CN1234376A - Leadfree lanthanum-contained crown glass and lanthanum-contained flint glass - Google Patents

Leadfree lanthanum-contained crown glass and lanthanum-contained flint glass Download PDF

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Publication number
CN1234376A
CN1234376A CN 99105396 CN99105396A CN1234376A CN 1234376 A CN1234376 A CN 1234376A CN 99105396 CN99105396 CN 99105396 CN 99105396 A CN99105396 A CN 99105396A CN 1234376 A CN1234376 A CN 1234376A
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glass
weight
lanthanum
contain
zno
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CN1200898C (en
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D·格拉波夫斯基
U·科尔贝格
M·温克勒－特鲁德维格
S·沃尔夫
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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
    • C03C3/062—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

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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)
  • Glass Compositions (AREA)

Abstract

A lead-free lanthanum crown glass and a lead-free lanthanum flint glass have a refractive index nd of 1.66-1.76 and an Abbe number vd of 46-57. The glasses have a composition consisting of, by weight on the oxide basis, 1-9% SiO2, 29-43.5% B2O3, 27-40% La2O3, 5.5-10% CaO, 0-3.5% SrO, 0-4.5% MgO, 3.5-10% ZnO, 0.1-3.5% TiO2 and 3.5-9% ZrO2.

Description

Unleadedly contain lanthanum crown glass and contain lanthanum flint glass
The present invention relates to unleadedly contain lanthanum crown glass and contain lanthanum flint glass, the refractive index n of these glass dBe 1.66-1.76, Abb v dBe 46-57.
Because glass ingredient plumbous oxide and white arsenic become the topic that the public discusses because of environment is polluted, thus opticinstrument manufacturers needs unleaded and preferably also be not trioxygen-containingization two arsenic have the glass of optical property separately.
Only adopt one or more compositions to replace plumbous oxide can not cause forming required optics and the glass properties of bringing by plumbous oxide usually.Opposite with it, must form glass and carry out new exploitation and change widely.
As said hereinafter, description of the Prior Art have these zone and crown glasss of near zone optical numerical value, but there is number of drawbacks in these glass.
DE-B1 061976 has described a kind of parent glass, and it is from having higher La 2O 3The B of content 2O 3-SiO 2-La 2O 3The glass that is made by this parent glass has also been described by system, the document, and it is to add aluminum oxide and/or yttrium oxide and metal oxide, particularly alkaline earth metal oxide, zirconium white, zinc oxide and/or Cadmium oxide or only randomly have Al 2O 3And Y 2O 3And have lower B under the situation of other additive 2O 3Content.These glass are owing to these compositions become very expensive, and they are difficult to fusing or have inappropriate devitrification stability.
English Patent 1136239 has been described a kind of electroluminescence bulb, and it comprises contains the glass that a kind of oxide compound by rare earth metal, network former and bivalent metal oxide are formed, and has wherein imbedded phosphorus.Comprise other some additives, composition that it is possible and weight percent change in the scope of a broad.These glass can not satisfy the high request of opticglass.
JP55-121925A has described a kind of lanthanum dense flint glass that contains, and promptly has the glass of high refractive index and low Abb, and it contains ZnO and SrO and/or BaO as bivalent metal oxide.Other possible additive is MgO and a spot of CaO.SiO 2It only is optional ingredients.These have with the glass of said different optical grade herein and also do not have good devitrification stability.
German Patent 2265703 C2 have described by B 2O 3-Gd 2O 3-La 2O 3The opticglass that system forms.For stable to devitrification, the Gd that these glass need 2% weight at least and are up to 50% weight 2O 3Make these glass very expensive with the composition that has this costliness so in a large number.
JP62-100449A has described maximum needs 2% weight Sb 2O 3Glass.If use this composition with this quantity, just must adopt higher security measures protecting relevant personnel in process of production, and the also decline greatly of the transmittance of this glass.This glass must contain Li in addition 2O, this composition has increased the possibility of devitrification.
Also must contain Li like the category of glass among the JP60-221338A 2O.In addition, they are except La 2O 3Also need to be up to the very expensive composition Y of 20% weight in addition 2O 3, to change specific refractory power.The glass of said high ZnO content also contains Y among the JP54-6243B 2O 3
The glass of mentioning among the JP53-4023A needs HfO 2Be used for replacing La 2O 3This composition make this glass very expensive equally.
