CN102267801A - Optical glass - Google Patents
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- CN102267801A CN102267801A CN201110168324A CN201110168324A CN102267801A CN 102267801 A CN102267801 A CN 102267801A CN 201110168324 A CN201110168324 A CN 201110168324A CN 201110168324 A CN201110168324 A CN 201110168324A CN 102267801 A CN102267801 A CN 102267801A
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Abstract
The invention provides optical glass with B2O3, La2O3 and Gd2O3 as the main components, and the optical glass contains no thorium, cadmium and arsenic, and preferably contains no lead and fluorine. The refractive index (nd) of the optical glass is in a range of 1.80 to 1.81, and the Abbe number (vd) of the optical glass is in a range of 45 to 48. According to tests by the method of GB/T17129, water resistance (DW) of the optical glass is of grade 1, and acid resistance (DA) is of grade 3 or of a higher grade. On a mass percentage basis, the optical glass comprises 0 to 5% of SiO2, 23 to 32% of B2O3, 28 to 36% of La2O3, 3 to 7% of ZrO2, 0 to 6% of Nb2O5, 0 to 5% of ZnO, less than 2% of Y2O3, 20 to 28% of Gd2O3, 0 to 4% of WO3, 0 to 3% of TiO2, 0 to 2% of Sb2O3 and 0 to 5% of sigma(R2O + RO). The optical glass has good crystallization performance and is suitable for production.
Description
Technical field
The present invention relates to a kind of opticglass, specifically relate to a kind of specific refractory power (nd) between 1.80~1.81, the heavy-lanthanide flint class opticglass of Abbe number (ud) between 45~48.
Background technology
In recent years, in order to satisfy the requirement of the high pixel of high-grade digital product, small portable, the demand of heavy-lanthanide flint class opticglass with advantages such as high refraction, medium chromatic dispersion, proportion are little is increasing.In order to make glass have above performance, the La in the glass
2O
3, TiO
2, Nb
2O
5Component content is also increasing gradually, but these compositions too much can cause that glass viscosity is little, the moulding difficulty big, be difficult for obtaining defectives such as better quality striped and crystallization be serious.
Among the patent CN 1510002A disclosed with the invention belongs to similar glass, but contain the ZnO more than 10% in its component, too much ZnO can make glass devitrification resistance and chemical stability variation.In addition, among the CN 1510002A because of containing the expensive Ta more than 15.5%
2O
5Composition and the glass cost is significantly improved.
Among the patent CN 100352781C disclosed with the invention belongs to similar glass, but it contains as Ta necessary component, expensive
2O
5Composition and can destroy the glass network structure, make the Li of devitrification of glass degradation
2The O composition, this does not meet purpose of the present invention.
Among the patent CN 101003417A disclosed with the invention belongs to similar glass, but it contains the SiO more than 20%
2, different with protection scope of the present invention, in addition, too much SiO in this glass system
2Can make the devitrification resistance variation of glass, can make glass be difficult for melting, transition temperature rising simultaneously, thereby be unfavorable for that glass molds is molded, contain among the CN 101003417A in addition as TiO necessary component, more than 5%
2, different with protection scope of the present invention, in addition, too much TiO
2Can make the crystallization property variation of glass, can make glass coloring simultaneously, thereby influence the spectral transmittance of glass.
Among the patent CN 1972918A disclosed with the invention belongs to similar glass, but it contains the ZnO of 20% above molar content, has with protection scope of the present invention to have significant difference, in addition, the chemical stability that too much ZnO can make glass is variation gradually.
Among the patent CN 1270991C disclosed with the invention belongs to similar glass, but it contains the ∑ (ZnO+Li of 25% above molar content
2O), have with protection scope of the present invention to have significant difference, in addition, the chemical stability that too much ZnO can make glass is variation gradually, and too much Li
2O then can destroy glass network, thereby makes the crystallization property variation of glass.
Among the patent CN 101367611A disclosed with the invention belongs to similar glass, but it is as the Y of necessary component
2O
3Content is more than 2%, with protection scope of the present invention difference to some extent, in addition, more Y
2O
3The crystallization property that can make glass is variation gradually.
Among the patent CN 1935717A disclosed with the invention belongs to similar glass, but its contain as necessary component, content is at the Li more than 0.5%
2O and content then can not contain Li at the ZnO more than 8% among the present invention
2O, in addition, the chemical stability that too much ZnO can make glass is variation gradually.
