CN110002747A - A kind of not deliquescent high-purity sulfur-halogen glass and its purification preparation method - Google Patents
A kind of not deliquescent high-purity sulfur-halogen glass and its purification preparation method Download PDFInfo
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- CN110002747A CN110002747A CN201910303937.9A CN201910303937A CN110002747A CN 110002747 A CN110002747 A CN 110002747A CN 201910303937 A CN201910303937 A CN 201910303937A CN 110002747 A CN110002747 A CN 110002747A
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- glass
- halogen
- tube
- purity
- sulfur
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- 239000011521 glass Substances 0.000 title claims abstract description 230
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 99
- 238000000746 purification Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 26
- 239000005387 chalcogenide glass Substances 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 76
- 239000002994 raw material Substances 0.000 claims description 64
- 238000007670 refining Methods 0.000 claims description 44
- 239000010453 quartz Substances 0.000 claims description 30
- 239000003708 ampul Substances 0.000 claims description 26
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 22
- 239000011669 selenium Substances 0.000 claims description 21
- 238000005906 dihydroxylation reaction Methods 0.000 claims description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- 239000011630 iodine Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000002309 gasification Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000006392 deoxygenation reaction Methods 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 14
- 230000003287 optical effect Effects 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 239000013307 optical fiber Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000470 constituent Substances 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004566 IR spectroscopy Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- -1 water) wanted Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/02—Pretreated ingredients
- C03C1/022—Purification of silica sand or other minerals
-
- 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
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
- C03C3/323—Chalcogenide glasses, e.g. containing S, Se, Te containing halogen, e.g. chalcohalide glasses
-
- 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
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
Abstract
The invention discloses a kind of not deliquescent high-purity sulfur-halogen glass and its purification preparation method, mole composition of high-purity sulfur-halogen glass is expressed as (Ge-As-Se) by chemical formula100‑xIx, wherein x=0 ~ 40.I is added in Ge-As-Se chalcogenide glass matrix in the present invention, proposes a kind of not deliquescent high-purity sulfur-halogen glass system of constituent optimization, while proposing a kind of purification preparation method that can be efficiently separated the impurity in sulfur-halogen glass and reduce its deliquescence.Purification preparation method of the present invention can effectively remove main oxygenatedchemicals and hydroxy-containing compounds (including water) in sulfur-halogen glass, its purity is improved while obtaining not deliquescent sulfur-halogen glass.High-purity sulfur-halogen glass optical quality is uniform, and infrared transmittivity is good, can prepare not deliquescent high-purity sulfur-halogen glass optical fiber.
Description
Technical field
The invention belongs to sulfur-halogen glass and its preparation technical fields, and in particular to a kind of not deliquescent high-purity sulfur-halogen glass
And its purification preparation method.
Background technique
Sulfur-halogen glass is a kind of nonoxide glass based on chalcogen and halogen.Sulfur-halogen glass combines chalcogenide glass
With the double dominant of halide, such as high non-linear property, excellent anti-crystallization ability, good thermal stability and chemical stabilization
Property and excellent IR transmission.Therefore, sulfur-halogen glass is more satisfactory Infrared Transmission material, while being also potential red
Outer laser, fiber amplifier, all optical network switch and fast-ionic conductor host material.In addition, sulfur-halogen glass can also prepare low damage
Fibre is depleted, sulfur-halogen glass low loss fiber is a kind of applied to splendid nonlinear opticals in fields such as generation broadband infrared super continuous spectrums
Learn material.
But it is limited by preparation process, oxide (As-O, Ge-O, Si-O etc.), hydroxyl in existing sulfur-halogen glass
(H2O, O-H, S-H, Se-H etc.) etc. impurity contents it is higher, leading to sulfur-halogen glass, there are deliquescent defects, so that sulfur-halogen glass
Optical fiber made of drawing also easily deliquesces, and limits the application of sulfur-halogen glass optical fiber.In addition, the infrared transmission performance of sulfur-halogen glass
It is highly prone to the influence of impurity, these impurity cause the presence of the oxide absorption band of various sulfur-halogen glass elements, and these oxygen
Compound absorption band is the greatest problem for influencing glass far infrared region transmitance.Impurity in sulfur-halogen glass mostlys come from original
Material, raw material surface, quartz ampoule and sealing-in process.In addition, in carbon impurity, metal impurities, quartz ampoule in initial feed
SiO2Particle will increase the backscatter loss of light, to reduce the transmitance of sulfur-halogen glass.Finally, generally containing in sulfur-halogen glass
There is the volatile halogen component easily to distil, is generally difficult to adopt traditional heating and gasifying method and is purified.