The objective of the invention is to find lead-free optical to contain lanthanum crown glass and contain lanthanum flint glass, the refractive index n of these glass dBe 1.66-1.76, Abb v dBe 46-57, these glass have good fusing and processing property and can produce at an easy rate.This also comprises the crystallization-stable that needs are suitable.
This purpose realizes by said glass in the claim 1.
This glass contains 29-43.5% weight (preferably mostly being most 43% weight) glass forming substances B 2O 3Under higher content, chemical stability will reduce.Because minimum B 2O 3Content is higher, glass forming substances SiO 2Content can remain in the 1-9% weight range.This lower SiO 2Content at first can produce positive effect to the melting properties of admixtion, promptly reduces fusing point and shortens fusing time.Secondly can more easily import quite a large amount of lanthanum trioxides.
This is because this glass contains 27-40% weight (being preferably 29-40% weight) La 2O 3This scope obtains required optical grade, particularly Shi Du Abb, simultaneously higher specific refractory power easily.La in addition 2O 3The transparency of glass and its crystallization-stable of raising have been increased.Further increase La 2O 3Content will cause different n dAnd v dNumerical value and the cost of admixtion is increased with there is no need.
This glass contains 0.1-3.5% weight (being preferably 0.1-3% weight) TiO 2With 3.5-9% weight (being preferably 4-9% weight) ZrO 2Under these minimum content, these two kinds of compositions have improved chemical stability.They not only help said high B 2O 3Content, even exceed people and unexpectedly compare the alkaline-resisting and acid resistance of also having improved glass with the flint glass with identical optical grade of routine.
This glass contains 3.5-10% weight (being preferably 4-10% weight) ZnO.Under this minimum content, can improve resistance to fouling and reduce devitrification.
Though increase TiO 2, ZrO 2Make it to surpass given separately maximum value with the content of ZnO, can have positive effect to devitrification behavior at the beginning, promptly further improve devitrification stability, but it can have a negative impact the melting properties of admixtion.
In order not to be subjected to the melting properties restriction to be issued to high devitrification stability basically, it is 5.5-10% weight (being preferably 5.5-9.5% weight) CaO that this glass contains quantity.Under lower content, the devitrification stability of glass will reduce, and under higher content, chemical resistant properties will reduce.
In order further to improve devitrification stability, this glass can contain and be up to 3.5% weight (preferably being up to 3% weight) SrO and be up to 4.5% weight (be preferably and be up to 4% weight) MgO.If surpass high-content separately, chemical resistant properties can reduce.
In a kind of specific embodiment of the present invention, this contains lanthanum crown glass and contains lanthanum flint glass and do not contain SrO or MgO.These glass contain quite few ZnO (maximum 6% weight) and the quite few CaO (mostly being 7.5% weight most) and the La of at least 35% weight 2O 3
Therefore, they preferably contain (% weight is based on oxide compound) SiO 21-9, B 2O 329-43, La 2O 335-40, CaO 5.5-7.5, ZnO 4-6, TiO 20.1-3, ZrO 24-9, and its refractive index n dBe 1.69-1.76 and Abb v dBe 46-54.
In the specific embodiment of another kind of the present invention, this glass contains SrO and/or MgO, more precisely, is at least 0.1% weight SrO+MgO.This glass is to have better devitrification stability and lower density with the glassy phase that does not contain MgO and do not contain SrO than its advantage.
In this group glass, at first contain SrO but the glass that do not contain MgO is represented a kind of specific variation scheme of the present invention.They are different from the said hereinafter SrO of not conforming to but contain the glass of MgO, and they have lower density and lower thermal expansivity and preferably have following composition (% weight is based on oxide compound):
SiO 2(2.5-4.5 being preferably 2.5-4);
B 2O 335 (being preferably more than 35)-42 (being preferably 37-40);
La 2O 331-40 (being preferably 32-38);
CaO 6-8 (being preferably 7-8);
SrO 0.1-2 (being preferably 0.5-1.5);
ZnO 4.5-7.5 (being preferably 5-7);
TiO 2(0.5-2.5 being preferably 1-2.5);
ZrO 25-9 (being preferably 6-7).
The refractive index n of this glass dBe 1.69-1.75, Abb v dBe 48-54, the optical data with glass of preferred composition is 1.70≤n d≤ 1.72 and 48≤v d≤ 51.
Secondly above-mentioned MgO of containing but do not contain SrO glass and represent a kind of specific embodiment of the present invention.Preferably they have following composition (weight percent is based on oxide compound): SiO 25 (being preferably)-7.5, B greater than 5 2O 330-39, La 2O 330-39, CaO 6-8, MgO 1-3, ZnO 6-9, TiO 20.5-2.5, ZrO 25-8.
