CN1171817C - Lead-free optical light flint and double-light flint glasses - Google Patents

Lead-free optical light flint and double-light flint glasses Download PDF

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Publication number
CN1171817C
CN1171817C CNB971215731A CN97121573A CN1171817C CN 1171817 C CN1171817 C CN 1171817C CN B971215731 A CNB971215731 A CN B971215731A CN 97121573 A CN97121573 A CN 97121573A CN 1171817 C CN1171817 C CN 1171817C
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China
Prior art keywords
light flint
glass
weight
double
lead
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Expired - Fee Related
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CNB971215731A
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Chinese (zh)
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CN1182721A (en
Inventor
D・格拉鲍斯基
D·格拉鲍斯基
伯格
U·科尔伯格
叨
A·魏策尔
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Schott AG
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Schott Glaswerke AG
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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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium

Abstract

Lead-free optical light flint and double-light flint glasses having a refractive index n d of between 1.52 and 1.57 and an Abbe coefficient small Greek nu d of between 43 and 52 are described, which have the following composition (in % by weight based on oxides): SiO 2 48-55, B 2 O 3 7-9, K 2 O 18-20, Al 2 O 3 7-9, La 2 O 3 0.1-2, ZrO 2 0-1, capital Greek sigma La 2 O 3 +ZrO 2 0.5-2, TiO 2 5.5-12, F - 1.5-6, (Al 2 O 3 +La 2 O 3 )/(TiO 2 +ZrO 2 ) = 0.73-1.15. The glasses show outstanding crystallization stability and very good chemical resistance.