Summary of the invention
The technical problems to be solved by the present invention are: in view of the deficiencies of the prior art, providing a kind of not deliquescent high-purity
Sulfur-halogen glass and its purification preparation method.
The technical scheme of the invention to solve the technical problem is: a kind of not deliquescent high-purity sulfur-halogen glass,
Mole composition of high-purity sulfur-halogen glass is expressed as (Ge-As-Se) by chemical formula100-xIx, wherein x=0~40.
Preferably, mole composition of high-purity sulfur-halogen glass is expressed as (Ge by chemical formula10As22Se68)100-xIx, wherein
X=0~15.
Further, mole composition of x=10, high-purity sulfur-halogen glass are expressed as (Ge by chemical formula10As22Se68)90I10。
Alternatively, further, a mole composition of x=12, high-purity sulfur-halogen glass are expressed as by chemical formula
(Ge10As22Se68)88I12。
Preferably, mole composition of high-purity sulfur-halogen glass is expressed as (Ge by chemical formula33As12Se55)100-xIx, wherein
X=0~40.
Further, mole composition of x=15, high-purity sulfur-halogen glass are expressed as (Ge by chemical formula33As12Se55)85I15。
Alternatively, further, a mole composition of x=20, high-purity sulfur-halogen glass are expressed as by chemical formula
(Ge33As12Se55)80I20。
The purification preparation method of above-mentioned not deliquescent high-purity sulfur-halogen glass, comprising the following steps:
1) elemental Germanium, elemental arsenic and the elemental selenium of chunky shape are weighed by chemical formula, are uniformly mixed, are obtained mixture；It weighs
Oxygen scavenger, the amount of weighing of oxygen scavenger are 0.03~0.1wt% of mixture total amount；
2) prepare one and pass through the two-tube quartz ampoule of the pretreated H-type of dehydroxylation, the two-tube quartz ampoule of the H-type includes glass original
Expects pipe and refining glass pipe, glass raw material pipe and refining glass pipe are communicated through connecting tube, glass raw material pipe and refining glass pipe
Upper end is open respectively；Mixture obtained in step 1) and oxygen scavenger are uniformly mixed and are put into the glass of the two-tube quartz ampoule of H-type
In glass mother tube, with the upper end opening of oxyhydrogen flame closed glass mother tube, vacuum pump is connected in the upper end of refining glass pipe, is taken out
Vacuum, while glass raw material pipe is heated, when the vacuum degree in the two-tube quartz ampoule of H-type reaches 2 × 10-3When Pa or less, hydrogen-oxygen is used
The upper end opening of flame closing refining glass pipe；
3) glass raw material pipe is heated at high temperature, while is placed in refining glass pipe under room temperature, made in glass raw material pipe
Raw material high-temperature gasification and distill through connecting tube to cryogenic condensation in refining glass pipe, in glass raw material pipe raw material all steam
After evaporating, with oxyhydrogen flame envelope disconnection adapter tube；
4) refining glass pipe is put into rocking furnace, is to slowly warm up to 600~950 DEG C, after waving melted 12~18 hours
Taking-up is cooled to room temperature, and is then made annealing treatment, and chalcogenide glass matrix is obtained；
5) chalcogenide glass matrix is taken out, is put into one by vacuumizing, together in the pretreated straight type quartz glass tube of dehydroxylation
The straight type quartz glass tube of Shi Jiare 1~4 hour is to remove the water to dissociate in straight type quartz glass tube, after being cooled to room temperature, straight
Iodine is added in type quartz glass tube, closes the nozzle of straight type quartz glass tube after vacuumizing with oxyhydrogen flame；
6) straight type quartz glass tube is put into rocking furnace, is to slowly warm up to 600~950 DEG C, it is small to wave melted 12~18
When after take out and be cooled to room temperature, then made annealing treatment, obtain not deliquescent high-purity sulfur-halogen glass.
