CN107324660A - A kind of colourless glass of high refractive index and preparation method thereof - Google Patents
A kind of colourless glass of high refractive index and preparation method thereof Download PDFInfo
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- CN107324660A CN107324660A CN201710777055.7A CN201710777055A CN107324660A CN 107324660 A CN107324660 A CN 107324660A CN 201710777055 A CN201710777055 A CN 201710777055A CN 107324660 A CN107324660 A CN 107324660A
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- glass
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- 239000011521 glass Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000007711 solidification Methods 0.000 claims abstract description 10
- 230000008023 solidification Effects 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 238000000265 homogenisation Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000004093 laser heating Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 239000005308 flint glass Substances 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000005304 optical glass Substances 0.000 description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000007712 rapid solidification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 229910017592 La4Ti9O24 Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001304 sample melting Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
- C03B19/1005—Forming solid beads
- C03B19/102—Forming solid beads by blowing a gas onto a stream of molten glass or onto particulate materials, e.g. pulverising
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/60—Silica-free oxide glasses
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a kind of colourless glass of high refractive index and preparation method thereof.Its key component of the glass is (1 x y) La2O3‑xTiO2‑yNb2O5, wherein 0.75≤x≤0.85 or 0.6≤y≤0.8, and 0.5≤x+y≤0.85, preferably 0.6≤x+y≤0.8.Its preparation method comprises the following steps：(1) by the raw material sheet material sintered heat insulating by pretreatment, presoma is obtained；(2) presoma is heated to molten state, and the presoma of the molten state is suspended in homogenizing in air-flow environment, obtain homogenizing presoma；(3) presoma cooling solidification will be homogenized, that is, the glass is made.The optical material that the colourless glass of high refractive index that the present invention is provided is a kind of high comprehensive performance, can be practical, is advantageously implemented device application.The preparation method technique is simple, and following process is simple, is conducive to large-scale production.
Description
Technical field
The invention belongs to optical material field, more particularly, to a kind of colourless glass of high refractive index and preparation method thereof.
Background technology
Refractive index is the fundamental physical quantity of optical material, is the important parameter for developing high optics component.With movement
The popularization of smart machine, the equipment such as mobile phone, tablet personal computer is also increasing to the demand of camera, it is desirable to also more and more higher, needs
More frivolous, higher definition, bigger shooting wide-angle etc..The glass of glass of high refractive index, particularly refractive index more than 2.0
Glass is the effective means for solving this series of problems, and refractive index is higher, and it is thinner that eyeglass can be done, and further reduces camera lens chi
It is very little.σ=λ/NA, NA=nsin θ, σ are minimum resolution distance, and refractive index is higher, and angular aperture θ is bigger, and improving refractive index can
Numerical aperture is improved, thus improves the resolution ratio of camera lens.Refractive index is bigger, and the incidence angle of incident ray is also bigger, and camera lens can be
The bigger visual field is included in shorter distance.In addition, glass of high refractive index also can be applicable to microscope, it is on-vehicle lens, small
On type detector, in terms of digital camera and DVD read heads.The lenticule that optical glass having high refractive index makes, focal length can be with
Narrow down to below 0.5mm, can as between active device in optic communication, the active coupling element between passive device, improve
Coupling efficiency.Available for new infrared optical material is developed into, glass of high refractive index material is widely used in glass microballoon side
To as retroreflecting material, applying in the facilities such as road, bridge, harbour, mine.Glass of high refractive index has stronger
Reflecting power, available for Jewelry Accessories such as high-grade handicraft, artificial diamond rings.Colourless optical glass having high refractive index is used to make optics
The elements such as prism, optical lens, due to its refractive index and dispersion, can effectively reduce the volume of optical component, and
The visual angle of optical component can be increased.In optical design and optic communication, optical glass of the refractive index between 1.9-2.3 is to letter
Changing optical system, raising imaging mole has highly important effect, information is stored, the progress of optical communication technique also has depth
Remote meaning.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of colourless glass of high refractive index, its
Purpose is to form the glass without Network former under given conditions by ternary system material, with high index of refraction
Meanwhile, composition is uniform, high-purity few miscellaneous, compact structure, thus solves existing glass of high refractive index dispersion or other physics and chemistry
The not good technical problem of performance.
