CN104003615A - Environmentally friendly optical glass, glass preform, optical element and optical instrument - Google Patents

Environmentally friendly optical glass, glass preform, optical element and optical instrument Download PDF

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Publication number
CN104003615A
CN104003615A CN201310058615.5A CN201310058615A CN104003615A CN 104003615 A CN104003615 A CN 104003615A CN 201310058615 A CN201310058615 A CN 201310058615A CN 104003615 A CN104003615 A CN 104003615A
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China
Prior art keywords
optical glass
environmental protection
glass
protection optical
optical
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CN201310058615.5A
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Chinese (zh)
Inventor
毛露路
匡波
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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Priority to CN201310058615.5A priority Critical patent/CN104003615A/en
Priority to CN201710874397.0A priority patent/CN107473584A/en
Publication of CN104003615A publication Critical patent/CN104003615A/en
Pending legal-status Critical Current

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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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • 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)
  • Physics & Mathematics (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)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)

Abstract

The invention provides an environmentally friendly optical glass. Expensive Nb2O5 and Li2O, and environmental pollution PbO and As2O3 are not contained in the optical glass, and the optical performances of the optical glass can satisfy that the refractive index is 1.58-1.65 and the Abbe number is 40-50. The environmentally friendly optical glass comprises 40-60wt% of SiO2, 1-10wt% of B2O3, 12-32wt% of BaO, 1-8wt% of ZnO, 2-12wt% of TiO2, 2-12wt% of K2O, 1-8wt% of Na2O, 0-8wt% of CaO, 0-5wt% of ZrO2 and 0-0.1wt% of Sb2O3. The TiO2 component is reasonably adjusted in the invention, so the light transmission rate of the glass is excellent, the wavelength lambda80 is less than 390nm when the transmittance reaches 80%, and the wavelength lambda5 is less than 350nm when the transmittance reaches 5%.