Description

Lead-free optical light flint and double-light flint glasses
The present invention relates to refractive index n dBe 1.52-1.57, Abbe coefficient ν dLead-free optical light flint and double-light flint glasses (double-light flint glass) for 43-52.
Because the public thinks glass ingredient PbO and As in recent years 2O 3Be environmental pollutant, so the manufacturers of some consumer's goods and opticinstrument only changes using and does not contain PbO, also do not contain As into 2O 3Glass.Therefore, this class glass with special optical performance can have been bought at market uh.
In order to produce the light flint component, that is to say low density glass, also need to save PbO.
The result replaces plumbous oxide in not success aspect the regeneration product of required optical property that influenced by PbO and glasswork performance simply with one or more components.On the contrary, aspect glass ingredient, carry out new development or to change widely be necessary.
In patent documentation, have been found that the specification sheets of describing crown glass with described optical value.Yet, these glass show significant disadvantages.
Therefore, at JP 1-133, the optical fiber glass of describing in the 956 A specification sheetss belongs to SiO 2-Al 2O 3-M 2O-F -Glass system, PbO belongs to selectable components.In order to obtain enough crystallization-stables, these glass need high Al 2O 3Content, but this reduces meltability.In order to improve meltability, they can contain the Li of 25% (mole) at the most 2O.Yet, high like this Li 2O content can reduce crystallization-stable again.
JP 6-107, the glass of describing among 425 A contains BaO, and its optical value changes in very wide scope.Sometimes the glass while B that obtains 2O 3The content height, M 2The content of O is also high, chemically unstable, and the crystallization instability, but this can be by using the Nb of 25% (weight) at the most 2O 5Compensate.Yet the component of this costliness has greatly increased the price of mixture, has therefore also increased production cost.
The glass of describing among patent specification EP 0,645,349 B1 also contains Nb 2O 5They do not contain B 2O 3In order to improve the meltability of glass, they contain the alkalimetal oxide of 40% (weight) at the most, at F -Content under the situation of 8% (weight), will make that the crystallization-stable of glass is low, the chemical resistant properties deficiency at the most.
The glass of German patent specification DE 973,350 belongs to SiO 2-M 2The O-F glass system.These glass neither contain La 2O 3, do not contain ZrO yet 2PbO is optional component.These glass also demonstrate very wide optical value.When above-mentioned value, the F of glass -The content height.These glass particularly do not have enough acid resistances and alkali resistance because their composition does not show good chemical stability.They also tend to layering (opaque), and the viscograph that shows in limited time on crystallization is not good.
At specification sheets JP 6-92, described by SiO among the 674A 2-M 2O-P 2O 5The opticglass that glass system constitutes.Na 2O (at least 12.5% (weight)) must exist as alkalimetal oxide.Because M 2O and P 2O 5Content height (up to 15% (weight)), the crystallization-stable of these glass is also not enough, the chemical resistant properties that shows is poor.
The purpose of this invention is to provide refractive index n dFor 1.52-1.57, Abbe coefficient are unleaded light flint or the double-light flint glasses of 43-52, the low (p≤2.60g/cm of its density 3), melting properties and good processability comprise that also crystallization-stable is good, have the viscosity that permission is produced in bigger melting appartus (for example at the optics tank furnace), that is to say the viscosity 〉=1000dPas that prescribes a time limit on crystallization.In addition, glass should have favorable chemical resistance, and this is very important to the further processing such as grinding and polishing etc., and its production cost should be low.
Reached this purpose by following glass:
1. refractive index n dBe 1.52-1.57, Abbe coefficient v dBe lead-free optical light flint and the double-light flint glasses of 43-52,
It is characterized in that following (based on the weight % of oxide compound) composed as follows:
SiO 2 48-55
B 2O 3 7-9
K 2O 18-20
Al 2O 3 7-9
La 2O 3 0.1-2
ZrO 2 0-1
But La 2O 3+ ZrO 20.5-2
TiO2 5.5-12
F - 1.5-6
0.73-1.15
The finings that can also comprise in case of necessity, convention amount.
This glass contains the glass-former SiO of 48-55% (weight) 2When content was low, the crystallization tendency increased, and chemical resistant properties reduces; When content was higher, glass became and more is difficult to fusing.This scope is preferably 50-52% (weight).
B 2O 3Exist as another glass-former, its content is 7-9% (weight).The minimum content that provides is that the meltability of improvement glass and the vaporization that reduces fluorine are essential.Should not surpass the high-content provide, otherwise hydrolytic resistance reduces.High-content is preferably 8% (weight).
Glass contains the Al of 7-9% (weight) 2O 3This component with minimum content is improved crystallization-stable and chemical resistant properties.When content was higher, the excess stickiness of glass increased.High-content preferably is restricted to 8.5% (weight).
In order to improve melting properties and to obtain good transmission, glass contains 18-20% (weight), is preferably the K of 19-20% (weight) 2O.