To achieve the above object, according to one aspect of the present invention there is provided a kind of glass, its key component is (1-x-
y)La2O3-xTiO2-yNb2O5, wherein 0.75≤x≤0.85 or 0.6≤y≤0.8, and 0.5≤x+y≤0.85, preferably 0.6
≤x+y≤0.8。
Preferably, the glass, its described key component accounts for molar percentage more than 50%.
Preferably, the glass, its glass also includes the high index of refraction additive that molar percentage is less than or equal to 50%, institute
High index of refraction additive is stated for BaO, ZrO2, and/or Al2O3。
Preferably, the glass, its high index of refraction additive composition formula is (1- alpha-betas) BaO- α ZrO2-βAl2O3, 0≤α≤
1 or 0≤β≤0.6,0.5≤alpha+beta≤1.
Preferably, the glass, its described glass is free of Network former.
A kind of preparation method of glass is provided according to another aspect of the present invention, it comprises the following steps：
(1) by the raw material sheet material sintered heat insulating by pretreatment, presoma is obtained；
(2) presoma obtained in step (1) is heated to molten state, and the presoma of the molten state is suspended in gas
Flow in environment and be homogenized, obtain homogenizing presoma；
(3) the homogenizing presoma cooling solidification that will be obtained in step (2), that is, be made the glass.
Preferably, the preparation method of the glass, the pretreatment described in its step (1) is specific as follows：
(1-1) will carry out ball milling drying according to formula rate raw material, obtain raw material powder；
The raw material powder obtained in step (1-1) is carried out tabletting by (1-2), obtains the raw material sheet by pretreatment.
Preferably, the preparation method of the glass, its step (2) described air-flow is oxygen, nitrogen or argon gas, flow 500
~2000sccm.
Preferably, the preparation method of the glass, its step (2) is heated using laser, homogenization temperature 1000~2500
DEG C, preferably 1300 DEG C to 1800 DEG C, 0.2~2min of homogenizing soaking time.
Preferably, the preparation method of the glass, its step (3) cooling solidification speed is 500~1000 DEG C/s.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect：
TiO2And Nb2O5It is good optical material, but its ability for forming vitreum is too poor, it is impossible to form stabilization
Glass form；The glass that the present invention is provided is by La2O3, TiO2, Nb2O5Ternary system is constituted, and three kinds of components are high index of refraction oxygen
Compound, and TiO2And Nb2O5It is good optical material, La2O3Addition be favorably improved the glass forming ability of system, and carry
High index of refraction；Its vitreum formed is simultaneously without Network former, so as to achieve the breakthrough in flint glass refractive index；Separately
The colourless glass of high refractive index that the outer present invention is provided also has a clear superiority in other physicochemical properties, and prepared by the present invention subsphaeroidal
1~10mm of glass diameter, refractive index ndFor 2.1~2.4, higher than existing glass of high refractive index, Abbe number 15~30, printing opacity model
300~7000nm is enclosed, penetrating region is without light absorbs, it is seen that light transmission rate is not less than under 70%, 300g load, micro-vickers hardness
600~850 or so, slightly below quartz glass, higher than general glass, especially greater than existing glass of high refractive index.Thus may be used
See, the colourless glass of high refractive index of the system is a kind of high comprehensive performance, optical material that can be practical, is advantageously implemented device
Change application.
The preparation of the colourless glass of high refractive index of the present invention uses gas suspension laser heating furnace melting, enables various elements
It is sufficiently mixed uniformly, with high index of refraction, preferable heat endurance, and the preparation method technique is simple, following process is simple, has
Beneficial to large-scale production.
