CN102267801B - Optical glass - Google Patents

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CN102267801B
CN102267801B CN 201110168324 CN201110168324A CN102267801B CN 102267801 B CN102267801 B CN 102267801B CN 201110168324 CN201110168324 CN 201110168324 CN 201110168324 A CN201110168324 A CN 201110168324A CN 102267801 B CN102267801 B CN 102267801B
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glass
opticglass
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optical glass
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CN102267801A (en
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霍金龙
杨爱清
张卫
唐雪琼
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Hubei New Huaguang Information Materials Co Ltd
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Hubei New Huaguang Information Materials Co Ltd
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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

Opticglass
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 meet 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 dispersion, proportion are little is increasing.In order to make glass there is above performance, the La in glass 2o 3, TiO 2, Nb 2o 5component content is also increasing gradually, but the defect such as these compositions too much can cause that glass viscosity is little, the moulding difficulty large, be difficult for obtaining the better quality striped and crystallization is serious.
In 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, in CN 1510002A because containing the expensive Ta more than 15.5% 2o 5composition and the glass cost is significantly improved.
In 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.
In 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 in CN 101003417A in addition as necessary component, TiO 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 affect the spectral transmittance of glass.
In patent CN 1972918A disclosed with the invention belongs to similar glass, but its ZnO that contains 20% above molar content has and has significant difference with protection scope of the present invention, in addition, the chemical stability that too much ZnO can make glass is variation gradually.
In patent CN 1270991C disclosed with the invention belongs to similar glass, but its ∑ (ZnO+Li that contains 25% above molar content 2o), with protection scope of the present invention, have and have significant difference, in addition, the chemical stability that too much ZnO can make glass is variation gradually, and too much Li 2o can destroy glass network, thereby makes the crystallization property variation of glass.
In 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.
In 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, at the ZnO more than 8%, can not contain Li in the present invention 2o, in addition, the chemical stability that too much ZnO can make glass is variation gradually.
In 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 and there is significant difference with protection scope of the present invention, 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, the disclosed glass such as patent CN 100344564C, CN 1237018C, CN 1187277C are at aspect and the obvious differences of the present invention such as optical property of composition, Application Areas and purposes, concern and requirement.
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 there is chemical stability and enough good crystallization property, require to reduce the production cost of glass simultaneously, and can easily realize batch production.
for the scheme of dealing with problems
The present invention specifically provides:
A kind of 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: 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, be less than 2% Y 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 is one of CaO, SrO and BaO or its mixture; Do not contain Yb in 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 that the total content of O is less than 2%, 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, not leaded and fluorine wherein.
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 opticglass of the present invention 2o 3with expensive Ta 2o 5composition, the present invention has reduced the production cost of opticglass, and can easily realize batch production, 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 in the present invention.
Embodiment
In the flint optical glass with heavy lanthanum made in the present invention, selected 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, the content of each component means with mass percent.
B 2o 3in heavy-lanthanide flint glass, be that glass network generates body, simultaneously, B 2o 3can also improve melting properties, the raising chemical durability of glass of glass, work as B 2o 3when content is less than 23%, the melting properties of glass and thermostability meeting variation, and when its content is greater than 32%, the specific refractory power of glass is difficult for reaching the purpose of local invention, is difficult to obtain the optical property of expection, 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 interpolation in the present invention can improve the mechanical property of glass devitrification resistance and chemical stability glass.But its amount is higher than 5% the time, the devitrification resistance of glass on the contrary can variation, can make glass be difficult for melting, transition temperature raises simultaneously, 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 relatively high specific refractory power and lower 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 together the optical constant of glass, the coupling that mode more is conducive to optical glass refractive index and dispersion, La are adjusted in such combination 2o 3amount be difficult to realize preferably above advantage while being less than 28%, the crystallization property that can make glass when its content is greater than 36% is variation gradually, so, La 2o 3content should be controlled between 28%～36%, preferably be controlled between 30%～35%.
Y 2o 3can improve specific refractory power and the devitrification resistance of glass, but after its content reaches 2%, the crystallization property of glass is variation gradually, so Y 2o 3content should be controlled at and be less than 2%, preferably more than 1% but be less than 2%.
