CN107601850A - Environment friendly heavy-lanthanide flint optical glass - Google Patents

Environment friendly heavy-lanthanide flint optical glass Download PDF

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Publication number
CN107601850A
CN107601850A CN201710970267.7A CN201710970267A CN107601850A CN 107601850 A CN107601850 A CN 107601850A CN 201710970267 A CN201710970267 A CN 201710970267A CN 107601850 A CN107601850 A CN 107601850A
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China
Prior art keywords
glass
optical glass
environment friendly
sro
friendly heavy
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CN201710970267.7A
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Chinese (zh)
Inventor
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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Publication of CN107601850A publication Critical patent/CN107601850A/en
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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 present invention provides a kind of TiO2The relatively low environment friendly heavy-lanthanide flint optical glass of content, its percentage by weight composition contains：La2O3：30~50%, TiO2：3~15%, Nb2O5：5~12%, density 4.56g/cm3Hereinafter, refractive index is 1.85~1.95, and Abbe number is 25~35, and transition temperature is less than 670 DEG C.The present invention can improve the refractive index of glass, reduce softening point, improve chemical resistance by introducing SrO and BaO components simultaneously, the component that the present invention is not leaded, arsenic, cadmium etc. pollute to environment.

Description

Environment friendly heavy-lanthanide flint optical glass
The application is to be directed to Application No. 201380048545.3 (PCT/CN2013/084422), and the applying date is 2013 9 The moon 27, the divisional application of the application for a patent for invention of entitled " environment friendly heavy-lanthanide flint optical glass ".
Technical field
The present invention relates to a kind of environmental protection optical glass, is 1.85-1.95 more particularly to a kind of refractive index, and Abbe number is 25-35 environment friendly heavy-lanthanide flint optical glass.
Background technology
In recent years, with the development of photovoltaic industry, miniaturization is proposed to optical element, lightweight, high performance are wanted Ask, this allow for high refraction, medium dispersion, low-density flint optical glass with heavy lanthanum demand it is increasing.To make Optical glass has an above-mentioned performance, the La in glass ingredient2O3、Nb2O5、TiO2Also should accordingly increase, but these components can cause The consequences such as viscosity of glass metal is small in production process, crystallization is serious, optical constant fluctuation is big, big to equipment corrosion, make glass cord Of low quality, production difficulty is big.It is general all containing elements such as lead, arsenic, cadmiums in traditional lanthanide optical glass component, because oxidation Lead can improve refractive index and the dispersion of optical glass, and arsenic oxide arsenoxide has clarification, and cadmium oxide can improve the chemistry of glass Stability.However as the enhancing of people's environmental consciousness, the optical glass containing harmful element of this quasi-tradition is just gradually by ring Optical glass is protected to be substituted.CN1931755A discloses the optical glass that a kind of refractive index is less than 30 more than 1.80, Abbe number, its TiO2Content be 22-37% (weight percent content, as follows), in so high TiO2Under content, the easy devitrification of glass, light Absorbent properties are poor, glass easy coloring, and the softening temperature height of glass, hardness are high, add the difficulty of secondary press and machining.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of TiO2The relatively low environment friendly heavy-lanthanide flint light of content Glass is learned, the refractive index of the optical glass is 1.85~1.95, and Abbe number is 25~35, and transition temperature is less than 670 DEG C.
The technical proposal for solving the technical problem of the invention is：Environment friendly heavy-lanthanide flint optical glass, its weight percent Contain than composition：La2O3：30~50%, TiO2：3~15%, Nb2O5：5~12%, density 4.56g/cm3Hereinafter, refractive index For 1.85~1.95, Abbe number is 25~35, and transition temperature is less than 670 DEG C.
Further, its percentage by weight composition is：SiO2：2~15%, B2O3：10~25%, La2O3：30~50%, ZrO2：2~15%, TiO2：3~15%, Nb2O5：5~12%, SrO：More than 5% but less than 20%, BaO：4~15%.
Further, wherein：SiO2：2~10%, ZrO2：4~10%.
Further, wherein：B2O3：12~20%, SrO：More than 5.5% but less than 15%.
Further, wherein：SrO：More than 5.5% but less than 15%, BaO：6~12%.
Further, wherein：La2O3：32~40%, TiO2：5~12%, Nb2O5：8~12%.
Further, wherein：SiO2、B2O3、La2O3、ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 85%.