Brief description of the drawings
Fig. 1 is the preparation method cooling schematic diagram for the colourless glass of high refractive index that the present invention is provided；
Fig. 2 is refractometry schematic diagram provided in an embodiment of the present invention；
Fig. 3 is the dispersion of refractive index figure for the colourless glass of high refractive index that the embodiment of the present invention 1 is provided；
Fig. 4 is the light transmittance figure for the colourless glass of high refractive index that the embodiment of the present invention 1 is provided；
Fig. 5 is the dispersion of refractive index figure for the colourless glass of high refractive index that the embodiment of the present invention 5 is provided.
In all of the figs, identical reference is used for representing identical element or structure, wherein：1 light source, 2 polarizations
Piece, 3 compensators, 4 encapsulating epoxy resins, 5 glass samples, 6 compensators, 7 analyzers, 8 detectors.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Not constituting conflict each other can just be mutually combined.
The glass that the present invention is provided, its key component is (1-x-y) La2O3-xTiO2-yNb2O5, wherein 0.75≤x≤
0.85 or 0.6≤y≤0.8, and 0.5≤x+y≤0.85, preferably 0.6≤x+y≤0.8.The key component accounts for molar percentage
More than 50%.Also include the high index of refraction additive that molar percentage is less than or equal to 50%, the high index of refraction additive is
BaO、ZrO2, and/or Al2O3, high index of refraction additive composition formula is (1- alpha-betas) BaO- α ZrO2-βAl2O3, 0≤α≤1 or 0≤β
≤ 0.6,0.5≤alpha+beta≤1.The glass is free of Network former, such as SiO2、B2O3、P2O5。
TiO2And Nb2O5It is good optical material, but only by TiO2And Nb2O5It is difficult to form glass material, if plus
Enter Network former, such as SiO2、B2O3、P2O5, then glass materials refractive index is greatly lowered.Therefore, the invention
Add La2O3, and the proportioning groped by many experiments between three, the glass material of ternary system is formed, network is not being introduced
On the premise of forming body, the glass forming ability of system is improved, while further improving refractive index.
Premised on maintaining high index of refraction, while improving glass preparation condition, glass forming ability is improved, has obtained various
Additive ratio, expression formula is (1- alpha-betas) BaO- α ZrO2-βAl2O3, wherein 0≤α≤1,0≤β≤0.6,0.5≤alpha+beta≤1.
BaO refractive indexes are less than 2, for regulating and controlling glass melt viscosity, are but unlikely to excessively to reduce refractive index.ZrO2With more than 2 height
Refractive index, beneficial to raising glass sample refractive index, but its fusing point is higher, and excessive add can improve melting temperature, Al2O3It is a kind of
Network intermediate, beneficial to the formation of vitreum, but its refractive index is relatively low, should not excessively add.
The present invention prepares colourless glass of high refractive index, and refractive index nd is 2.1~2.4, breaches the refractive index of existing glass
The limit；Meanwhile, Abbe number 15~30,300~7000nm of transparency range, penetrating region is without light absorbs, it is seen that light transmission rate is not low
In under 70%, 300g load, micro-vickers hardness 600~850 or so, slightly below quartz glass, higher than general glass, are particularly
Higher than existing glass of high refractive index, without harmful heavy metal, physicochemical property is excellent.As can be seen here, the colourless high refraction of the present invention
The optical material that rate glass is a kind of high comprehensive performance, can be practical, is advantageously implemented device application.
The preparation method for the colourless glass of high refractive index that the present invention is provided, heats melting using gas suspension, makes various elements
It is able to be sufficiently mixed uniformly, glass material could be formed on the premise of without glass network former raw material, with height folding
Penetrate rate, preferable heat endurance, and the preparation method technique simple, following process is simple, is conducive to large-scale production.
The preparation method for the glass that the present invention is provided, comprises the following steps：
(1) by the raw material sheet material sintered heat insulating by pretreatment, presoma is obtained；800~1200 DEG C of sintering temperature, is protected
6~12h of temperature.
