CN105461222A - High-refraction high-dispersion optical glass - Google Patents

High-refraction high-dispersion optical glass Download PDF

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Publication number
CN105461222A
CN105461222A CN201610017725.0A CN201610017725A CN105461222A CN 105461222 A CN105461222 A CN 105461222A CN 201610017725 A CN201610017725 A CN 201610017725A CN 105461222 A CN105461222 A CN 105461222A
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CN
China
Prior art keywords
glass
optical glass
refractive
refraction
tio
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Pending
Application number
CN201610017725.0A
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Chinese (zh)
Inventor
胡斌
于天来
王培新
苏学剑
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CDGM Glass Co Ltd
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CDGM Glass Co Ltd
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Publication date
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Priority to CN201610017725.0A priority Critical patent/CN105461222A/en
Publication of CN105461222A publication Critical patent/CN105461222A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235—Heating the 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2211/00—Heating processes for glass melting in glass melting furnaces
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties

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  • 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)
  • Glass Compositions (AREA)

Abstract

The invention provides high-refraction high-dispersion optical glass which can be used for achromatic lenses and micro lenses or high-grade art crafts and jewelry accessories. The high-refraction high-dispersion optical glass is prepared from, by weight, 6%-25% of SiO2, 20%-45% of TiO2, 15%-45% of BaO, 1%-6% of CaO and 2%-15% of R2O3, wherein one or more of La2O3, Y2O3 and Nd2O3 is/are adopted as R2O3. By reasonably selecting the components of the optical glass and the component content, the high-refraction high-dispersion optical glass material is obtained, the good optical uniformity and chemical stability and the higher mechanical strength and rigidity are achieved, and therefore the optimal comprehensive performance of the optical material is achieved; lead oxide, cadmium oxide, arsenic oxide, thallium oxide and the like are not contained in the components, and pollution to human bodies and the environment cannot be caused.