Among the patent CN 101397189A disclosed with the invention belongs to similar glass, but its contain as necessary component, content is at the ∑ (ZnO+Nb more than 13%
2O
5), have with protection scope of the present invention to have significant difference, in addition, the chemical stability that too much ZnO can make glass is variation gradually, and too much Nb
2O
5The crystallization property that also can make glass is variation gradually, and is difficult for reaching the optical property of the present invention's expection.
In addition, disclosed glass such as patent CN 100344564C, CN 1237018C, CN 1187277C then have obvious difference at aspects such as the optical property of composition, Application Areas and purposes, concern and requirement and the present invention.
Summary of the invention
The problem that invention will solve
The purpose of this invention is to provide a kind of heavy-lanthanide flint class opticglass, its specific refractory power (nd) is between 1.80~1.81, Abbe number (υ d) is between 45~48, and require this glass to have chemical stability and enough good crystallization property, require to reduce the production cost of glass simultaneously, and can realize easily producing in batches.
The scheme that is used to deal with problems
The present invention specifically provides:
A kind of opticglass, its main component are B
2O
3, La
2O
3And Gd
2O
3, not thoriated, cadmium and arsenic, specific refractory power is between 1.80~1.81, and Abbe number is between 45~48, and in the mass percentage content of compound, described opticglass comprises: 0~5% SiO
2, 23~32% B
2O
3, 28~36% La
2O
3, 3~7% ZrO
2, 0~6% Nb
2O
5, 0~5% ZnO, Y less than 2%
2O
3, 20~28% Gd
2O
3, 0~4% WO
3, 0~3% TiO
2, 0~2% Sb
2O
3, 0~5% R
2O and RO; R wherein
2O is Li
2O, Na
2O and K
2One of O or its mixture, RO are one of CaO, SrO and BaO or its mixture; Do not contain Yb in the described opticglass
2O
3And Ta
2O
5
According to opticglass of the present invention, in mass percentage content, Li
2O, Na
2O and K
2The total content of O is less than 2%, and the total content of CaO, SrO and BaO is less than 4%, La
2O
3, Gd
2O
3And Y
2O
3Total content 50% in 60%.
According to opticglass of the present invention, wherein not leaded and fluorine.
According to opticglass of the present invention, it is characterized in that its recrystallization temperature is less than 1080 ℃.
According to opticglass of the present invention, according to the testing method test of GB/T17129, its water tolerance is 1 grade, and acid resistance is 3 grades or better.
The effect of invention
Do not contain the Yb that absorption peak is arranged at near-infrared band in the opticglass of the present invention
2O
3With expensive Ta
2O
5Composition, the present invention has reduced the production cost of opticglass, and can realize easily producing in batches, and opticglass of the present invention has higher chemical stability and enough good crystallization property.In addition, also preferably do not contain environmentally hazardous substance PbO and environmentally hazardous substance and volatile fluorochemical composition among the present invention.
Embodiment
In the flint optical glass with heavy lanthanum that the present invention makes, select every kind of component of above-mentioned content by reason described below.Raw material introducing mode allows to adopt the various ways that can introduce its corresponding content oxide compound, for example Na
2O can carbonate, the form of nitrate, vitriol is introduced.In as described below, each components contents is represented with mass percent.
B
2O
3Be that glass network generates body in heavy-lanthanide flint glass, simultaneously, B
2O
3Can also improve melting properties, the raising glass chemistry stability of glass, work as B
2O
3Content is less than at 23% o'clock, and the melting properties of glass and thermostability can variation, and when its content greater than 32% the time, the specific refractory power of glass then is difficult for reaching local purpose of inventing, and is difficult to the optical property that obtains to expect, so, B
2O
3Content should be controlled between 23%~32%, preferably be controlled between 25%~30%.
SiO
2Can improve the glass high temperature viscosity, a small amount of in the present invention interpolation can improve the mechanical property of glass devitrification resistance and chemical stability glass.But its amount is higher than at 5% o'clock, and the devitrification resistance of glass on the contrary can variation, can make glass be difficult for melting simultaneously, transition temperature raises, thereby is unfavorable for that glass molds is molded, so, SiO
2Content should be controlled at below 5%, preferably be controlled between 1%~4%.
La
2O
3Having higher relatively specific refractory power and lower chromatic dispersion, is one of main component of group of the lanthanides glass of high refractive index, and this optical characteristics makes itself and WO
3, Nb
2O
5Regulate the optical constant of glass together, the coupling that mode more helps optical glass refractive index and chromatic dispersion, La are adjusted in such combination
2O
3Amount less than then being difficult to realize preferably above advantage at 28% o'clock, its content is greater than the crystallization property that then can make glass at 36% o'clock variation gradually, so, La
2O
3Content should be controlled between 28%~36%, preferably be controlled between 30%~35%.