Purification preparation method of the present invention during the preparation process, is vacuumized and is heated to glass raw material pipe in step 2), can be removed
Remove the hydrone adhered in the two-tube quartz ampoule of H-type and raw material；By high-temperature heating glass raw material pipe in step 3), keep glass former
While raw material in expects pipe obtains distilation, the impurity such as oxygenatedchemicals and transition metal in raw material are gone by oxygen scavenger
It removes；By heating straight type quartz glass tube and vacuumizing in step 5), the water to dissociate in straight type quartz glass tube can remove, finally
Obtain not deliquescent high-purity sulfur-halogen glass.
Preferably, the oxygen scavenger is aluminum strip or magnesium rod.
Preferably, the elemental Germanium, elemental arsenic, elemental selenium and iodine purity be not less than 99.9% respectively, with
Further promote the purity of sulfur-halogen glass obtained.
Compared with the prior art, the advantages of the present invention are as follows: I is added in Ge-As-Se chalcogenide glass matrix in the present invention,
It is proposed a kind of not deliquescent high-purity sulfur-halogen glass system of constituent optimization, at the same propose it is a kind of can be by the impurity in sulfur-halogen glass
Efficiently separate and reduce the purification preparation method of its deliquescence.Purification preparation method of the present invention can effectively remove main in sulfur-halogen glass
The oxygenatedchemicals and hydroxy-containing compounds (including water) wanted, it is pure to improve its while obtaining not deliquescent sulfur-halogen glass
Degree.High-purity sulfur-halogen glass optical quality is uniform, and infrared transmittivity is good, can prepare not deliquescent high-purity sulfur-halogen glass optical fiber.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the two-tube quartz ampoule of H-type in embodiment；
Fig. 2 is not deliquescent high-purity sulfur-halogen glass (Ge of embodiment 110As22Se68)90I10With the sulphur halogen glass of comparative example 1
The infrared of glass compares through spectrum；
Fig. 3 is not deliquescent high-purity sulfur-halogen glass (Ge of embodiment 333As12Se55)85I15With the sulphur halogen glass of comparative example 2
The infrared of glass compares through spectrum；
Fig. 4 is the phasor of sulfur-halogen glass of the present invention.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
Mole composition of not deliquescent high-purity sulfur-halogen glass of embodiment 1 is expressed as (Ge by chemical formula10As22Se68)90I10, comprising the following steps:
1) it is not less than 99.9% elemental Germanium, elemental arsenic and elemental selenium respectively by the purity that chemical formula weighs chunky shape, mixes
It closes uniformly, obtains mixture；Magnesium rod is weighed as oxygen scavenger, the amount of weighing of oxygen scavenger is the 0.035wt% of mixture total amount；2)
Prepare one and pass through the two-tube quartz ampoule of the pretreated H-type of dehydroxylation, as shown in Figure 1, the two-tube quartz ampoule of the H-type includes glass original
Expects pipe A and refining glass pipe B, glass raw material pipe A and refining glass pipe B are communicated through connecting tube C, glass raw material pipe A and purification glass
The upper end of glass pipe B is open respectively；Mixture obtained in step 1) and oxygen scavenger are uniformly mixed and are put into the two-tube quartz peace of H-type
In the glass raw material pipe A of small jar, with the upper end opening of oxyhydrogen flame closed glass mother tube A, connected in the upper end of refining glass pipe B
Vacuum pump (not shown), vacuumizes, while heating glass raw material pipe A to 120 DEG C, when true in the two-tube quartz ampoule of H-type
Reciprocal of duty cycle reaches 2 × 10-3When Pa or less, with the upper end opening of oxyhydrogen flame closing refining glass pipe B；3) resistance-heated furnace or stone are used
Black heating furnace is heated at high temperature to glass raw material pipe A and (keeps the temperature 5 hours at a temperature of 750 DEG C), while is placed in refining glass pipe B
Under room temperature, using the draught head between refining glass pipe B and glass raw material pipe A, make the raw material high-temperature gasification in glass raw material pipe A
And distill through connecting tube C to cryogenic condensation in refining glass pipe B, and high boiling C, SiO2And the impurity such as MgO stay in glass