Description

High-refractive and high-dispersive optical glass
Technical field
The present invention relates to a kind of opticglass, particularly relate to a kind of high-refractive and high-dispersive optical glass.
Background technology
Along with the develop rapidly in the fields such as precision optical instrument, optical information communication, O-E Products, the opticglass with high refractive index height dispersion is subject to extensive concern, and its requirement is also more and more higher.In optical design and optical communication, the opticglass of specific refractory power more than 1.79 to simplification optical system, improve image quality and have very important meaning, and to the further miniaturization of optical system, have profound significance to the progress of optical communication technique.The specific refractory power of usual camera lens material is higher, and lens just can design thinner, and focal length is larger, and the distance between lens combination is less, and the optical system of optical articles just can design thinner.Because lens are different at the light focal length of different wave length, therefore ratio of enlargement is different, the different color light of pointolite can not converge to same point as in plane, cause the fuzzy of imaging, and utilize the glass combination of different refractivity, different dispersion, the aberration that different wave length causes can be eliminated, adopt the camera lens of this technology manufacture to be called achromat.
High-refractive and high-dispersive optical glass has good optical homogeneity, chemical stability, high physical strength and hardness.In the imaging system of mobile communication, digital camera, adopt the microlens that the mould pressing technology of optical glass having high refractive index makes, resolving power can be increased substantially, in large digital aperture, anaberration optical system, adopt extra-high index optical glasses to simplify optical system, improve image quality, as aspects such as photographic camera, powerful microscope, visual telescope, zooming systems, and glass of high refractive index has brighter effect on apparent, can be used for high-grade artwork and Jewelry Accessories.Therefore, high refractivity high dispersion glass can be widely used in, in the manufacture of various opticinstrument and product, in national defense construction and the development of the national economy, having vital role.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of opticglass with high-refraction high-dispersion that can be used in achromat, microlens or high-grade artwork and Jewelry Accessories.
The technical scheme that technical solution problem of the present invention adopts is: high-refractive and high-dispersive optical glass, and its weight percent composition comprises: SiO 26 ~ 25wt%; TiO 220 ~ 45wt%; BaO15 ~ 45wt%; CaO1 ~ 6wt%; R 2o 32 ~ 15wt%, wherein, R 2o 3for La 2o 3, Y 2o 3, Nd 2o 3in one or more.
Further, also comprise: ZrO 20 ~ 8wt%; Al 2o 30 ~ 8wt%; B 2o 30 ~ 8wt%, ZnO0 ~ 4wt%; R 2o0 ~ 3wt%, wherein, R 2o is Na 2o, K 2one or both in O.
Further, wherein, ZrO 22 ~ 5wt% and/or Al 2o 31 ~ 4wt% and/or B 2o 32 ~ 5wt% and/or ZnO0 ~ 3wt% and/or R 2o0 ~ 2wt%.
Further, wherein, (R 2o+RO)/B 2o 3it is one or more in BaO, CaO, ZnO that mol ratio is greater than 1, RO.
Further, wherein, SiO 28 ~ 20wt% and/or TiO 230 ~ 40wt% and/or BaO20 ~ 40wt% and/or CaO2 ~ 3wt% and/or R 2o 32 ~ 10wt%.
Further, wherein, TiO 2the mol ratio of/BaO is less than 1.96.
Further, wherein, not containing PbO, CdO, As 2o 3and Ta 2o 5.
Further, the specific refractory power of described glass is 1.79 ~ 1.99.
Further, the middle part dispersion of described glass is 0.025 ~ 0.055.
The invention has the beneficial effects as follows: the present invention is by carrying out choose reasonable to the component of opticglass and content thereof, obtain a kind of optical glass material of high-refraction high-dispersion, and obtain good optical homogeneity, chemical stability and higher physical strength and hardness, make optical material over-all properties reach best; Not containing oxide compounds such as lead, cadmium, arsenic, thalliums in instant component, can not to human body and environment.Opticglass of the present invention is applicable to achromat, microlens or high-grade artwork and Jewelry Accessories, and owing to having higher dispersion, on apparent, has brighter abundant color effect.
Embodiment
The present invention by obtaining the glass material of high refractive index height dispersion to the appropriate design of composition, and obtains higher hardness, chemical stability, physical strength and hardness; The opticglass had good uniformity is obtained by rational melting and moulding process; By the control to melting atmosphere, in suppression glass, titanium ion is painted, thus forms water white opticglass, makes material over-all properties reach best.
To describe in detail moiety of the present invention and effect thereof below, and it should be noted that if no special instructions, following component is all represent with weight percent.
SiO 2being glass-former oxide compound, forming irregular contiguous network with the structural unit of silicon-oxy tetrahedron, is the skeleton forming opticglass.Work as SiO 2when content is less than 6wt%, the easy crystallization of glass, can not form transparent glass; But work as SiO 2content higher than 25wt% time, the specific refractory power of glass can be reduced, therefore, SiO 2content range be 6 ~ 25wt%, be preferably 8 ~ 20wt%.
