | 陕西华特新材料股份有限公司 | Preparation method of high silica glass melt capable of improving liquid level melting capacity |
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