Pretreatment is specific as follows：
(1-1) will carry out ball milling drying according to formula rate raw material, obtain raw material powder；The concrete operations that ball milling is dried
For：Raw material powder is added into absolute ethyl alcohol, ground 2~4 times in agate mortar, or with 6~12h of ball mill grinding；Raw material
Dried in drying box, 60~150 DEG C of temperature, 20~120min of time.
The raw material powder obtained in step (1-1) is carried out tabletting by (1-2), obtains the raw material sheet by pretreatment.
(2) presoma obtained in step (1) is heated to molten state, and the presoma of the molten state is suspended in gas
Flow in environment and be homogenized, obtain homogenizing presoma；It is preferred to use laser heating, concrete operations are as follows：
Raw material sheet is placed in gas suspension laser heating furnace nozzle, regulation laser power, air-flow size make it melt completely
Melt and be in suspended state, insulation homogenizing, 1000~2500 DEG C of homogenization temperature, preferably 1300 DEG C to 1800 DEG C, during homogenizing insulation
Between 0.2~2min, close laser
The air-flow is oxygen, nitrogen or argon gas, 500~2000sccm of flow.
(3) the homogenizing presoma cooling solidification that will be obtained in step (2), that is, be made the glass.Cooling solidification speed is
500~1000 DEG C/s, as shown in Figure 1.
It is embodiment below：
A kind of colourless glass of high refractive index, its key component is (1-x-y) La2O3-xTiO2-yNb2O5, wherein 0.75≤x
≤ 0.85 or 0.6≤y≤0.8, and 0.5≤x+y≤0.85, preferably 0.6≤x+y≤0.8.The key component accounts for moles hundred
Divide ratio more than 50%.Also include the high index of refraction additive that molar percentage is less than or equal to 50%, the high index of refraction additive
For BaO, ZrO2, and/or Al2O3, it is (1- alpha-betas) BaO- α ZrO that it, which constitutes expression formula,2-βAl2O3, wherein 0≤α≤1 or 0≤β≤
0.6,0.5≤alpha+beta≤1.
It is prepared as follows：
A) prepared by vitreum：
(1) by the raw material sheet material sintered heat insulating by pretreatment, presoma is obtained；
Sintering operation is：
The heat-agglomerating in Muffle furnace, 10 DEG C/min of programming rate is incubated cold with stove after 6~12h at 800~1200 DEG C
But.
Pretreatment is specific as follows：
(1-1) will carry out ball milling drying according to formula rate raw material, obtain raw material powder；The concrete operations that ball milling is dried
For：Powder stock number gram is stoichiometrically weighed to tens of grams, absolute ethyl alcohol is added, is in starchiness to powder, is ground in agate
Grinding mill is dry 2~4 times, preferably 3 times in alms bowl；Or with 6~12h of ball mill grinding, preferably 8h, add amount of alcohol and just soak powder
It is advisable；Raw material is dried in drying box, 60~150 DEG C of temperature, 20~120min of time.
The raw material powder obtained in step (1-1) is carried out tabletting by (1-2), obtains the raw material sheet by pretreatment.
It is compressed into tablet form with tablet press machine with 8~20MPa, preferably 10~15MPa of pressure, the excessive easy layer of the piece being pressed into of pressure
Split, the too small consistency of pressure is not enough easily crushed.
(2) presoma obtained in step (1) is heated to molten state, and the presoma of the molten state is suspended in gas
Flow in environment and be homogenized, obtain homogenizing presoma；It is preferred to use laser heating, concrete operations are as follows：
Raw material sheet is placed in gas suspension laser heating furnace nozzle, being passed through oxygen from nozzle bottom makes sample suspend, swashed
Light from top heating sample make its melt globulate, separate unit laser power 20-100W, 1000~2500 DEG C of holding temperature, preferably
1300 DEG C to 1800 DEG C, holding temperature is slightly above sample melting temperature, and temperature is too low, and melt homogenization is slow, below melt easily
Forming core solidifies；Temperature is too high, and smelt surface tension is weak, under a gas flow, and melt is easily burst, and the glass spherical degree of formation is poor.To sample
Product are heated up and cooled regulation and control, and air entrapment is discharged using the change of melt viscosity, and regulation air-flow size makes sample stable outstanding
Floating, 0.2~2min is incubated at steady state makes melt homogenization, closes laser.
