CN102964062A - Environment-friendly heavy lanthanum flint optical glass - Google Patents

Environment-friendly heavy lanthanum flint optical glass Download PDF

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Publication number
CN102964062A
CN102964062A CN2012103724877A CN201210372487A CN102964062A CN 102964062 A CN102964062 A CN 102964062A CN 2012103724877 A CN2012103724877 A CN 2012103724877A CN 201210372487 A CN201210372487 A CN 201210372487A CN 102964062 A CN102964062 A CN 102964062A
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optical glass
glass
flint optical
environment friendly
friendly heavy
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孙伟
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CDGM Glass Co Ltd
Chengdu Guangming Optoelectronics Co Ltd
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Chengdu Guangming Optoelectronics Co Ltd
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Priority to CN2012103724877A priority Critical patent/CN102964062A/en
Publication of CN102964062A publication Critical patent/CN102964062A/en
Priority to JP2015533440A priority patent/JP5972469B2/en
Priority to CN201710970267.7A priority patent/CN107601850A/en
Priority to PCT/CN2013/084422 priority patent/WO2014048362A1/en
Priority to CN201380048545.3A priority patent/CN104736490A/en
Priority to HK15106706.5A priority patent/HK1205998A1/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
    • 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
    • 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
    • C03C3/12—Silica-free oxide glass compositions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides an environment-friendly heavy lanthanum flint optical glass with a relatively low TiO2 content. The flint optical glass comprises, by weight: 30-50% of La2O3, 3-15% of TiO2, and 5-12% of Nb2O5. The flint optical glass has a density of 4.56g/cm<3>, a refractive index of 1.85-1.95, an Abbe number of 25-35, and a transition temperature below 670DEG C. In the invention, by introducing SrO and BaO at the same time, the refractive index of the glass can be enhanced, the softening point can be reduced, and the chemical resistance can be improved. The flint optical glass provided in the invention is free of lead, arsenic, cadmium and other components causing environmental pollution.