In the glass structure of high titanium content, Ti 4+mainly with [TiO 4] form formation glass network structure, the specific refractory power of glass can be made to be greatly improved, to make Ti when there is no more oxonium ion 4+form [TiO 4] participate in glass network time, then have part [TiO 6] be present in outside glass network, glass structure can be made to loosen, cause density to diminish, the coefficient of expansion becomes large, specific refractory power reduces.Meanwhile, TiO 2the painted of glass is caused to be vulnerable to the acid-basicity of glass, the impact of factor such as fusing atmosphere and glass melting temperature etc.In oxidizing atmosphere or in admixtion, add suitable oxygenant, coloring ion can be made to transform to high price direction, therefore, TiO of the present invention 2content range be 20 ~ 45wt%, be preferably 30 ~ 40wt%; Meanwhile, if when there is BaO, ZrO in glass system 2time, can TiO be promoted 2change [TiO into 4] tetrahedron.Therefore the present invention adopts TiO 2, BaO, ZrO 2as improve glass refraction oxide compound introduce, Ba in alkaline-earth metal, ordination number and ionic radius maximum, easily polarized, the specific refractory power of glass can be raised within the specific limits significantly, but work as TiO 2when/BaO mol ratio is greater than 1.96, tendency towards devitrification obviously increases, therefore, and TiO 2the content range that/BaO mol ratio is less than 1.96, BaO is 15 ~ 45wt%, is preferably 20 ~ 40wt%.
ZrO 2only has cubes [ZrO 6] a kind of coordination, it can improve the specific refractory power of glass, but due to its solubleness in glass network structure very little, exceed and a certain amount ofly easily cause glass generation crystallization afterwards.Research through contriver finds, works as ZrO 2content range lower than 8wt% time, the glass obtained is better, and preferred content is 2 ~ 5wt%.
With TiO 2-SiO 2based on-BaO system, composition introduces CaO, R 2o, ZrO 2, high refractive index, low dispersion, low-density opticglass can be obtained.In the present invention, it is proper that CaO introduces 1 ~ 6wt%, is preferably 2 ~ 3wt%.
For in alkali-free silicate glass, if not containing R 2o or R 2during O < 2wt%, glass has very high chemical stability and intensity, wherein, and R 2o is Na 2o, K 2one or both in O, R 2the total content of O is no more than 3wt%, is preferably 0-2wt%.
Al 2o 3introducing greatly can reduce the crystallization property of glass, and intensity and the hardness of glass can be improved, and Al 2o 3existence the shaping scope of glass in three-dimensional phase diagram is increased, the chemical stability of reinforcing glass, can improve the transparency etc. of glass simultaneously.Al of the present invention 2o 3content be defined as 0 ~ 8wt%, be preferably 1 ~ 4wt%.
B 2o 3the chemical stability of glass can be improved, B with the introducing of ZnO 3+first co-ordination state in glass depends on R in glass 2the molar fraction of O or RO, wherein, RO refer in BaO, CaO, ZnO one or more, both play a part to provide free oxygen jointly, only have as mol ratio (R 2o+RO)/B 2when O is greater than 1, R 2o or RO just can provide enough free oxygens to make B 3+form [BO 4], and work as (R 2o+RO)/B 2o 3during <1, free oxygen is not enough, will make [BO 4] split into [BO 3], reduce the specific refractory power of glass.Zn 2+form [ZnO 6] ligand ratio formation [ZnO 4] time glass structure compacter, but [ZnO 4] content can increase with the increase of alkali metal content, the therefore too high tendency towards devitrification that can increase glass of ZnO content, thus affect the transmitance of glass and reduce the specific refractory power of glass.In the present invention, B 2o 3content be 0 ~ 8wt%, be preferably 2 ~ 5wt%; The content of ZnO is defined as 0 ~ 4wt%, is preferably 0 ~ 3wt%.
Rare earth oxide R 2o 3all have higher specific refractory power to add and coefficient (contribution of different material refractive index is different, and add the raw material higher with coefficient and introduce more, the specific refractory power of glass is higher), be Al simultaneously 2o 3, TiO 2free oxygen is provided, wherein, R 2o 3for Y 2o 3, La 2o 3, Nd 2o 3in one or more.R in the present invention 2o 3total content be defined as 2 ~ 15wt%, be preferably 2 ~ 10wt%.
The preparation method of opticglass of the present invention, comprise the following steps: selected glass formula, weigh according to the weight percent of the corresponding raw material of the composition in table 1, fully add in platinum crucible after mixing, melt at 1400 ~ 1450 DEG C and lower the temperature after noting control climate, clarification, homogenizing; The glass metal of melting is poured in the metal die being preheating to about 200 DEG C shaping, and passes into circulating cooling air, guarantee glass not crystallization; The melten glass of the metal pattern after injection preheating is put into the annealing of annealing furnace inside holding together with metal die, and then power-off furnace cooling, obtains the glass of not crystallization, not devitrification.
Embodiment and the test index of glass of the present invention are as follows:
Specific refractory power refers to light velocity of propagation in a vacuum and the ratio of light velocity of propagation in the medium, and dispersion represents the difference of the spectral line specific refractory power of different wave length.Wherein nF-nC is called middle part dispersion, and nd, nF, nC refer to d light (587.56nm), F light (486.13nm), C light (656.28nm) specific refractory power in media as well respectively.
Table 1
As can be seen from above-described embodiment 1-10, the refractive index n d of opticglass of the present invention is 1.79 ~ 1.99, and middle part dispersion is 0.025 ~ 0.055, meets artwork, Jewelry Accessories and achromatic lens service requirements completely.