The air-flow is oxygen, nitrogen or argon gas, and suitable gas flow is adjusted according to sample quality, flow 500~
2000sccm, preferably oxygen, maintain oxidizing atmosphere, prevent metal ion appraises at the current rate from producing coloring..
(3) the homogenizing presoma cooling solidification that will be obtained in step (2), cooling solidification speed refers to stable heating-up temperature T1
Subtract glass crystallization temperature Tx, difference divided by temperature section temperature fall time t,
V (t)=(T1-Tx)/t
Cooling solidification speed is 500~1000 DEG C/s, 1~10mm of rapid solidification formation diameter flint glass spheroid.
B) vitreum is polished：
C) characterization test
(4) refraction index test
As shown in Fig. 2 measuring glass refraction using elliptical polarized light tester, the instrument is incident by analyzing glass surface
The change of light and reflection polarization state, refractive index is obtained by Cauchy Formula fitting.Because the recurrence for polishing later half spherical sample is anti-
Penetrate lower camber side in principle, glass and reflect light to the reflected light of collection almost without influence, improve test accuracy.Test wavelength model
Enclose 300-1000nm, 55 ° of test angle.
(5) light transmittance is tested
Such as foregoing polishing operation, by packaging body polished backside to optical mirror plane, maintain two sides parallel, thickness after polishing
1.5mm, after the completion of sample is taken out, using Fourier infrared spectrograph test light transmittance, test scope is from ultraviolet to infrared section
Only.
(6) hardness test
Micro Vickers tests above-mentioned sheet glass hardness, and load 300g, different zones are repeatedly tested and averaged.
The mol ratio of ternary system glass formation regions is what many experiments were drawn in the present invention, is not intended to limit the present invention
In use of the method in other components material.Though it is shown that the step for characterization test in above-mentioned steps, but the step
Suddenly necessary to not being the preparation method of the colourless glass of high refractive index, and it is intended merely to divide the result of this method
Analysis.
The colourless glass of high refractive index section Example composition of the present invention and preparation parameter are as shown in Table 1：
Table one：(mol%)
Using the detailed process of embodiment 1 as：
18.2La2O3-81.8TiO2(La4Ti9O24)
Colourless glass of high refractive index preparation technology is as it was previously stated, stoichiometrically weigh raw material La2O3、TiO2Common 5g, puts
With absolute ethyl alcohol wet-milling three times in agate mortar.Powder is dried in 100 DEG C of drying boxes, is pressed into tablet press machine with 10MPa
Diameter 4mm sheets.The pre-burning in high-temperature electric resistance furnace by the piece being pressed into, 10 DEG C/min of programming rate, at 1100 DEG C be incubated 10h after with
Stove is cooled down.In the nozzle that sheet-shaped material is placed in gas suspension laser heating furnace, O is passed through from nozzle bottom2Sample is set to be in half outstanding
Floating state, power 50W laser makes it melt globulate from top heating sample, and in the process, progressively adjusting gas flow, makes
Melt complete stability suspends.Laser power is adjusted, sample is heated up and the regulation and control that cool, is discharged using the change of melt viscosity
Bubble, melt is incubated 1min under stable suspersion state is homogenized it, closes laser, and sample cools rapidly, rapid solidification shape
Into diameter about 5mm flint glass ball.Such as Fig. 3, the system glass refraction is shown with wavelength change graph of a relation, 587.6nm
Locate ndFor 2.317, Abbe number 17.1, test Vickers hardness is 758 under 300g load.Such as Fig. 4, light transmittance curve figure display transparent
Wave-length coverage 370-6500nm, maximum transmission rate is more than 70%.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (10)
1. a kind of glass, it is characterised in that its key component is (1-x-y) La2O3-xTiO2-yNb2O5, wherein 0.75≤x≤
0.85 or 0.6≤y≤0.8, and 0.5≤x+y≤0.85, preferably 0.6≤x+y≤0.8.