Its refractive index n of this glass dBe 1.69-1.75 and Abb v dBe 48-54.
In the compositing range of being mentioned in main claim, also have two groups of preferred glass, they contain different TiO 2Content.
At first be to contain magnesium oxide and TiO 2Content promptly has the glass (weight percent is based on oxide compound) of following composition: SiO at the glass of said range limit 23.5-4.5, B 2O 341-43, La 2O 327-41, CaO 8-10, MgO 3.5-4.5, ZnO 3.5-4.5, TiO 22.5-3.5, ZrO 23.5-4.5.Its refractive index n of this glass dBe 1.68-1.70 and Abb v dBe 49-51.
Second group of glass is by containing MgO and SrO and low TiO 2The glass of content is formed.These glass have following composition (weight percent is based on oxide compound): SiO 23.5-4.5, B 2O 341-43, La 2O 327-31, CaO 8.5-9.5, SrO 2.5-3.5, MgO 3.5-4.5, ZnO 3.5-4.5, TiO 20.1-1, ZrO 23.5-4.5.These glass are to contain lanthanum crown glass, its Abb v dBe 54-56 and refractive index n dBe 1.66-1.69.
In order to improve the quality of glass, can in admixtion, add known multiple finings with convention amount, with fining glass.Therefore this glass has good especially inner glass quality, does not have bubble and band vitta line.
If used finings is not As 2O 3But Sb for example 2O 3, preferably its amount mostly is 0.3% weight most, not loss aspect glass quality, and crown glass of the present invention does not contain arsenic.
The present invention to have suitable optical property and do not have alkalimetal oxide, BaO, Al except the impurity of routine in order to make 2O 3, Nb 2O 5, Y 2O 3And Ta 2O 3Glass.This is for melting properties and crystallization-stable and have multiple benefit for low cost is made glass.
This novel glass has following advantage:
This glass does not contain PbO and is not preferably containing As in the embodiment yet 2O 3With traditional glassy phase ratio that contains PbO and have identical optical grade, they are " long property ", and promptly the manipulable temperature range of this glass is bigger.
These glass have higher chemical resistant properties, particularly very high alkali resistance.Therefore with traditional glassy phase ratio that contains bright PbO and have the identical optical grade, they have better acid resistance (the 8th flint glass F (referring to embodiment and table 2) for example, the acid resistance level that has is 52.0, rather than 52.3 (containing PbO's)) and better alkali resistance (for example the alkali resistance level that has of the 8th flint glass F is 1.0, rather than 1.2 (containing PbO's)).The high chemical resistance of this glass is outbalance for its further mechanical treatment as grinding and polishing.
This glass has higher crystallization-stable.This makes that this glass can be at sizable melting unit, as making in the optics kiln.Measuring of crystallization-stable is the devitrification upper limit or the viscosity under this temperature.For continuous production, it should 〉=1000 fens handkerchiefs.This can realize by this novel glass.
This glass is fusing and processing easily.The density of this glass is quite low, is≤4.0 gram/cubic centimetres.
Embodiment
Make 8 examples of novel glass by the raw material of routine.
Table 2 expression composition (weight percent is based on oxide compound), refractive index n separately d, Abb v d, density p (gram/cubic centimetre), thermalexpansioncoefficient 20/300(10 -6/ K) and the glass transformation temperature Tg of this glass (℃).
These novel glass are produced as follows: with the raw material of oxide compound, preferably carbonate and oxide compound are weighed.Add finings, then these compositions are mixed fully.Glass batch about 1200-1360 ℃ of fusing down, is then clarified also homogenizing well.Teeming temperature is 1000-1080 ℃.
Melt example of table 1 expression.
Table 1
Melt example for the glass of 100 kilograms of calculating
Oxide compound % weight raw material starting weight [kg]
SiO 2 1.0 SiO 2 1.00
B 2O 3 42.9 H 3BO 3?76.23
CaO 5.5 CaCO 3 9.75
TiO 2 0.1 TiO 2 0.10
ZnO 5.00 ZnO 5.01
ZrO 25.4 ZrO 25.51La 2O 340.0 La 2O 340.08Sb 2O 30.10 Sb 2O 30.10 the performance of the glass that is obtained is shown in the example 1 of table 2.
Table 2 glass is formed (weight % is based on oxide compound)
And the salient features of this glass
1 2 3 4 5 6 7 8SiO 2 1.0 8.9 3.9 9.0 3.9 2.9 3.7 6.2B 2O 3 42.9 29.0 42.9 29.9 43.0 38.8 38.8 34.6CaO 5.5 9.0 9.0 5.5 9.0 7.5 7.5 7.5SrO - 3.0 3.0 - - 1.0 1.0 -MgO - 4.0 4.0 - 4.0 - - 2.0ZnO 5.0 10.0 4.0 4.0 4.0 5.9 5.9 7.5TiO 2 0.1 0.1 0.1 3.0 3.0 2.5 1.5 1.4ZrO 2 5.4 6.9 4.0 8.5 4.0 6.1 6.4 6.5La 2O 3 40.0 29.0 29.0 40.0 29.0 35.2 35.1 34.3Sb 2O 3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1n d 1.7033?1.7086 1.6752?1.7481 1.6898?1.7144?1.7091?1.7182v d 53.78 51.47 55.39 46.43 50.55 48.20 50.10?50.16ρ[g/cm 3]?3.66 3.70 3.41 3.88 3.39 3.02 3.00 3.70α 20/300 6.50 7.56 6.99 6.87 6.73 4.86 4.81 6.98[10 -6/K]Tg[℃] 646 615 634 652 634 713 713 622