ZrO 2there is the effect that improves optical constant and improve devitrification resistance and chemical stability, can also play the effect that improves specific refractory power and reduce dispersion in lanthanide glass, be the necessary component of adding in the present invention, but when it contains quantity not sufficient 3%, DeGrain, and when its content is greater than 8%, the crystallization property of glass meeting 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 surpasses 8%, the crystallization property of glass is variation gradually on the contrary, and is 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, there is relatively high specific refractory power and lower dispersion, this optical characteristics makes itself and WO 3, Nb 2o 5regulate together the optical constant of glass, the coupling that mode more is conducive to optical glass refractive index and dispersion is adjusted in such combination, in the present invention, and Gd 2o 3amount be difficult to realize preferably above advantage while being less than 20%, the crystallization property that can make glass when its content is greater than 28% is 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 surpasses 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 specific refractory power and the dispersion of glass, a small amount of introducing can be adjusted the matching of specific refractory power and dispersion more flexibly, if but introducing can make glass coloring deepen more at most, so TiO 2content should be controlled at below 3%, preferably below 2%.
WO 3can improve specific refractory power and the dispersion of glass, a small amount of introducing can be adjusted the matching of specific refractory power and dispersion more flexibly, has the effect that changes the devitrification of glass performance simultaneously, but the transmitance of its content glass short-wave band while surpassing 4% 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 1% with interior just enough, and Sb 2o 3to become large if surpass 1% glass coloring degree.So Sb 2o 3component concentration is limited to 0～1%, preferably 0～0.5%.
Can add a small amount of alkalimetal oxide (R except above composition, that can help melting in the present invention 2o), as Li 2o, Na 2o and K 2o.But alkalimetal oxide, because of more serious to Web Grafiti, so its total amount should be controlled at below 2%, does not preferably contain.
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 chemical durability of glass better, but its total content is 4% when above, 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.
For guaranteeing the spectral transmittance of the type part that the present invention suppresses, opticglass provided by the invention is not artificially introduced the element that other except above component 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.
Melting 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 is coordinated according to the proportioning of glass oxide compound and mixing, drop in smelting apparatus (as 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 finally by post-processed such as annealing, processing, or pass through the moulding of precise compression molding technology direct pressing.
Below by embodiment, the present invention is carried out to more specific description, but the present invention is not limited to these embodiment.
Embodiment
Below the embodiment 1～5th that lists in table 1, the present invention 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 for illustrating.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 provided in table 1, weighing, mix these raw materials, and the admixtion of making is dropped in smelting apparatus (in view of application requiring of the present invention, smelting apparatus need to 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.Finally by post-processed such as annealing, processing, or, by the moulding of precise compression molding technology direct pressing, can make this environment-friendly type heavy-lanthanide flint class opticglass or optical type part.
Then use powder method according to the GB/T17129 standard, gained opticglass is tested, by the chemical stability data of gained: acid resistance (D a) and water tolerance (D w) list in table 1.
Recrystallization temperature (Lt) is 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, wherein measure temperature corresponding to thermal absorption peak that in curve, temperature is the highest and be Lt, the results are shown in Table 1.
Table 1
Figure BSA00000522382800081
* annotate: ∑ R in 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 table 1, can be found out, 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 45～48, and do not contain Ta 2o 5the opticglass of comparative example B compare, there is better chemical stability (acid resistance and water tolerance), there is lower recrystallization temperature; With contain Ta 2o 5the opticglass of Comparative examples A compare, reduced manufacturing cost, and there is lower recrystallization temperature.

Claims (5)

1. an 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:
Figure FFW00000084012000011
R wherein 2o is Li 2o, Na 2o and K 2one of O or mixture, RO is one of CaO, SrO and BaO or its mixture;
Do not contain Yb in 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 that the total content of O is less than 2%, 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 the described opticglass of claim 1-3 any one, it is characterized in that its recrystallization temperature is less than 1080 ℃.
5. according to the described opticglass of claim 1-3 any one, according to the testing method test of GB/T17129, its water tolerance is 1 grade, and acid resistance is 3 grades or better.
CN 201110168324 2011-06-17 2011-06-17 Optical glass Active CN102267801B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5979723B2 (en) * 2013-07-31 2016-08-31 株式会社オハラ Optical glass 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
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
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
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
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
CN111285602B (en) * 2018-12-07 2022-03-08 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
CN111285601B (en) * 2018-12-07 2022-03-08 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
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

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US4111707A (en) * 1977-12-14 1978-09-05 Kabushiki Kaisha Ohara Kogaku Garasu Seizosho Optical glass
CN1377847A (en) * 2001-03-27 2002-11-06 保谷株式会社 Optical glass and optical part

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