Further, wherein：SiO2、B2O3、La2O3、ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 88%.
Further, wherein：SiO2、B2O3、La2O3、ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 90%.
Environment friendly heavy-lanthanide flint optical glass, its percentage by weight composition are：SiO2：2~15%, B2O3：10~25%, La2O3：30~50%, ZrO2：2~15%, TiO2：3~15%, Nb2O5：5~12%, SrO：More than 5% but less than 20%, BaO：4~15%.
Further, wherein：SiO2：2~10%.
Further, wherein：ZrO2：4~10%.
Further, wherein：B2O3：12~20%, SrO：More than 5.5% but less than 15%.
Further, wherein：SrO：More than 5.5% but less than 15%, BaO：6~12%.
Further, wherein：TiO2：5~12%.
Further, wherein：La2O3：32~40%, TiO2：5~12%, Nb2O5：8~12%.
Further, wherein：SiO2、B2O3、La2O3、ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 85%.
Further, wherein：SiO2、B2O3、La2O3、ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 88%.
Further, wherein：SiO2、B2O3、La2O3、ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 90%.
Using gas preform made of above-mentioned environment friendly heavy-lanthanide flint optical glass.
Using optical element made of above-mentioned environment friendly heavy-lanthanide flint optical glass.
Using optical instrument made of above-mentioned environment friendly heavy-lanthanide flint optical glass.
The beneficial effects of the invention are as follows：The present invention by simultaneously introduce SrO and BaO components, the refractive index of glass can be improved, Softening point is reduced, improves chemical resistance；Work as B2O3When content is high, the volatilization in fusion process can cause constant of glass and bar ripple It is dynamic, the quality stability of glass is reduced, so as to cause complex manufacturing, the present invention is by introducing a certain amount of SrO, effectively Eliminate by B2O3The various problems brought, particularly as the B for adding 12% or more2O3When, remain to be made with steady enough Qualitatively optical glass；The component that the not leaded, arsenic of the present invention, cadmium etc. pollute to environment, refractive index is still can be made into as 1.85 ~1.95, Abbe number is 25~35, and transition temperature is less than 670 DEG C of optical glass.
Embodiment
Each component of optical glass of the present invention is described below, unless otherwise indicated, the content of each component is all with weight % is measured to represent.
SiO2It is the network generation oxide body to form glass, adds a certain amount of SiO2The high temperature viscosity of glass can be increased, Improve the devitrification resistance property of glass.When its content is less than 2%, effect is insufficient；When its content is higher than 15%, glass melts Melting property is deteriorated, and bubble is difficult to eliminate.Therefore, SiO2Content be defined to 2~15%, more preferably content is 2~10%.
B2O3And the oxide of glass is formed, to La as the present invention2O3For the more glass of content, B2O3It is not It can lack.If its content is less than 10%, the meltdown property of glass is poor, and the tendency towards devitrification of glass is big；And when its content exceedes When 25%, the refractive index of glass is too low and the chemical stability of glass is deteriorated, to obtain having desired optical constant scope And the optical glass with excellent chemical stability, B2O3Content be defined to 10~25%, more preferably content be 12~ 20%.
La2O3It is the main component of high refractive optics glass, the refractive index and unobvious that can increase glass improve glass Dispersion, in inventive formulation system, B2O3With La2O3Combination exist, the devitrification resistance property of glass can be effectively improved, Improve the chemical stability of glass.Work as La2O3Content when being less than 30%, it is impossible to obtain the effect of the above, but when its content exceedes When 50%, the crystallization property of glass deteriorates, therefore its content is defined into 30~50%, and preferred content is 32~40%.
ZrO2With the effect for improving glass devitrification resistance, improving chemical stability, in lanthanide glass, raising is also acted as Refractive index and the effect for reducing dispersion.When its content is less than 2%, above-mentioned effect is not had；When its content is higher than 15%, meeting Glass transition temperature is caused to rise, while glass devitrification resistance deteriorates.Therefore ZrO2Content be defined to 2~15%, more preferably For 4~10%.
TiO2It is very effective for the refractive index and dispersion of raising glass, and the water resistance of glass can be improved, reduce glass ratio Weight.In the present invention, TiO2Also act as increase glass high temperature viscosity and improve the effect of devitrification of glass performance, but its content mistake Height can make glass coloration, therefore, TiO2Content be defined to 3~15%, preferably 5~12%.