In mother tube A, after all distilling to the raw material in glass raw material pipe A, disconnection adapter tube C is sealed with oxyhydrogen flame；It 4) will purification
Glass tube B is put into rocking furnace, is to slowly warm up to 850 DEG C, is taken out and is cooled to room temperature after waving melted 12 hours, is then moved back
Fire processing (keeping the temperature 2 hours at glass transition temperature ± 5 DEG C, be then down to room temperature at 10 hours), it is equal to obtain optical quality
The chalcogenide glass matrix even, infrared transmittivity is good；5) chalcogenide glass matrix is taken out, one is put into and passes through the pretreated straight type of dehydroxylation
In quartz glass tube, vacuumize, at the same heat straight type quartz glass tube 1 hour with remove in straight type quartz glass tube dissociate
Water after being cooled to room temperature, the iodine that purity is not less than 99.9% is added in straight type quartz glass tube, uses hydrogen-oxygen after vacuumizing
Flame closes the nozzle of straight type quartz glass tube；6) straight type quartz glass tube is put into rocking furnace, is to slowly warm up to 700 DEG C,
It waves melted 12 hours, further takes out and be cooled to room temperature, then made annealing treatment and (keep the temperature 2 at glass transition temperature ± 5 DEG C
Hour, then room temperature was down at 10 hours), obtain not deliquescent high-purity sulfur-halogen glass of embodiment 1.
Not deliquescent high-purity sulfur-halogen glass of embodiment 1 is taken out from straight type quartz glass tube, is cut to thickness 1.4mm
Hereinafter, obtaining sample using grinding and twin polishing.Infrared spectroscopy performance test, test are carried out to the sulfur-halogen glass sample
As a result as shown in Figure 2.
Mole composition of not deliquescent high-purity sulfur-halogen glass of embodiment 2 is expressed as (Ge by chemical formula10As22Se68)88I12, comprising the following steps:
1) it is not less than 99.9% elemental Germanium, elemental arsenic and elemental selenium respectively by the purity that chemical formula weighs chunky shape, mixes
It closes uniformly, obtains mixture；Magnesium rod is weighed as oxygen scavenger, the amount of weighing of oxygen scavenger is the 0.035wt% of mixture total amount；2)
Prepare one and pass through the two-tube quartz ampoule of the pretreated H-type of dehydroxylation, as shown in Figure 1, the two-tube quartz ampoule of the H-type includes glass original
Expects pipe A and refining glass pipe B, glass raw material pipe A and refining glass pipe B are communicated through connecting tube C, glass raw material pipe A and purification glass
The upper end of glass pipe B is open respectively；Mixture obtained in step 1) and oxygen scavenger are uniformly mixed and are put into the two-tube quartz peace of H-type
In the glass raw material pipe A of small jar, with the upper end opening of oxyhydrogen flame closed glass mother tube A, connected in the upper end of refining glass pipe B
Vacuum pump (not shown), vacuumizes, while heating glass raw material pipe A to 120 DEG C, when true in the two-tube quartz ampoule of H-type
Reciprocal of duty cycle reaches 2 × 10-3When Pa or less, with the upper end opening of oxyhydrogen flame closing refining glass pipe B；3) resistance-heated furnace or stone are used
Black heating furnace is heated at high temperature to glass raw material pipe A and (keeps the temperature 6 hours at a temperature of 760 DEG C), while is placed in refining glass pipe B
Under room temperature, using the draught head between refining glass pipe B and glass raw material pipe A, make the raw material high-temperature gasification in glass raw material pipe A
And distill through connecting tube C to cryogenic condensation in refining glass pipe B, and high boiling C, SiO2And the impurity such as MgO stay in glass
In mother tube A, after all distilling to the raw material in glass raw material pipe A, disconnection adapter tube C is sealed with oxyhydrogen flame；It 4) will purification
Glass tube B is put into rocking furnace, is to slowly warm up to 850 DEG C, is taken out and is cooled to room temperature after waving melted 18 hours, is then moved back
Fire processing (keeping the temperature 3 hours at glass transition temperature ± 5 DEG C, be then down to room temperature at 10 hours), it is equal to obtain optical quality
The chalcogenide glass matrix even, infrared transmittivity is good；5) chalcogenide glass matrix is taken out, one is put into and passes through the pretreated straight type of dehydroxylation