Y
2O
3Can improve the specific refractory power and the devitrification resistance of glass, but after its content reaches 2%, the crystallization property of glass is variation gradually then, so Y
2O
3Content should be controlled at less than 2%, preferably more than 1% but less than 2%.
ZrO
2Has the effect that improves optical constant and improve devitrification resistance and chemical stability, in group of the lanthanides glass, can also play the effect that improves specific refractory power and reduce chromatic dispersion, be the necessary component of adding in the present invention, but when it contains quantity not sufficient 3%, DeGrain, and when its content greater than 8% the time, the crystallization property of glass can variation, so, ZrO
2Content should be controlled between 3%~8%, preferably be controlled between 4%~7%.
Nb
2O
5Have the effect that improves specific refractory power, improves chemical stability and crystallization property, in the present invention, when its amount surpassed 8%, the crystallization property of glass is variation gradually on the contrary, and was difficult for reaching the optical property of the present invention's expection, so Nb
2O
5Content should be controlled at below 6%, preferably between 2%~6%.
Gd
2O
3Effect and La
2O
3Similar, have higher relatively specific refractory power and lower chromatic dispersion, this optical characteristics makes itself and WO
3, Nb
2O
5Regulate the optical constant of glass together, the coupling that mode more helps optical glass refractive index and chromatic dispersion is adjusted in such combination, in the present invention, and Gd
2O
3Amount less than then being difficult to realize preferably above advantage at 20% o'clock, its content is greater than the crystallization property that then can make glass at 28% o'clock variation gradually, so, Gd
2O
3Content should be controlled between 20%~28%, preferably be controlled between 22%~26%.
ZnO can reduce the tendency towards devitrification of glass, but after its content surpassed 5% in the present invention, the chemical stability of glass is variation gradually, thus the content of ZnO should be controlled at below 5%, preferably between 1%~4%.
TiO
2Can effectively improve the specific refractory power and the chromatic dispersion of glass, a small amount of introducing can be adjusted the matching of specific refractory power and chromatic dispersion more flexibly, but if introducing can make glass coloring deepen more at most, so TiO
2Content should be controlled at below 3%, preferably below 2%.
WO
3Can improve the specific refractory power and the chromatic dispersion of glass, a small amount of introducing can be adjusted the matching of specific refractory power and chromatic dispersion more flexibly, has the effect that changes the devitrification of glass performance simultaneously, but the transmitance that its content surpasses 4% o'clock glass short-wave band variation gradually, so WO
3Content should be controlled at below 4%, preferably below 2%.
Sb
2O
3Can be used as defrother and add arbitrarily, but its content is 1% with interior just enough, and Sb
2O
3To become big if surpass 1% glass coloring degree.So Sb
2O
3Component concentration is limited to 0~1%, preferably 0~0.5%.
Can add small amounts of alkali metal oxides (R except that above composition, that can help melting among the present invention
2O), as Li
2O, Na
2O and K
2O.But alkalimetal oxide, does not preferably contain so its total amount should be controlled at below 2% because of more serious to Web Grafiti.
A small amount of alkaline earth metal oxide (RO) that adds: one of CaO, SrO and BaO or mixture, can adjust the glass microtexture, make glass chemistry stability better, but its total content is 4% when above, then similar with alkalimetal oxide, the destruction of glass network is strengthened gradually, thus the crystallization property that makes glass variation gradually, so its total amount should be controlled at below 4%, does not preferably contain.Total amount ∑ (the R of alkalimetal oxide and alkaline earth metal oxide
2O+RO) should be controlled at below 5%, be preferably zero.
Be to guarantee the spectral transmittance of the type spare that the present invention suppressed, opticglass provided by the invention is not artificially introduced the element that except that above component other can be painted: V, Mo, Cr, Mn, Fe, Co, Ni, Cu and Ag.Simultaneously, artificially do not introduce the compound that contains following harmful element: Th, Cd, T1, Os, Be, Se and fluorochemical yet.In addition, target call to better implement the present invention, the present invention emphasizes not contain the Yb that absorption peak is arranged at near-infrared band
2O
3With expensive Ta
2O
5Composition.
Fusion and the forming method of producing opticglass can adopt the method for well known to a person skilled in the art, for example, after frit cooperated according to the proportioning of glass oxide compound and mixing, drop in the smelting apparatus (as platinum crucible), then 1200 ℃~1300 ℃ take suitable stirring, clarification, temperature reduction technology to carry out melting after, cast or leakage are annotated in forming mould after post-processed such as annealing, processing are perhaps passed through the direct compression moulding of precise compression molding technology.