2. glass as claimed in claim 1, it is characterised in that the key component accounts for molar percentage more than 50%.
3. glass as claimed in claim 1, it is characterised in that the glass also includes molar percentage and is less than or equal to 50%
High index of refraction additive, the high index of refraction additive is BaO, ZrO2, and/or Al2O3。
4. glass as claimed in claim 3, it is characterised in that high index of refraction additive composition formula is (1- alpha-betas) BaO- α ZrO2-
βAl2O3, 0≤α≤1 or 0≤β≤0.6,0.5≤alpha+beta≤1.
5. glass as claimed in claim 1, it is characterised in that the glass is free of Network former.
6. a kind of preparation method of glass, it is characterised in that comprise the following steps：
(1) by the raw material sheet material sintered heat insulating by pretreatment, presoma is obtained；
(2) presoma obtained in step (1) is heated to molten state, and the presoma of the molten state is suspended in air ring
It is homogenized in border, obtains homogenizing presoma；
(3) the homogenizing presoma cooling solidification that will be obtained in step (2), that is, be made the glass.
7. the preparation method of glass as claimed in claim 6, it is characterised in that the pretreatment described in step (1) is specific as follows：
(1-1) will carry out ball milling drying according to formula rate raw material, obtain raw material powder；
The raw material powder obtained in step (1-1) is carried out tabletting by (1-2), obtains the raw material sheet by pretreatment.
8. the preparation method of glass as claimed in claim 6, it is characterised in that step (2) described air-flow be oxygen, nitrogen or
Argon gas, 500~2000sccm of flow.
9. the preparation method of glass as claimed in claim 6, it is characterised in that step (2) is heated using laser, homogenization temperature
1000~2500 DEG C, preferably 1300 DEG C to 1800 DEG C, 0.2~2min of homogenizing soaking time.
10. the preparation method of glass as claimed in claim 6, it is characterised in that step (3) cooling solidification speed is 500~
1000℃/s。
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| CN109336381A (en) * | 2018-10-16 | 2019-02-15 | 中国科学院上海硅酸盐研究所 | A kind of black biological glass and its preparation method and application |
| CN109520797A (en) * | 2018-11-08 | 2019-03-26 | 长飞光纤光缆股份有限公司 | A kind of gas suspension heating device |
| JP2020105041A (en) * | 2018-12-26 | 2020-07-09 | スリーエム イノベイティブ プロパティズ カンパニー | Transparent solid spheres and method for producing the same |
| WO2020203309A1 (en) * | 2019-04-05 | 2020-10-08 | 日本電気硝子株式会社 | Decorative glass article |
| JP2020172427A (en) * | 2019-04-05 | 2020-10-22 | 日本電気硝子株式会社 | Decorative glass article |
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| CN109336381A (en) * | 2018-10-16 | 2019-02-15 | 中国科学院上海硅酸盐研究所 | A kind of black biological glass and its preparation method and application |
| CN109336381B (en) * | 2018-10-16 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Black bioglass and preparation method and application thereof |
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| JP2020105041A (en) * | 2018-12-26 | 2020-07-09 | スリーエム イノベイティブ プロパティズ カンパニー | Transparent solid spheres and method for producing the same |
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| CN113677640A (en) * | 2019-04-05 | 2021-11-19 | 日本电气硝子株式会社 | Glass article for decoration |
| JP7530034B2 (en) | 2019-04-05 | 2024-08-07 | 日本電気硝子株式会社 | Decorative glass articles |
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