In quartz glass tube, vacuumize, at the same heat straight type quartz glass tube 3 hours with remove in straight type quartz glass tube dissociate
Water after being cooled to room temperature, the iodine that purity is not less than 99.9% is added in straight type quartz glass tube, uses hydrogen-oxygen after vacuumizing
Flame closes the nozzle of straight type quartz glass tube；6) straight type quartz glass tube is put into rocking furnace, is to slowly warm up to 700 DEG C,
It waves melted 13 hours, further takes out and be cooled to room temperature, then made annealing treatment and (keep the temperature 3 at glass transition temperature ± 5 DEG C
Hour, then room temperature was down at 10 hours), obtain not deliquescent high-purity sulfur-halogen glass of embodiment 2.
Not deliquescent high-purity sulfur-halogen glass of embodiment 2 is taken out from straight type quartz glass tube, is cut to thickness 1.4mm
Hereinafter, obtaining sample using grinding and twin polishing.Infrared spectroscopy performance test is carried out to the sulfur-halogen glass sample.
Mole composition of not deliquescent high-purity sulfur-halogen glass of embodiment 3 is expressed as (Ge by chemical formula33As12Se55)85I15, comprising the following steps:
1) it is not less than 99.9% elemental Germanium, elemental arsenic and elemental selenium respectively by the purity that chemical formula weighs chunky shape, mixes
It closes uniformly, obtains mixture；Magnesium rod is weighed as oxygen scavenger, the amount of weighing of oxygen scavenger is the 0.065wt% of mixture total amount；2)
Prepare one and pass through the two-tube quartz ampoule of the pretreated H-type of dehydroxylation, as shown in Figure 1, the two-tube quartz ampoule of the H-type includes glass original
Expects pipe A and refining glass pipe B, glass raw material pipe A and refining glass pipe B are communicated through connecting tube C, glass raw material pipe A and purification glass
The upper end of glass pipe B is open respectively；Mixture obtained in step 1) and oxygen scavenger are uniformly mixed and are put into the two-tube quartz peace of H-type
In the glass raw material pipe A of small jar, with the upper end opening of oxyhydrogen flame closed glass mother tube A, connected in the upper end of refining glass pipe B
Vacuum pump (not shown), vacuumizes, while heating glass raw material pipe A to 120 DEG C, when true in the two-tube quartz ampoule of H-type
Reciprocal of duty cycle reaches 2 × 10-3When Pa or less, with the upper end opening of oxyhydrogen flame closing refining glass pipe B；3) resistance-heated furnace or stone are used
Black heating furnace is heated at high temperature to glass raw material pipe A and (keeps the temperature 5 hours at a temperature of 780 DEG C), while is placed in refining glass pipe B
Under room temperature, using the draught head between refining glass pipe B and glass raw material pipe A, make the raw material high-temperature gasification in glass raw material pipe A
And distill through connecting tube C to cryogenic condensation in refining glass pipe B, and high boiling C, SiO2And the impurity such as MgO stay in glass
In mother tube A, after all distilling to the raw material in glass raw material pipe A, disconnection adapter tube C is sealed with oxyhydrogen flame；It 4) will purification
Glass tube B is put into rocking furnace, is to slowly warm up to 750 DEG C, is taken out and is cooled to room temperature after waving melted 18 hours, is then moved back
Fire processing (keeping the temperature 2 hours at glass transition temperature ± 5 DEG C, be then down to room temperature at 10 hours), it is equal to obtain optical quality
The chalcogenide glass matrix even, infrared transmittivity is good；5) chalcogenide glass matrix is taken out, one is put into and passes through the pretreated straight type of dehydroxylation
In quartz glass tube, vacuumize, at the same heat straight type quartz glass tube 4 hours with remove in straight type quartz glass tube dissociate
Water after being cooled to room temperature, the iodine that purity is not less than 99.9% is added in straight type quartz glass tube, uses hydrogen-oxygen after vacuumizing
Flame closes the nozzle of straight type quartz glass tube；6) straight type quartz glass tube is put into rocking furnace, is to slowly warm up to 750 DEG C,
It takes out and is cooled to room temperature after waving melted 12 hours, then made annealing treatment and (keep the temperature 3 at glass transition temperature ± 5 DEG C
Hour, then room temperature was down at 10 hours), obtain not deliquescent high-purity sulfur-halogen glass of embodiment 3.