Description

Environment friendly heavy-lanthanide flint optical glass
Technical field
The present invention relates to a kind of environmental protection optical glass, particularly relating to a kind of specific refractory power is 1.85-1.95, and Abbe number is the environment friendly heavy-lanthanide flint optical glass of 25-35.
Background technology
In recent years, along with the development of photoelectricity industry, optical element has been proposed the requirement of miniaturization, lightweight, high performance, this is just to have the demand of high refraction, medium dispersion, low-density flint optical glass with heavy lanthanum increasing.For making opticglass have above-mentioned performance, the La in the glass ingredient 2O 3, Nb 2O 5, TiO 2Also should corresponding increase, but these components can cause that glass metal viscosity is little in the production process, crystallization serious, the optical constant fluctuation is large, to consequences such as equipment corrosion are large, make glass cord of low quality, production difficulty is large.Generally all contain the elements such as lead, arsenic, cadmium in traditional lanthanide optical glass component, because plumbous oxide can improve specific refractory power and the dispersion of opticglass, arsenic oxide arsenoxide has clarification, and Cadmium oxide can improve the chemical stability of glass.Yet along with the enhancing of people's environmental consciousness, the opticglass that contains harmful element of this quasi-tradition is replaced by environmental protection optical glass just gradually.CN1931755A disclose a kind of specific refractory power greater than 1.80, Abbe number is less than 30 opticglass, its TiO 2Content be 22-37% (weight percent content, as follows), at like this high TiO 2Under the content, the easy devitrification of glass, absorbing properties is poor, the glass easy coloring, the softening temperature of glass is high, hardness is high, has increased the difficulty of secondary press and mechanical workout.
Summary of the invention
Technical problem to be solved by this invention provides a kind of TiO 2The relatively low environment friendly heavy-lanthanide flint optical glass of content, the specific refractory power of this opticglass is 1.85～1.95, Abbe number is 25～35, transition temperature is below 670 ℃.
The technical scheme that technical solution problem of the present invention adopts is: environment friendly heavy-lanthanide flint optical glass, its weight percent forms and contains: La 2O 3: 30～50%, TiO 2: 3～15%, Nb 2O 5: 5～12%, density is 4.56g/cm 3Below, specific refractory power is 1.85～1.95, and Abbe number is 25～35, and transition temperature is below 670 ℃.
Further, its weight percent consists of: SiO 2: 2～15%, B 2O 3: 10～25%, La 2O 3: 30～50%, ZrO 2: 2～15%, TiO 2: 3～15%, Nb 2O 5: 5～12%, SrO: greater than 5% but less than 20%, BaO:4～15%.
Further, wherein: SiO 2: 2～10%, ZrO 2: 4～10%.
Further, wherein: B 2O 3: 12～20%, SrO: greater than 5.5% but less than 15%.
Further, wherein: SrO: greater than 5.5% but less than 15%, BaO:6～12%.
Further, wherein: La 2O 3: 32～40%, TiO 2: 5～12%, Nb 2O 5: 8～12%.
Environment friendly heavy-lanthanide flint optical glass, its weight percent consists of: SiO 2: 2～15%, B 2O 3: 10～25%, La 2O 3: 30～50%, ZrO 2: 2～15%, TiO 2: 3～15%, Nb 2O 5: 5～12%, SrO: greater than 5% but less than 20%, BaO:4～15%.
Further, wherein: SiO 2: 2～10%.
Further, wherein: ZrO 2: 4～10%.
Further, wherein: B 2O 3: 12～20%, SrO: greater than 5.5% but less than 15%.
Further, wherein: SrO: greater than 5.5% but less than 15%, BaO:6～12%.
Further, wherein: TiO 2: 5～12%.
Further, wherein: La 2O 3: 32～40%, TiO 2: 5～12%, Nb 2O 5: 8～12%.
The gas preform that adopts above-mentioned environment friendly heavy-lanthanide flint optical glass to make.
The optical element that adopts above-mentioned environment friendly heavy-lanthanide flint optical glass to make.
The opticinstrument that adopts above-mentioned environment friendly heavy-lanthanide flint optical glass to make.
The invention has the beneficial effects as follows: the present invention can improve the specific refractory power of glass by introducing simultaneously SrO and BaO component, reduces softening temperature, improves chemical resistant properties; Work as B 2O 3When content was high, the volatilization in the melting process can cause constant of glass and striped fluctuation, reduces the quality stability of glass, thereby causes complex manufacturing, and the present invention effectively eliminates by B by introducing a certain amount of SrO 2O 3The variety of issue that brings is particularly as adding 12% or more B 2O 3The time, still can make the opticglass with enough stability; The present invention is not leaded, arsenic, cadmium etc. is to the component of environment, and still can be made into specific refractory power is 1.85～1.95, and Abbe number is 25～35, and transition temperature is the opticglass below 670 ℃.
Embodiment
The below will describe each component of opticglass of the present invention, and except as otherwise noted, the content of each component all represents with % by weight.
SiO 2Be that the network that forms glass generates oxide body, add a certain amount of SiO 2Can increase the high temperature viscosity of glass, improve the devitrification resistance property of glass.When its content was lower than 2%, effect was insufficient; When its content is higher than 15%, the meltbility variation of glass, bubble is difficult to eliminate.Therefore, SiO 2Content be defined as 2～15%, more preferably content is 2～10%.
B 2O 3Also be the oxide compound that forms glass, to the such La of the present invention 2O 3The glass that content is more, B 2O 3Indispensable.When if it contains quantity not sufficient 10%, the melting properties of glass is poor, and the tendency towards devitrification of glass is large; And when its content surpassed 25%, the specific refractory power of glass was crossed the chemical stability variation of low and glass, was the opticglass that obtains having desired optical constant scope and have excellent chemical stability, B 2O 3Content be defined as 10～25%, more preferably content is 12～20%.