Claims (12)

1. unleadedly contain lanthanum crown glass and contain lanthanum flint glass, the refractive index n of this glass dBe 1.66-1.76, Abb v dBe 46-57, it is characterized in that this glass has following composition (% weight is based on oxide compound):
SiO 2 1-9
B 2O 3 29-43.5
La 2O 3 27-40
CaO 5.5-10
SrO 0-3.5
MgO 0-4.5
ZnO 3.5-10
TiO 2 0.1-3.5
ZrO 23.5-9 and the finings of conventional quantity if necessary.
According to claim 1 contain lanthanum crown glass and contain lanthanum flint glass, it is characterized in that this glass has following composition (% weight is based on oxide compound):
SiO 2 1-9
B 2O 3 29-43.5
La 2O 3 29-40
CaO 5.5-9.5
SrO 0-3
MgO 0-4
ZnO 4-10
TiO 2 0.1-3
ZrO 2The 4-9 and the finings of conventional quantity if necessary.
3. containing lanthanum crown glass and containing lanthanum flint glass, the refractive index n of this glass according to claim 1 or 2 dBe 1.69-1.76, Abb v dBe 46-54, it is characterized in that this glass has following composition (% weight is based on oxide compound):
SiO 2 1-9
B 2O 3 29-43
La 2O 3 35-40
CaO 5.5-7.5
ZnO 4-6
TiO 2 0.1-3
ZrO 2The 4-9 and the finings of conventional quantity if necessary.
According to claim 1 or 2 contain lanthanum crown glass and contain lanthanum flint glass, it is characterized in that this glass contains SrO and/or MgO that total amount is at least 0.1 weight.
5. according to claim 1,2 or 4 contain lanthanum crown glass and contain lanthanum flint glass, the refractive index n of this glass dBe 1.69-1.75, Abb v dBe 48-54, it is characterized in that this glass has following composition (% weight is based on oxide compound):
SiO 2 2.5-4.5
B 2O 3 35-42
La 2O 3 31-40
CaO 6-8
SrO 0.1-2
ZnO 4.5-7.5
TiO 2 0.5-2.5
ZrO 2The 5-9 and the finings of conventional quantity if necessary.
6. containing lanthanum crown glass and containing lanthanum flint glass, the refractive index n of this glass according to claim 5 dBe 1.70-1.72, Abb v dBe 48-51, it is characterized in that this glass has following composition (% weight is based on oxide compound):
SiO 2 2.5-4.5
B 2O 3 37-40
La 2O 3 32-38
CaO 7-8
SrO 0.5-1.5
ZnO 5-7
TiO 2 1-2.5
ZrO 2The 6-7 and the finings of conventional quantity if necessary.
7. according to claim 1,2 or 4 contain lanthanum crown glass and contain lanthanum flint glass, the refractive index n of this glass dBe 1.69-1.75, Abb v dBe 48-54, it is characterized in that this glass has following composition (% weight is based on oxide compound):
SiO 2 5-7.5
B 2O 3 30-39
La 2O 3 30-39
CaO 6-8
MgO 1-3
ZnO 6-9
TiO 2 0.5-2.5
ZrO 2The 5-8 and the finings of conventional quantity if necessary.
8. containing lanthanum crown glass and containing lanthanum flint glass, the refractive index n of this glass according to claim 1 dBe 1.68-1.70, Abb v dBe 49-51, it is characterized in that this glass has following composition (% weight is based on oxide compound):
SiO 2 3.5-4.5
B 2O 3 41-43
La 2O 3 27-31
CaO 8-10
MgO 3.5-4.5
ZnO 3.5-4.5
TiO 2 2.5-3.5
ZrO 23.5-4.5 and the finings of conventional quantity if necessary.
9. containing lanthanum crown glass and containing lanthanum flint glass, the refractive index n of this glass according to claim 1 dBe 1.66-1.69, Abb v dBe 54-56, it is characterized in that this glass has following composition (% weight is based on oxide compound):
SiO 2 3.5-4.5
B 2O 3 41-43
La 2O 3 27-31
CaO 8.5-9.5
SrO 2.5-3.5
MgO 3.5-4.5
ZnO 3.5-4.5
TiO 2 0.1-1
ZrO 23.5-4.5 and the finings of conventional quantity if necessary.
According among the claim 1-9 at least one contain lanthanum crown glass and contain lanthanum flint glass, it is characterized in that this glass contains 0-0.3% weight Sb 2O 3
11., it is characterized in that this glass oxygen-free arsenic except unavoidable impurities according to containing lanthanum crown glass and containing lanthanum flint glass one of at least among the claim 1-10.
12., it is characterized in that this glass oxygen-free neodymium, aluminum oxide, barium oxide and alkaline earth metal oxide except unavoidable impurities according to containing lanthanum crown glass and containing lanthanum flint glass one of at least among the claim 1-11.
CN 99105396 1998-05-06 1999-05-06 Leadfree lanthanum-contained crown glass and lanthanum-contained flint glass Expired - Lifetime CN1200898C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19820072.2 1998-05-06
DE1998120072 DE19820072C1 (en) 1998-05-06 1998-05-06 New lead-free optical lanthanum crown and flint glasses