Not deliquescent high-purity sulfur-halogen glass of embodiment 3 is taken out from straight type quartz glass tube, is cut to thickness 1.4mm
Hereinafter, obtaining sample using grinding and twin polishing.Infrared spectroscopy performance test, test are carried out to the sulfur-halogen glass sample
As a result as shown in Figure 3.
Mole composition of not deliquescent high-purity sulfur-halogen glass of embodiment 4 is expressed as (Ge by chemical formula33As12Se55)80I20, comprising the following steps:
1) it is not less than 99.9% elemental Germanium, elemental arsenic and elemental selenium respectively by the purity that chemical formula weighs chunky shape, mixes
It closes uniformly, obtains mixture；Magnesium rod is weighed as oxygen scavenger, the amount of weighing of oxygen scavenger is the 0.035wt% of mixture total amount；2)
Prepare one and pass through the two-tube quartz ampoule of the pretreated H-type of dehydroxylation, as shown in Figure 1, the two-tube quartz ampoule of the H-type includes glass original
Expects pipe A and refining glass pipe B, glass raw material pipe A and refining glass pipe B are communicated through connecting tube C, glass raw material pipe A and purification glass
The upper end of glass pipe B is open respectively；Mixture obtained in step 1) and oxygen scavenger are uniformly mixed and are put into the two-tube quartz peace of H-type
In the glass raw material pipe A of small jar, with the upper end opening of oxyhydrogen flame closed glass mother tube A, connected in the upper end of refining glass pipe B
Vacuum pump (not shown), vacuumizes, while heating glass raw material pipe A to 120 DEG C, when true in the two-tube quartz ampoule of H-type
Reciprocal of duty cycle reaches 2 × 10-3When Pa or less, with the upper end opening of oxyhydrogen flame closing refining glass pipe B；3) resistance-heated furnace or stone are used
Black heating furnace is heated at high temperature to glass raw material pipe A and (keeps the temperature 5 hours at a temperature of 780 DEG C), while is placed in refining glass pipe B
Under room temperature, using the draught head between refining glass pipe B and glass raw material pipe A, make the raw material high-temperature gasification in glass raw material pipe A
And distill through connecting tube C to cryogenic condensation in refining glass pipe B, and high boiling C, SiO2And the impurity such as MgO stay in glass
In mother tube A, after all distilling to the raw material in glass raw material pipe A, disconnection adapter tube C is sealed with oxyhydrogen flame；It 4) will purification
Glass tube B is put into rocking furnace, is to slowly warm up to 850 DEG C, is taken out and is cooled to room temperature after waving melted 18 hours, is then moved back
Fire processing (keeping the temperature 2 hours at glass transition temperature ± 5 DEG C, be then down to room temperature at 11 hours), it is equal to obtain optical quality
The chalcogenide glass matrix even, infrared transmittivity is good；5) chalcogenide glass matrix is taken out, one is put into and passes through the pretreated straight type of dehydroxylation
In quartz glass tube, vacuumize, at the same heat straight type quartz glass tube 1 hour with remove in straight type quartz glass tube dissociate
Water after being cooled to room temperature, the iodine that purity is not less than 99.9% is added in straight type quartz glass tube, uses hydrogen-oxygen after vacuumizing
Flame closes the nozzle of straight type quartz glass tube；6) straight type quartz glass tube is put into rocking furnace, is to slowly warm up to 800 DEG C,
It takes out and is cooled to room temperature after waving melted 15 hours, then made annealing treatment and (keep the temperature 2 at glass transition temperature ± 5 DEG C
Hour, then room temperature was down at 10 hours), obtain not deliquescent high-purity sulfur-halogen glass of embodiment 4.