La 2O 3Be the main component of high dioptrics glass, can increase the specific refractory power of glass and the dispersion of not obvious raising glass, in formula system of the present invention, B 2O 3With La 2O 3Combination exist, can effectively improve the devitrification resistance property of glass, improve the chemical stability of glass.Work as La 2O 3Content when being lower than 30%, can not obtain above effect, but when its content surpassed 50%, the crystallization property of glass worsened, so its content is defined as 30～50%, preferred content is 32～40%.
ZrO 2Have the effect of improving the glass devitrification resistance, improving chemical stability, in lanthanide glass, also play the effect that improves specific refractory power and reduce dispersion.When its content is lower than 2%, do not have above-mentioned effect; When its content is higher than 15%, can cause that glass transition temperature rises, the glass devitrification resistance worsens simultaneously.So ZrO 2Content be defined as 2～15%, more preferably 4～10%.
TiO 2Specific refractory power and dispersion for raising glass are very effective, and can improve the water tolerance of glass, reduce specific gravity of glass.In the present invention, TiO 2Also play the effect that increases the glass high temperature viscosity and improve the devitrification of glass performance, but its too high levels can make glass coloring, therefore, TiO 2Content be defined as 3～15%, be preferably 5～12%.
Nb 2O 5Be the effective constituent that improves glass refraction, when it contained quantity not sufficient 5%, the specific refractory power of glass did not reach design objective, and when its content is higher than 12%, can cause glass transition temperature to raise, and the transmitance of glass is declined to a great extent, so Nb 2O 5Content be defined as 5～12%, more preferably 8～12%.
SrO works as B to promoting glass froth breaking, inhibition devitrification of glass to have outstanding role 2O 3Content when high, can effectively eliminate by B 2O 3The variety of issue that brings is particularly as adding 12% or more B 2O 3The time, can by introducing a certain amount of SrO, still can make the opticglass with enough stability.But when SrO content is higher than 20%, glass smelting difficulty, so the content of SrO is preferably more than 5% but less than 20%, more preferably greater than 5.5% but less than 15%.
BaO is the effective constituent of adjusting glass refraction and Abbe number, raising chemical durability of glass and thermostability, and SrO and BaO introduce simultaneously can improve glass refraction, reduce glass softening point, improve chemical resistant properties.But the Abbe number of glass increases when its content surpasses 15%, and the tendency towards devitrification of glass increases, so the content of BaO is preferably 4～15%, more preferably 6～12%.
The below will describe the performance of environment friendly heavy-lanthanide flint optical glass of the present invention.
Wherein specific refractory power (nd) value for (2 ℃/h)～(6 ℃/h) annealing value, specific refractory power and Abbe number are tested according to " GB/T 7962.1-1987 colouless optical glass testing method specific refractory power and abbe number ".
Transition temperature (Tg) is tested according to " GB/T7962.16-1987 colouless optical glass testing method linear expansivity, transition temperature and sag temperature ", that is: sample is in certain temperature range, 1 ℃ of the every rising of temperature, on the expansion curve of sample, low-temperature region and the extension of high-temperature area straight line portion are intersected the corresponding temperature of its intersection point.
Density is tested according to " GB/T 7962.20-1987 colouless optical glass testing method density measurement method ".
Through test, opticglass provided by the invention has following performance: density (ρ) is 4.56g/cm 3Below; Specific refractory power (nd) is 1.85～1.95; Abbe number (vd) is 25～35; Transition temperature (Tg) is below 670 ℃.
The present invention also provides a kind of optical element, is formed according to method well known to those skilled in the art by the described opticglass of technique scheme.Because described opticglass has high refractive index, described optical element also has high refractive index, can be applied to the equipment such as digital camera, digital camera, camera cell phone.
In order further to understand technical scheme of the present invention, the embodiment of opticglass of the present invention will be described now.Should be noted that these embodiment are scope of the present invention without limits.
The opticglass (embodiment 1～30) that shows in table 1～table 3 is by weighing according to the ratio of each embodiment shown in table 1～table 3 and hybrid optical glass common raw material (such as oxide compound, oxyhydroxide, carbonate, nitrate and fluorochemical), mixing raw material is placed in the platinum crucible, melting in 1100 to 1300 ℃ temperature, and after fusing, clarification, stirring and homogenizing, obtain not having bubble and do not contain the not homogeneous melten glass of dissolved substance, this melten glass casting mold in mould is also annealed to be formed.
The composition of embodiments of the invention 1～30 represents in table 1～table 3 with the result of specific refractory power (nd), Abbe number (vd), density (ρ), glass transformation temperature (Tg).In these tables, the composition of each component represents with % by weight.
Table 1
Figure BDA00002215202100051
Table 2
Figure BDA00002215202100052
Table 3
Figure BDA00002215202100061
Can find out that by the embodiment among the table 1-3 density of glass of the present invention (ρ) is 4.56g/cm 3Below; Specific refractory power (nd) is 1.85～1.95; Abbe number (vd) is 25～35; Transition temperature (Tg) is below 670 ℃, and not leaded, arsenic, cadmium etc. are to the component of environment.