Below by embodiment the present invention is carried out more specific description, but the present invention is not limited to these embodiment.
Embodiment
Below the embodiment 1~5th that lists in the table 1, the present invention is used for explanation and obtains specific refractory power (nd) between 1.80~1.81, the specific embodiments of the heavy-lanthanide flint class opticglass of Abbe number (υ d) between 45~48.Comparative examples A and B be specific refractory power between 1.80~1.81, the contrast embodiment of Abbe number between 45~48.
According to the ratio calculating that provides in the table 1, weighing, mix these raw materials, and the admixtion of making dropped in the smelting apparatus (in view of application requiring of the present invention, smelting apparatus need adopt platinum crucible), then 1200 ℃~1300 ℃ take suitable stirring, clarification, temperature reduction technology to carry out melting after, cast or leak to annotate in forming mould.After post-processed such as annealing, processing perhaps by the direct compression moulding of precise compression molding technology, can make this environment-friendly type heavy-lanthanide flint class opticglass or optical type spare.
Use powder method according to the GB/T17129 standard then, gained opticglass is tested, with the chemical stability data of gained: acid resistance (D
A) and water tolerance (D
W) list in the table 1.
Recrystallization temperature (Lt) is a liquidus line curve temperature, it adopts DTA (differential thermal analysis) method to measure, what the present invention adopted is the DiamondTG-DTA type differential thermal analyzer that U.S. PE company produces, and the temperature of wherein measuring the thermal absorption peak correspondence that temperature is the highest in the curve is Lt, and the results are shown in Table 1.
Table 1
* annotate: ∑ R in the table
2O=Na
2O+K
2O+Li
2O, ∑ RO=BaO+SrO+CaO,
∑R
2O
3=La
2O
3+Gd
2O
3+Y
2O
3
By The performance test results listed in the table 1 as can be seen, specific refractory power of the present invention (nd) is between 1.80~1.81, and the borate lanthanide optical glass of Abbe number (υ d) between 39~41 and do not contain Ta
2O
5The opticglass of comparative example B compare, have better chemical stability (acid resistance and water tolerance), have lower recrystallization temperature; With contain Ta
2O
5The opticglass of Comparative examples A compare, reduced manufacturing cost, and had lower recrystallization temperature.
Claims (5)
1. opticglass, its main component is B
2O
3, La
2O
3And Gd
2O
3, not thoriated, cadmium and arsenic, specific refractory power is between 1.80~1.81, and Abbe number is between 45~48, and in the mass percentage content of compound, described opticglass comprises:
SiO
2 0~5%,
B
2O
3 23~32%,
La
2O
3 28~36%,
ZrO
2 3~7%,
Nb
2O
5 0~6%,
ZnO 0~5%,
Y
2O
3 <2%,
Gd
2O
3 20~28%,
WO
3 0~4%,
TiO
2 0~3%,
Sb
2O
3 0~2%,
R
2The total amount 0~5% of O and RO;
R wherein
2O is Li
2O, Na
2O and K
2One of O or mixture, RO are one of CaO, SrO and BaO or its mixture;
Do not contain Yb in the described opticglass
2O
3And Ta
2O
5
2. opticglass according to claim 1 is characterized in that, in mass percentage content, and Li
2O, Na
2O and K
2The total content of O is less than 2%, and the total content of CaO, SrO and BaO is less than 4%, La
2O
3, Gd
2O
3And Y
2O
3Total content 50% in 60%.
3. opticglass according to claim 2, wherein not leaded and fluorine.
4. according to each described opticglass of claim 1-3, it is characterized in that its recrystallization temperature is less than 1080 ℃.
5. according to each described opticglass of claim 1-3, according to the testing method test of GB/T17129, its water tolerance is 1 grade, and acid resistance is 3 grades or better.