Not deliquescent high-purity sulfur-halogen glass of embodiment 4 is taken out from straight type quartz glass tube, is cut to thickness 1.4mm
Hereinafter, obtaining sample using grinding and twin polishing.Infrared spectroscopy performance test is carried out to the sulfur-halogen glass sample.
Comparative example 1: the difference from embodiment 1 is that, oxygen scavenger is not used in purification preparation process, it is also not double in H-type
It is handled in pipe quartz ampoule by distilation, but uses art methods, after raw material is mixed directly in rocking furnace
It is melted and obtains chalcogenide glass, iodine is added later, be melted using rocking furnace and obtain the common sulfur-halogen glass of comparative example 1.It will
The sulfur-halogen glass of comparative example 1 is cut to thickness 1.4mm hereinafter, using grinding and twin polishing, obtains sample.To the sulphur halogen glass
Glass sample carries out infrared spectroscopy performance test, and test results are shown in figure 2.
Comparative example 2: the difference with embodiment 3 is, oxygen scavenger is not used in purification preparation process, also not double in H-type
It is handled in pipe quartz ampoule by distilation, but uses art methods, after raw material is mixed directly in rocking furnace
It is melted and obtains chalcogenide glass, iodine is added later, be melted using rocking furnace and obtain the common sulfur-halogen glass of comparative example 2.It will
The sulfur-halogen glass of comparative example 2 is cut to thickness 1.4mm hereinafter, using grinding and twin polishing, obtains sample.To the sulphur halogen glass
Glass sample carries out infrared spectroscopy performance test, and test results are shown in figure 3.
In Fig. 2 and Fig. 3, above a curve be respectively embodiment 1 and embodiment 3 high-purity sulfur-halogen glass infrared glass
Spectrogram, below a curve be respectively comparative example 1 and comparative example 2 sulfur-halogen glass infrared glass spectrogram.From Fig. 2 and figure
3 as can be seen that high-purity sulfur-halogen glass of embodiment 1 and embodiment 3 has higher light transmittance, OH- ,-H2The impurity such as O and Ge-O
Absorption peak is obviously weakened, water peak and oxygen peak be improved significantly, illustrate that purification preparation method of the present invention can effectively remove sulphur
Main oxygenatedchemicals and hydroxy-containing compounds (including water) in halogen glass can obtain not deliquescent sulfur-halogen glass
Its purity is improved simultaneously.
The phasor of high-purity sulfur-halogen glass is shown in Fig. 4 in above embodiments.For high-purity sulfur-halogen glass (Ge10As22Se68)100- xIx, x is capable of forming glass in the range of 0~15；For (Ge33As12Se55)100-xIx, x is then in the range of 0~40, energy
Form glass.
Claims (10)
1. a kind of not deliquescent high-purity sulfur-halogen glass, it is characterised in that a mole composition for high-purity sulfur-halogen glass presses chemical formula table
It is shown as (Ge-As-Se)100-xIx, wherein x=0~40.
2. a kind of not deliquescent high-purity sulfur-halogen glass according to claim 1, it is characterised in that high-purity sulfur-halogen glass
A mole composition by chemical formula be expressed as (Ge10As22Se68)100-xIx, wherein x=0~15.
3. a kind of not deliquescent high-purity sulfur-halogen glass according to claim 2, it is characterised in that x=10, the high purity sulphur
Mole composition of halogen glass is expressed as (Ge by chemical formula10As22Se68)90I10。
4. a kind of not deliquescent high-purity sulfur-halogen glass according to claim 2, it is characterised in that x=12, the high purity sulphur
Mole composition of halogen glass is expressed as (Ge by chemical formula10As22Se68)88I12。
5. a kind of not deliquescent high-purity sulfur-halogen glass according to claim 1, it is characterised in that high-purity sulfur-halogen glass
A mole composition by chemical formula be expressed as (Ge33As12Se55)100-xIx, wherein x=0~40.