Claims (16)

1. environment friendly heavy-lanthanide flint optical glass is characterized in that, its weight percent forms and contains: La 2O 3: 30～50%, TiO 2: 3～15%, Nb 2O 5: 5～12%, density is 4.56g/cm 3Below, specific refractory power is 1.85～1.95, and Abbe number is 25～35, and transition temperature is below 670 ℃.
2. environment friendly heavy-lanthanide flint optical glass as claimed in claim 1 is characterized in that, its weight percent consists of: SiO 2: 2～15%, B 2O 3: 10～25%, La 2O 3: 30～50%, ZrO 2: 2～15%, TiO 2: 3～15%, Nb 2O 5: 5～12%, SrO: greater than 5% but less than 20%, BaO:4～15%.
3. environment friendly heavy-lanthanide flint optical glass as claimed in claim 2 is characterized in that, wherein: SiO 2: 2～10%, ZrO 2: 4～10%.
4. environment friendly heavy-lanthanide flint optical glass as claimed in claim 2 is characterized in that, wherein: B 2O 3: 12～20%, SrO: greater than 5.5% but less than 15%.
5. environment friendly heavy-lanthanide flint optical glass as claimed in claim 2 is characterized in that, wherein: SrO: greater than 5.5% but less than 15%, BaO:6～12%.
6. environment friendly heavy-lanthanide flint optical glass as claimed in claim 1 or 2 is characterized in that, wherein: La 2O 3: 32～40%, TiO 2: 5～12%, Nb 2O 5: 8～12%.
7. environment friendly heavy-lanthanide flint optical glass is characterized in that, its weight percent consists of: SiO 2: 2～15%, B 2O 3: 10～25%, La 2O 3: 30～50%, ZrO 2: 2～15%, TiO 2: 3～15%, Nb 2O 5: 5～12%, SrO: greater than 5% but less than 20%, BaO:4～15%.
8. environment friendly heavy-lanthanide flint optical glass as claimed in claim 7 is characterized in that, wherein: SiO 2: 2～10%.
9. environment friendly heavy-lanthanide flint optical glass as claimed in claim 7 is characterized in that, wherein: ZrO 2: 4～10%.
10. environment friendly heavy-lanthanide flint optical glass as claimed in claim 7 is characterized in that, wherein: B 2O 3: 12～20%, SrO: greater than 5.5% but less than 15%.
11. environment friendly heavy-lanthanide flint optical glass as claimed in claim 7 is characterized in that, wherein: SrO: greater than 5.5% but less than 15%, BaO:6～12%.
12. environment friendly heavy-lanthanide flint optical glass as claimed in claim 7 is characterized in that, wherein: TiO 2: 5～12%.
13. environment friendly heavy-lanthanide flint optical glass as claimed in claim 7 is characterized in that, wherein: La 2O 3: 32～40%, TiO 2: 5～12%, Nb 2O 5: 8～12%.
14. adopt the gas preform of making such as the described environment friendly heavy-lanthanide flint optical glass of arbitrary claim in the claim 1～13.
15. adopt the optical element of making such as the described environment friendly heavy-lanthanide flint optical glass of the arbitrary claim of claim 1～13.
16. adopt the opticinstrument of making such as the described environment friendly heavy-lanthanide flint optical glass of the arbitrary claim of claim 1～13.
CN2012103724877A 2012-09-29 2012-09-29 Environment-friendly heavy lanthanum flint optical glass Pending CN102964062A (en)

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CN2012103724877A CN102964062A (en) 2012-09-29 2012-09-29 Environment-friendly heavy lanthanum flint optical glass
JP2015533440A JP5972469B2 (en) 2012-09-29 2013-09-27 Environmental measures heavy lanthanum flint glass
CN201710970267.7A CN107601850A (en) 2012-09-29 2013-09-27 Environment friendly heavy-lanthanide flint optical glass
PCT/CN2013/084422 WO2014048362A1 (en) 2012-09-29 2013-09-27 Environmentally-friendly heavy lanthanum flint optical glass
CN201380048545.3A CN104736490A (en) 2012-09-29 2013-09-27 Environmentally-friendly heavy lanthanum flint optical glass
HK15106706.5A HK1205998A1 (en) 2012-09-29 2015-07-14 Environmentally-friendly heavy lanthanum flint optical glass

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CN201710970267.7A Pending CN107601850A (en) 2012-09-29 2013-09-27 Environment friendly heavy-lanthanide flint optical glass

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WO2014048362A1 (en) * 2012-09-29 2014-04-03 成都光明光电股份有限公司 Environmentally-friendly heavy lanthanum flint optical glass
CN104341100A (en) * 2013-08-05 2015-02-11 成都光明光电股份有限公司 High-reflection high-dispersion optical glass, optical element and optical instrument
CN107324660A (en) * 2017-09-01 2017-11-07 长飞光纤光缆股份有限公司 A kind of colourless glass of high refractive index and preparation method thereof

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US11319243B2 (en) * 2018-01-17 2022-05-03 Corning Incorporated High refractive index optical borate glass
US11999651B2 (en) 2020-09-10 2024-06-04 Corning Incorporated Silicoborate and borosilicate glasses having high refractive index and low density
US11802073B2 (en) * 2020-09-10 2023-10-31 Corning Incorporated Silicoborate and borosilicate glasses with high refractive index and low density
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WO2014048362A1 (en) * 2012-09-29 2014-04-03 成都光明光电股份有限公司 Environmentally-friendly heavy lanthanum flint optical glass
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CN107324660A (en) * 2017-09-01 2017-11-07 长飞光纤光缆股份有限公司 A kind of colourless glass of high refractive index and preparation method thereof
CN107324660B (en) * 2017-09-01 2020-04-24 长飞光纤光缆股份有限公司 Colorless high-refractive-index glass and preparation method thereof

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JP2015532252A (en) 2015-11-09
CN107601850A (en) 2018-01-19

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Application publication date: 20130313