Nb2O5It is the active ingredient for improving glass refraction, when its content is less than 5%, the refractive index of glass, which does not reach, to be set Target is counted, and when its content is higher than 12%, glass transition temperature can be caused to raise, while under making the transmitance of glass significantly Drop, therefore Nb2O5Content be defined to 5~12%, more preferably 8~12%.
SrO has outstanding role to promoting glass defoaming, suppressing devitrification of glass, works as B2O3Content it is high when, can be effectively Eliminate by B2O3The various problems brought, particularly as the B for adding 12% or more2O3When, can be a certain amount of by introducing SrO, remain to that the optical glass with sufficiently stable property is made.But when SrO contents are higher than 20%, glass smelting is difficult, therefore SrO content is preferably greater than 5% but less than 20%, more preferably higher than 5.5% but less than 15%.
BaO is to adjust glass refraction and Abbe number, the active ingredient for improving chemical durability of glass and heat endurance, SrO and BaO is introduced simultaneously can improve glass refraction, reduce glass softening point, improve chemical resistance.But when its content exceedes The Abbe number increase of glass when 15%, the tendency towards devitrification increase of glass, therefore BaO content is preferably 4~15%, more preferably 6~12%.
Optical glass provided by the invention is ensureing that refractive index is 1.85~1.95, on the premise of Abbe number is 25~35, The present invention uses SiO2、B2O3、La2O3、ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 85%；Preferably, SiO2、 B2O3、La2O3、ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 88%；It is highly preferred that SiO2、B2O3、La2O3、 ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 90%, such glass is not easy devitrification, and absorbing properties are good, glass Not easy coloring, the softening temperature of glass is low, hardness is not high, is especially suitable for secondary press and machining.
The performance of the environment friendly heavy-lanthanide flint optical glass of the present invention is described below.
Wherein refractive index (nd) value is the annealing value of (- 2 DEG C/h)~(- 6 DEG C/h), refractive index and Abbe number according to《GB/T 7962.1-1987 colouless optical glass method of testing refractive indexes and abbe number》Test.
Transition temperature (Tg) according to《GB/T7962.16-1987 colouless optical glass method of testings linear expansion coefficient, transformation Temperature and sag temperature》Test, i.e.,：Sample is within the scope of certain temperature, and temperature often raises 1 DEG C, in sample On expansion curve, low-temperature region and high-temperature area straight line portion are extended into intersecting, the temperature corresponding to its intersection point.
Density according to《GB/T 7962.20-1987 colouless optical glass method of testing density measurement methods》Test.
By test, optical glass provided by the invention has following performance：Density (ρ) is 4.56g/cm3Below；Refraction Rate (nd) is 1.85~1.95；Abbe number (vd) is 25~35；Transition temperature (Tg) is less than 670 DEG C.
The present invention also provides a kind of optical element, as the optical glass described in above-mentioned technical proposal according to people in the art Method known to member is formed.Because described optical glass has high index of refraction, the optical element also has high index of refraction, can With applied to equipment such as digital camera, digital camera, camera cell phones.
In order to further appreciate that technical scheme, the embodiment of optical glass of the present invention will now be described.Should It is noted that these embodiments do not limit the scope of the present invention.
The optical glass (embodiment 1~30) shown in 1~table of table 3 is by according to each embodiment shown in 1~table of table 3 Ratio weigh and hybrid optical glass common raw material (such as oxide, hydroxide, carbonate, nitrate and fluoride), Mixed material is placed in platinum crucible, melted in 1100 to 1300 DEG C of temperature, and through melting, clarifying, stirring After homogenizing, obtain no bubble and the homogeneous melt glass without undissolved material, by this melten glass in mould casting mold And anneal and form.
The composition of embodiments of the invention 1~30 and refractive index (nd), Abbe number (vd), density (ρ), glass transformation temperature (Tg) result represents in 1~table of table 3 together.In these tables, the composition of each component is represented with weight %.
Table 1
Table 2
Table 3
The density (ρ) that glass of the present invention is can be seen that by the embodiment in table 1-3 is 4.56g/cm3Below；Refractive index (nd) it is 1.85~1.95；Abbe number (vd) is 25~35；Transition temperature (Tg) is less than 670 DEG C, not leaded, arsenic, cadmium etc. pair The component that environment pollutes.