In order to obtain required optical value and to arrive high chemical resistance, glass contains the La of 0.1-2% (weight) 2O 3When content is higher, do not reach required optical value, and the price of mixture increases unnecessarily.
ZrO 2Optical value also had intense influence.Because when the content of this oxide compound was higher, specific refractory power excessively increased, so the amount of this oxide compound can be up to 1% (weight).
Because each oxide compound produces described shortcoming up and down in these boundaries, so La 2O 3And ZrO 2Total amount should be 0.5-2% (weight).In the embodiment of special recommendation, the summation of two oxide compounds is 0.6-1.4% (weight).
Although because Al 2O 3And La 2O 3With B 2O 3The equilibrated ratio make K 2O content is quite high, but these glass show extraordinary crystallization-stable.In recommended embodiment of the present invention, (Al 2O 3+ La 2O 3)/B 2O 3Weight ratio should be greater than 1.We find, SiO 2Content should be at least 49% (weight), makes to have enough network formers.
In order to reach given optical value, glass contains another component TiO 2, its content is 5.5-12% (weight).In addition, when content was low, chemical resistant properties reduced; And content is when higher, and transmission reduces.Content is preferably 8-11% (weight).
Except that absolute magnitude, the outstanding chemical-resistant deciding factor of glass of the present invention is Al 2O 3And La 2O 3With TiO 2And ZrO 2Concrete ratio ((Al 2O 3+ La 2O 3)/(TiO 2+ ZrO 2)).This ratio should be 0.73-1.15.Weight ratio＜0.73 o'clock, chemical resistant properties, particularly acid resistance and alkali resistance reduce.This value＞1.15 o'clock, meltability reduces.Although can be by increasing K 2O and B 2O 3Content compensates, but this can damage crystallization-stable subsequently.And be very difficult to adjust required optical value, particularly Abbe coefficient, that is to say relevant with other shortcoming.In the embodiment of special recommendation, (Al 2O 3+ La 2O 3)/(TiO 2+ ZrO 2) weight ratio is 0.77-1.10.
In addition, glass also contains fluorion, is 1.5-6% (weight), is preferably 2-5.5% (weight).Like this, " inherence " glass quality that reaches (about not containing bubble and drawing lines) is very good, light transmission τ in the 400-1600nm scope 25nm(that is to say when thickness of sample is 25nm) is very good, is at least 80%.The F that surpasses 6% (weight) -High-content causes layering, causes glass opaque thus.
The glass of all components in given recommended range is represented refractive index n dFor 1.52-1.55, Abbe coefficient are the double-light flint glasses of 45-50.
In order further to improve glass quality, own known one or more finingss of constant can be added in the mixture, with fining glass.
If do not use As 2O 3, but for example use Sb 2O 3Replace, this not loss relevant with glass quality, crown glass so of the present invention does not also contain arsenic.
In another recommended embodiment of the present invention, glass contains following finings: Sb 2O 3Be 0-0.5% (weight), Cl -During for 0-0.5% (weight), Sb 2O 3+ Cl -Be 0.1-0.5% (weight).
Therefore, the scope of glass composition of the present invention is made unleaded light flint and/or the folding double-light flint glasses that another group has given optical property.Compare with double-light flint glasses with conventional light flint, its difference is the low (ρ≤2.6g/cm of density 3) and following performance: glass shows extraordinary chemical resistant properties and outstanding crystallization-stable, very high " inherence " glass quality, high transition temperature and very high light transmission in the 400-1600nm wavelength region.In addition, particularly because saved expensive Nb 2O 5Component, so their production cost is low.Another advantage is that glass does not only contain PbO, and in a recommended embodiment, does not contain As yet 2O 3
Embodiment:
Embodiment by 7 of the present invention glass of conventional raw material melting in recommending compositing range.The composition of glass (based on the weight % of oxide compound) and (part is as embodiment) fundamental property are listed in the table 2.
Glass of the present invention is produced by the following method: weighing oxide compound and fluoride raw material, preferably carbonate, nitrate and fluorochemical; Add one or more finingss, for example Sb 2O 3, uniform mixing then.In the continuous melting device, in 1250-1300 ℃ of molten glass mixture, clarification and thoroughly homogenizing then.Glass is cast in 1200 ℃, places cool furnace in 550 ℃, is cooled to room temperature, to reach unstress state.
Table 1 shows a fusing embodiment:
Oxide compound % (weight) Raw material Weighed amount (kg)
SiO 2 51.60 SiO 2 51.60
Al 2O 3 8.10 AlO(OH) 10.33
B 2O 3 7.79 H 3BO 3 13.83
K 2O 19.60 KNO 3 36.79
F - 2.00 KHF 2 4.14
La 2O 3 0.10 La 2O 3 0.10
TiO 2 10.12 TiO 2 10.17
ZrO 2 0.51 ZrO 2 0.52
Sb 2O 3 0.18 Sb 2O 3 0.20
Add up to 100 127.69
Thus obtained glass properties is shown among table 2, the embodiment 7.
Table 2 glass is formed (based on the weight % of oxide compound) and fundamental property
Wherein:
Tg: transition temperature
AR: according to the alkali resistance of ISO 10,629 drafts
SR: according to the acid resistance of ISO 8424
P G.F: at the relative partial dispersion of described wavelength
△ P G.F: with the relative partial dispersion deviation value of " normal straight "
τ 400nm/25nm: the spectral transmittance when wavelength X=400nm and thickness of sample d=25nm