Publications (2)

Publication Number Publication Date
CN1234376A true CN1234376A (en) 1999-11-10
CN1200898C CN1200898C (en) 2005-05-11

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CN 99105396 Expired - Lifetime CN1200898C (en) 1998-05-06 1999-05-06 Leadfree lanthanum-contained crown glass and lanthanum-contained flint glass

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JP (1) JP4213293B2 (en)
CN (1) CN1200898C (en)
DE (1) DE19820072C1 (en)
FR (1) FR2778398B1 (en)
GB (1) GB2337046B (en)
MY (1) MY122335A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100377449C (en) * 2003-04-28 2008-03-26 3M创新有限公司 Use of glasses containing rare earth oxide, alumina, and zirconia and dopant in optical waveguides
CN101982434A (en) * 2010-10-29 2011-03-02 南通晶鑫光学玻璃有限公司 Environment-friendly lanthanum optical glass TZLaF4 with high refractive index and low chromatic dispersion
CN109761492A (en) * 2019-03-27 2019-05-17 湖北戈碧迦光电科技股份有限公司 Environmentally friendly lanthanum crown optical glass and its preparation method and application

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DE10227494C1 (en) 2002-06-19 2003-12-04 Schott Glas Lead-free optical glass with specified refractive index and Abbe number, for optics, laser technology and communications, has specified composition
DE102005023134A1 (en) * 2005-05-19 2006-11-23 Patent-Treuhand-Gesellschaft für elektrische Glühlampen mbH Luminescence conversion LED
JP5727691B2 (en) * 2008-04-30 2015-06-03 株式会社オハラ Optical glass, optical element and optical instrument
JP2014196244A (en) * 2014-07-03 2014-10-16 株式会社オハラ Optical glass
JP6808385B2 (en) * 2015-11-06 2021-01-06 株式会社オハラ Optical glass, preform materials and optical elements

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100377449C (en) * 2003-04-28 2008-03-26 3M创新有限公司 Use of glasses containing rare earth oxide, alumina, and zirconia and dopant in optical waveguides
CN101982434A (en) * 2010-10-29 2011-03-02 南通晶鑫光学玻璃有限公司 Environment-friendly lanthanum optical glass TZLaF4 with high refractive index and low chromatic dispersion
CN109761492A (en) * 2019-03-27 2019-05-17 湖北戈碧迦光电科技股份有限公司 Environmentally friendly lanthanum crown optical glass and its preparation method and application

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FR2778398B1 (en) 2003-01-31
JP2000026133A (en) 2000-01-25
FR2778398A1 (en) 1999-11-12
GB2337046A (en) 1999-11-10
CN1200898C (en) 2005-05-11
GB2337046B (en) 2001-10-17
GB9909134D0 (en) 1999-06-16
MY122335A (en) 2006-04-29
DE19820072C1 (en) 1999-06-24
JP4213293B2 (en) 2009-01-21

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