Claims (9)

1. high-refractive and high-dispersive optical glass, is characterized in that, its weight percent composition comprises: SiO 26 ~ 25wt%; TiO 220 ~ 45wt%; BaO15 ~ 45wt%; CaO1 ~ 6wt%; R 2o 32 ~ 15wt%, wherein, R 2o 3for La 2o 3, Y 2o 3, Nd 2o 3in one or more.
2. high-refractive and high-dispersive optical glass as claimed in claim 1, is characterized in that, also comprise: ZrO 20 ~ 8wt%; Al 2o 30 ~ 8wt%; B 2o 30 ~ 8wt%, ZnO0 ~ 4wt%; R 2o0 ~ 3wt%, wherein, R 2o is Na 2o, K 2one or both in O.
3. high-refractive and high-dispersive optical glass as claimed in claim 2, is characterized in that, wherein, and ZrO 22 ~ 5wt% and/or Al 2o 31 ~ 4wt% and/or B 2o 32 ~ 5wt% and/or ZnO0 ~ 3wt% and/or R 2o0 ~ 2wt%.
4. high-refractive and high-dispersive optical glass as claimed in claim 2, is characterized in that, wherein, and (R 2o+RO)/B 2o 3it is one or more in BaO, CaO, ZnO that mol ratio is greater than 1, RO.
5. high-refractive and high-dispersive optical glass as claimed in claim 1 or 2, is characterized in that, wherein, and SiO 28 ~ 20wt% and/or TiO 230 ~ 40wt% and/or BaO20 ~ 40wt% and/or CaO2 ~ 3wt% and/or R 2o 32 ~ 10wt%.
6. high-refractive and high-dispersive optical glass as claimed in claim 1 or 2, is characterized in that, wherein, and TiO 2the mol ratio of/BaO is less than 1.96.
7. high-refractive and high-dispersive optical glass as claimed in claim 1 or 2, is characterized in that, wherein, not containing PbO, CdO, As 2o 3and Ta 2o 5.
8. high-refractive and high-dispersive optical glass as claimed in claim 1 or 2, it is characterized in that, the specific refractory power of described glass is 1.79 ~ 1.99.
9. high-refractive and high-dispersive optical glass as claimed in claim 1 or 2, it is characterized in that, the middle part dispersion of described glass is 0.025 ~ 0.055.
CN201610017725.0A 2016-01-12 2016-01-12 High-refraction high-dispersion optical glass Pending CN105461222A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106365443A (en) * 2016-08-26 2017-02-01 湖北戈碧迦光电科技股份有限公司 Zircon-imitated glass as well as preparation method and application thereof
CN109734303A (en) * 2019-03-26 2019-05-10 成都奇彩珠宝有限公司 Height reflects colorless and transparent artificial synthesized jewel
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
CN112125511A (en) * 2020-09-28 2020-12-25 成都光明光电股份有限公司 Optical glass
WO2021230229A1 (en) * 2020-05-15 2021-11-18 日本電気硝子株式会社 Glass material

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WO2013180082A1 (en) * 2012-05-28 2013-12-05 株式会社オハラ Optical glass
CN104445925A (en) * 2014-12-01 2015-03-25 河北省沙河玻璃技术研究院 Ultra-high-refractivity environment-friendly cameo glass and preparation method thereof
CN104703935A (en) * 2012-10-12 2015-06-10 Hoya株式会社 Optical glass, glass material for press-molding, optical element and method for manufacturing same, and bonding optical element
CN104944767A (en) * 2014-03-26 2015-09-30 成都光明光电股份有限公司 High-refractivity high-dispersion optical glass

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013180082A1 (en) * 2012-05-28 2013-12-05 株式会社オハラ Optical glass
CN104703935A (en) * 2012-10-12 2015-06-10 Hoya株式会社 Optical glass, glass material for press-molding, optical element and method for manufacturing same, and bonding optical element
CN104944767A (en) * 2014-03-26 2015-09-30 成都光明光电股份有限公司 High-refractivity high-dispersion optical glass
CN104445925A (en) * 2014-12-01 2015-03-25 河北省沙河玻璃技术研究院 Ultra-high-refractivity environment-friendly cameo glass and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106365443A (en) * 2016-08-26 2017-02-01 湖北戈碧迦光电科技股份有限公司 Zircon-imitated glass as well as preparation method and application thereof
CN106365443B (en) * 2016-08-26 2019-02-01 湖北戈碧迦光电科技股份有限公司 Imitative zircon glass and its preparation method and application
CN109734303A (en) * 2019-03-26 2019-05-10 成都奇彩珠宝有限公司 Height reflects colorless and transparent artificial synthesized jewel
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
CN113677640A (en) * 2019-04-05 2021-11-19 日本电气硝子株式会社 Glass article for decoration
WO2021230229A1 (en) * 2020-05-15 2021-11-18 日本電気硝子株式会社 Glass material
CN112125511A (en) * 2020-09-28 2020-12-25 成都光明光电股份有限公司 Optical glass

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