Claims (7)

1. refractive index n dBe 1.52-1.57, Abbe coefficient ν dBe lead-free optical light flint and the double-light flint glasses of 43-52,
It is characterized in that following (based on the weight % of oxide compound) composed as follows:
SiO 2 48-55
B 2O 3 7-9
K 2O 18-20
Al 2O 3 7-9
La 2O 3 0.1-2
ZrO 2 0-1
But La 2O 3+ ZrO 20.5-2
TiO 2 5.5-12
F - 1.5-6
0.73-1.15
The finings that can also comprise in case of necessity, convention amount.
2. according to the lead-free optical light flint and the double-light flint glasses of claim 1, it is characterized in that weight ratio
Figure C971215730002C2
The SiO greater than 1 2Content is at least 49% (weight).
According to claim 1 or 2, refractive index n dBe 1.52-1.55, Abbe coefficient ν dBe the lead-free optical double-light flint glasses of 45-50, it is characterized in that following composition (based on the weight % of oxide compound):
SiO 2 50-52
B 2O 3 7-8
K 2O 19-20
Al 2O 3 7-8.5
La 2O 3 0.1-2
ZrO 2 0-1
But La 2O 3+ ZrO 20.5-2
TiO 2 8-11
F - 2-5.5
Figure C971215730003C1
0.73-1.15 can also comprise in case of necessity, the finings of convention amount.
4. according to the lead-free optical light flint and the double-light flint glasses of at least one claim among the claim 1-3, it is characterized in that La 2O 3+ ZrO 2Sum is 0.6-1.4% (weight).
5. according to the lead-free optical light flint and the double-light flint glasses of at least one claim among the claim 1-4, it is characterized in that weight ratio
Figure C971215730003C2
Be 0.77-1.10.
6. according to the lead-free optical light flint and the double-light flint glasses of at least one claim among the claim 1-5, it is characterized in that the finings (based on the weight % of oxide compound) that they contain is:
Sb 2O 3 0-0.5
Cl - 0-0.5
But Sb 2O 3+ Cl -0.1-0.5
7. according to the lead-free optical light flint and the double-light flint glasses of at least one claim among the claim 1-6, it is characterized in that except that inevitable pollution their oxygen-free arsenic.
CNB971215731A 1996-10-28 1997-10-27 Lead-free optical light flint and double-light flint glasses Expired - Fee Related CN1171817C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1996144736 DE19644736C1 (en) 1996-10-28 1996-10-28 Light flint glass composition used in optical applications
DE19644736.4 1996-10-28

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CN1171817C true CN1171817C (en) 2004-10-20

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JP (1) JP3073474B2 (en)
CN (1) CN1171817C (en)
DE (1) DE19644736C1 (en)
FR (1) FR2755125B1 (en)
GB (1) GB2318576B (en)
MY (1) MY122044A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11306021B2 (en) 2018-11-26 2022-04-19 Owens Coming Intellectual Capital, LLC High performance fiberglass composition with improved elastic modulus
US11524918B2 (en) 2018-11-26 2022-12-13 Owens Corning Intellectual Capital, Llc High performance fiberglass composition with improved specific modulus

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104445928B (en) * 2014-11-11 2018-10-26 湖北新华光信息材料有限公司 A kind of light flint

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE973350C (en) * 1940-06-10 1960-01-28 Jenaer Glaswerk Schott & Gen Optical silicate glasses with a refractive index that is low in relation to the mean dispersion or the ª † value
JPH01133956A (en) * 1987-11-20 1989-05-26 Canon Inc Glass composition for distributed refractive index lens
JP2795326B2 (en) * 1991-04-05 1998-09-10 株式会社オハラ Optical glass
JP2908604B2 (en) * 1991-04-09 1999-06-21 株式会社オハラ Optical glass
US5320985A (en) * 1992-10-01 1994-06-14 Kabushiki Kaisha Ohara Low refractive optical glass of a flint glass type
DE4402537C2 (en) * 1994-01-28 1996-07-25 Schott Glaswerke Lead-free optical heavy flint glass

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11306021B2 (en) 2018-11-26 2022-04-19 Owens Coming Intellectual Capital, LLC High performance fiberglass composition with improved elastic modulus
US11524918B2 (en) 2018-11-26 2022-12-13 Owens Corning Intellectual Capital, Llc High performance fiberglass composition with improved specific modulus

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JP3073474B2 (en) 2000-08-07
FR2755125B1 (en) 2000-01-07
GB9720752D0 (en) 1997-12-03
JPH10139473A (en) 1998-05-26
GB2318576A (en) 1998-04-29
DE19644736C1 (en) 1997-11-27
MY122044A (en) 2006-03-31
GB2318576B (en) 2000-03-15
FR2755125A1 (en) 1998-04-30
CN1182721A (en) 1998-05-27

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