6. a kind of not deliquescent high-purity sulfur-halogen glass according to claim 5, it is characterised in that x=15, the high purity sulphur
Mole composition of halogen glass is expressed as (Ge by chemical formula33As12Se55)85I15。
7. a kind of not deliquescent high-purity sulfur-halogen glass according to claim 5, it is characterised in that x=20, the high purity sulphur
Mole composition of halogen glass is expressed as (Ge by chemical formula33As12Se55)80I20。
8. a kind of purification preparation method of not deliquescent high-purity sulfur-halogen glass of any of claims 1-7, special
Sign be the following steps are included:
1) elemental Germanium, elemental arsenic and the elemental selenium of chunky shape are weighed by chemical formula, are uniformly mixed, are obtained mixture；Weigh deoxygenation
Agent, the amount of weighing of oxygen scavenger are 0.03~0.1wt% of mixture total amount；
2) prepare one and pass through the two-tube quartz ampoule of the pretreated H-type of dehydroxylation, the two-tube quartz ampoule of the H-type includes glass raw material pipe
With refining glass pipe, glass raw material pipe and refining glass pipe are communicated through connecting tube, the upper end of glass raw material pipe and refining glass pipe
It is open respectively；Mixture obtained in step 1) and oxygen scavenger are uniformly mixed and the glass for being put into the two-tube quartz ampoule of H-type is former
In expects pipe, with the upper end opening of oxyhydrogen flame closed glass mother tube, vacuum pump is connected in the upper end of refining glass pipe, is taken out true
Sky, while glass raw material pipe is heated, when the vacuum degree in the two-tube quartz ampoule of H-type reaches 2 × 10-3When Pa or less, with hydrogen-oxygen fire
The upper end opening of flame closing refining glass pipe；
3) glass raw material pipe is heated at high temperature 5~6 hours at a temperature of 750~800 DEG C, while refining glass pipe is made to be placed in room temperature
Under, make the raw material high-temperature gasification in glass raw material pipe and distill through connecting tube to cryogenic condensation in refining glass pipe, to glass original
After raw material in expects pipe all distills, with oxyhydrogen flame envelope disconnection adapter tube；
4) refining glass pipe is put into rocking furnace, is to slowly warm up to 600~950 DEG C, taken out after waving melted 12~18 hours
It is cooled to room temperature, is then made annealing treatment, i.e., keep the temperature 2~3 hours at glass transition temperature ± 5 DEG C and small 10~11
When it is interior be down to room temperature, obtain chalcogenide glass matrix；
5) chalcogenide glass matrix is taken out, one is put by vacuumizing in the pretreated straight type quartz glass tube of dehydroxylation, adds simultaneously
Hot straight type quartz glass tube 1~4 hour to remove the water to dissociate in straight type quartz glass tube, after being cooled to room temperature, in straight type stone
Iodine is added in English glass tube, closes the nozzle of straight type quartz glass tube after vacuumizing with oxyhydrogen flame；
6) straight type quartz glass tube is put into rocking furnace, is to slowly warm up to 600~950 DEG C, after waving melted 12~18 hours
Taking-up is cooled to room temperature, and is then made annealing treatment, i.e., 2~3 hours are kept the temperature at glass transition temperature ± 5 DEG C and 10~
It is down to room temperature in 11 hours, obtains not deliquescent high-purity sulfur-halogen glass.
9. a kind of purification preparation method of not deliquescent high-purity sulfur-halogen glass according to claim 8, it is characterised in that
The oxygen scavenger is aluminum strip or magnesium rod.
10. a kind of purification preparation method of not deliquescent high-purity sulfur-halogen glass according to claim 8, it is characterised in that
The elemental Germanium, elemental arsenic, elemental selenium and iodine purity be not less than 99.9% respectively.
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