Claims (10)

1. environment friendly heavy-lanthanide flint optical glass, it is characterised in that density 4.56g/cm3Hereinafter, refractive index is 1.85~1.95, Abbe number is 25~35, and transition temperature is less than 670 DEG C, and its percentage by weight composition contains：SiO2：2~15%, B2O3：10~ 25%th, La2O3：30~50%, ZrO2：2~15%, TiO2：3~15%, Nb2O5：5~12%, SrO：More than 5% but it is less than 20%th, BaO：4~15%, wherein：SiO2、B2O3、La2O3、ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 85%.
2. environment friendly heavy-lanthanide flint optical glass as claimed in claim 1, it is characterised in that wherein：SiO2：2~10%, ZrO2： 4~10%.
3. environment friendly heavy-lanthanide flint optical glass as claimed in claim 1, it is characterised in that wherein：B2O3：12~20%, SrO： More than 5% but less than 15%.
4. environment friendly heavy-lanthanide flint optical glass as claimed in claim 1, it is characterised in that wherein：SrO：It is more than 5.5% but small In 15%, BaO：6~12%.
5. environment friendly heavy-lanthanide flint optical glass as claimed in claim 1, it is characterised in that wherein：La2O3：32~40%, TiO2：5~12%, Nb2O5：8~12%.
6. environment friendly heavy-lanthanide flint optical glass as claimed in claim 1, it is characterised in that wherein：SiO2、B2O3、La2O3、 ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 88%.
7. environment friendly heavy-lanthanide flint optical glass as claimed in claim 1, it is characterised in that wherein：SiO2、B2O3、La2O3、 ZrO2、Nb2O5, SrO, BaO total amount be more than or equal to 90%.
8. using prefabricated glass made of the environment friendly heavy-lanthanide flint optical glass described in any claim in claim 1~7 Part.
9. using optical element made of the environment friendly heavy-lanthanide flint optical glass described in any claim in claim 1~7.
10. using optics instrument made of the environment friendly heavy-lanthanide flint optical glass described in any claim in claim 1~7 Device.
CN201710970267.7A 2012-09-29 2013-09-27 Environment friendly heavy-lanthanide flint optical glass Pending CN107601850A (en)

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CN2012103724877 2012-09-29
CN2012103724877A CN102964062A (en) 2012-09-29 2012-09-29 Environment-friendly heavy lanthanum flint optical glass
CN201380048545.3A CN104736490A (en) 2012-09-29 2013-09-27 Environmentally-friendly heavy lanthanum flint optical glass

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CN102964062A (en) * 2012-09-29 2013-03-13 成都光明光电股份有限公司 Environment-friendly heavy lanthanum flint optical glass
CN107686237B (en) * 2013-08-05 2019-04-30 成都光明光电股份有限公司 High-refractive and high-dispersive optical glass, optical element and optical instrument
JP6973902B2 (en) * 2016-09-27 2021-12-01 株式会社オハラ Optical glass, preforms and optics
US20190233323A1 (en) * 2016-10-03 2019-08-01 Ohara Inc. Optical glass, preform, and optical element
JP7224099B2 (en) * 2016-10-03 2023-02-17 株式会社オハラ Optical glass, preforms and optical elements
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
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
US11976004B2 (en) 2020-09-10 2024-05-07 Corning Incorporated Silicoborate and borosilicate glasses having high refractive index and high transmittance to blue light
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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JP5972469B2 (en) 2016-08-17
CN104736490A (en) 2015-06-24

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