Priority Applications (1)
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CN 201110168324 CN102267801B (en) | 2011-06-17 | 2011-06-17 | Optical glass |
Applications Claiming Priority (1)
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---|---|---|---|
CN 201110168324 CN102267801B (en) | 2011-06-17 | 2011-06-17 | Optical glass |
Publications (2)
Publication Number | Publication Date |
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CN102267801A true CN102267801A (en) | 2011-12-07 |
CN102267801B CN102267801B (en) | 2013-12-18 |
Family
ID=45050284
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104341102A (en) * | 2013-07-31 | 2015-02-11 | 株式会社小原 | Optical glass and optical element |
CN107244803A (en) * | 2017-07-11 | 2017-10-13 | 湖北新华光信息材料有限公司 | Flint optical glass with heavy lanthanum and preparation method thereof and optical element |
CN109970338A (en) * | 2019-04-28 | 2019-07-05 | 成都光明光电股份有限公司 | Optical glass, gas preform, optical element and optical instrument |
CN109970337A (en) * | 2019-04-28 | 2019-07-05 | 成都光明光电股份有限公司 | Optical glass, gas preform, optical element and optical instrument |
CN110835232A (en) * | 2018-08-17 | 2020-02-25 | 成都光明光电股份有限公司 | Optical glass, glass preform or optical element prepared from optical glass, and optical instrument |
CN110835228A (en) * | 2018-08-17 | 2020-02-25 | 成都光明光电股份有限公司 | Optical glass, glass preform or optical element prepared from optical glass, and optical instrument |
CN110835227A (en) * | 2018-08-17 | 2020-02-25 | 成都光明光电股份有限公司 | Optical glass, glass preform or optical element prepared from optical glass, and optical instrument |
CN110835231A (en) * | 2018-08-17 | 2020-02-25 | 成都光明光电股份有限公司 | Optical glass, glass preform or optical element prepared from optical glass, and optical instrument |
CN111285602A (en) * | 2018-12-07 | 2020-06-16 | 成都光明光电股份有限公司 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
CN111285601A (en) * | 2018-12-07 | 2020-06-16 | 成都光明光电股份有限公司 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
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CN1377847A (en) * | 2001-03-27 | 2002-11-06 | 保谷株式会社 | Optical glass and optical part |
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US4111707A (en) * | 1977-12-14 | 1978-09-05 | Kabushiki Kaisha Ohara Kogaku Garasu Seizosho | Optical glass |
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Cited By (16)
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CN104341102B (en) * | 2013-07-31 | 2018-08-07 | 株式会社小原 | Optical glass and optical element |
CN104341102A (en) * | 2013-07-31 | 2015-02-11 | 株式会社小原 | Optical glass and optical element |
CN107244803A (en) * | 2017-07-11 | 2017-10-13 | 湖北新华光信息材料有限公司 | Flint optical glass with heavy lanthanum and preparation method thereof and optical element |
CN107244803B (en) * | 2017-07-11 | 2023-02-03 | 湖北新华光信息材料有限公司 | Heavy lanthanum flint optical glass, preparation method thereof and optical element |
CN110835232B (en) * | 2018-08-17 | 2022-10-14 | 成都光明光电股份有限公司 | Optical glass, glass preform or optical element prepared from optical glass, and optical instrument |
CN110835232A (en) * | 2018-08-17 | 2020-02-25 | 成都光明光电股份有限公司 | Optical glass, glass preform or optical element prepared from optical glass, and optical instrument |
CN110835228A (en) * | 2018-08-17 | 2020-02-25 | 成都光明光电股份有限公司 | Optical glass, glass preform or optical element prepared from optical glass, and optical instrument |
CN110835227A (en) * | 2018-08-17 | 2020-02-25 | 成都光明光电股份有限公司 | Optical glass, glass preform or optical element prepared from optical glass, and optical instrument |
CN110835231A (en) * | 2018-08-17 | 2020-02-25 | 成都光明光电股份有限公司 | Optical glass, glass preform or optical element prepared from optical glass, and optical instrument |
CN110835231B (en) * | 2018-08-17 | 2022-10-18 | 成都光明光电股份有限公司 | Optical glass, glass preform or optical element prepared from optical glass, and optical instrument |
CN111285602A (en) * | 2018-12-07 | 2020-06-16 | 成都光明光电股份有限公司 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
CN111285601A (en) * | 2018-12-07 | 2020-06-16 | 成都光明光电股份有限公司 | Heavy lanthanum flint glass and prefabricated member, optical element and optical instrument thereof |
CN109970337A (en) * | 2019-04-28 | 2019-07-05 | 成都光明光电股份有限公司 | Optical glass, gas preform, optical element and optical instrument |
CN109970338B (en) * | 2019-04-28 | 2022-05-06 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument |
CN109970337B (en) * | 2019-04-28 | 2021-12-07 | 成都光明光电股份有限公司 | Optical glass, glass preform, optical element and optical instrument |
CN109970338A (en) * | 2019-04-28 | 2019-07-05 | 成都光明光电股份有限公司 | Optical glass, gas preform, optical element and optical instrument |
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