Description

Environmental protection optical glass, gas preform, optical element and opticinstrument
Technical field
The present invention relates to a kind of opticglass, the environmental protection optical glass that particularly relate to a kind of specific refractory power (nd) and be 1.58～1.65, Abbe number (vd) is 40～50, and the prefabricated component being formed by this opticglass, optical element and opticinstrument.
Background technology
In traditional barium flint optical glass component, contain a large amount of PbO and as the As of finings 2o 3.Along with the increasingly stringent of legislations of environmental protection, the most countries regulations such as Europe, the U.S., China except allowing to add PbO and As in military glass and radiation shielding glass 2o 3in addition, other purposes glass can not contain without exception to human body and harmful PbO and the As of environment 2o 3.So Ge great opticinstrument manufacturers refusal is used and contains PbO and As 2o 3opticglass.This just requires us to develop a kind of new glass ingredient, can meet service requirements, can not contain environmentally harmful material again, requires cost of material cheap simultaneously, can produce continuously at low cost in a large number.
For specific refractory power between between 1.58～1.65, the unleaded barium flint optical glass of Abbe number between 40～50, in previous patent document, comprised some optical constants at this scope or the approaching crown glass of scope therewith.Yet just opticglass production field low cost, quantity-produced require at present, more or less there are some shortcomings in these glass ingredients.
CN101549955A discloses a kind of opticglass, wherein contains a large amount of PbO, can not meet above-mentioned environmental requirement.JP8048538A discloses a kind of opticglass, the Nb that contains 6-35% 2o 5, contain the fluorochemical of 0.1-10% simultaneously.Nb 2o 5be a kind of very expensive raw material, in this component, add so a large amount of Nb 2o 5will certainly cause raw materials cost to rise.In addition, add the fluorochemical of 0.1-10%, in actual production process, can discharge fluoride gas and dust, increase carrying capacity of environment and processing cost.
In the disclosed opticglass of CN1207230C and CN1044223C, TiO 2content higher, in CN1044223C component, contain the TiO up to 21-25.2% 2although, TiO 2add specific refractory power and the dispersion that can promote significantly glass, but along with TiO 2content increase, opticglass is easily painted, an important indicator light transmission rate of opticglass can significantly worsen.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of expensive Nb that do not contain 2o 5and Li 2o, and the PbO of contaminate environment and As 2o 3, it is 1.58～1.65 that while optical property meets specific refractory power, the environmental protection optical glass that Abbe number is 40～50.
The technical scheme that technical solution problem of the present invention adopts is: environmental protection optical glass, glass density is 3.3g/cm 3below, specific refractory power is 1.58～1.65, and Abbe number is 40～50, and transition temperature is below 600 ℃, corresponding wavelength X when transmittance reaches 80% 80be less than 390nm, corresponding wavelength X when transmittance reaches 5% 5be less than 350nm; Water-fastly act as 1 grade, acidproofly act as 1 grade, do not add Nb 2o 5, Li 2o, PbO, As 2o 3and fluorochemical.
Further, consist of by weight percentage: SiO 2: 40～60%, B 2o 3: 1～10%, BaO:12～32%, ZnO:1～8%, TiO 2: 2～12%, K 2o:2～12%, Na 2o:1～8%, CaO:0～8%, ZrO 2: 0～5%, Sb 2o 3: 0～0.1%.
Further, NaO 2with K 2the total amount of O is 10～20%.
Further, SiO 2: 40～55%.
Further, B 2o 3: 2～6%.
Further, BaO:15～30%.
Further, ZnO:2～5%.
Further, TiO 2: 5～10%.
Further, K 2o:6～10%.
Further, Na 2o:1～5%.
Further, CaO:0～5%.
Further, ZrO 2: 0～3%.
Environmental protection optical glass, consists of by weight percentage: SiO 2: 40～60%, B 2o 3: 1～10%, BaO:12～32%, ZnO:1～8%, TiO 2: 2～12%, K 2o:2～12%, Na 2o:1～8%, CaO:0～8%, ZrO 2: 0～5%, Sb 2o 3: 0～0.1%.
Further, NaO 2with K 2the total amount of O is 10～20%.
Further, SiO 2: 40～55%.
Further, B 2o 3: 2～6%.
Further, BaO:15～30%.
Further, ZnO:2～5%.
Further, TiO 2: 5～10%.
Further, K 2o:6～10%.
Further, Na 2o:1～5%.
Further, CaO:0～5%.
Further, ZrO 2: 0～3%.
The gas preform that adopts above-mentioned environmental protection optical glass to make.
The optical element that adopts above-mentioned environmental protection optical glass to make.
The opticinstrument that adopts above-mentioned environmental protection optical glass to make.
The invention has the beneficial effects as follows: do not add expensive Nb 2o 5, Li 2o, has reduced production cost, has saved resource; By reasonable adjustment TiO 2component, makes the light transmission rate of glass excellent; Do not contain PbO, As 2o 3with pollution components such as fluorochemicals, the specific refractory power of the environmental protection optical glass obtaining is 1.58～1.65, and Abbe number is 40～50, and the transition temperature of glass is below 600 ℃, and density is 3.3g/cm 3corresponding wavelength X when below, transmittance reaches 80% 80be less than 390nm, corresponding wavelength X when transmittance reaches 5% 5be less than 350nm.
Embodiment
To describe each component of opticglass of the present invention below, except as otherwise noted, the ratio of each component concentration is to represent by % by weight.
SiO 2being important glass-former oxide compound, playing skeleton function in glass structure, is the basis that opticglass is realized optical constant, and the number of its content is closely related with melt characteristic with the chemical stability of glass.In the present invention, work as SiO 2during containing quantity not sufficient 40%, the chemical stability of glass can reduce; But when its content surpasses 60%, be difficult to maintain the optical constant of glass, also can significantly improve the melt temperature of glass simultaneously.In order to obtain the glass that chemical stability is excellent especially, take into account its melt characteristic, SiO of the present invention simultaneously 2content is 40～60%, is preferably 40～55%.
B 2o 3be the component that must contain in the present invention, when it is when the quantity not sufficient 1%, the melt characteristic of glass is bad, if when its content is higher than 10% time, glass volatility when melting increases, the devitrification characteristic variation of while glass, therefore, B 2o 3content is defined as 1～10%, is preferably 2～6%.
BaO is the component that must contain in the present invention, can improve specific refractory power and the devitrification resistance property of glass.In the present invention, when the content of BaO is lower than 12% time, can not reach required optical constant, if when content surpasses 32%, easily data are unstable in continuous smelting, also can add heavy corrosion and produce body of heater.Therefore, BaO content is defined as 12～32%, is preferably 15～30%.
TiO 2in the present invention for improving specific refractory power and the dispersion of glass, to reach needed optical constant.Meanwhile, TiO 2can also improve significantly mechanical property and the chemical stability of glass.But, if TiO 2content lower than 2%, glass can not reach desired optical constant so, if content, higher than 12%, can cause the remarkable deterioration of light transmission rate.Therefore, TiO 2content is 2～12%, is preferably 5～10%.
The Main Function of ZnO is to regulate the optical constant of glass, also can improve the surface gloss of glass and the softening temperature that reduces glass simultaneously.If the content of ZnO, lower than 1%, improves DeGrain; If content surpasses 8%, can cause the remarkable increase of frit cost.Therefore, ZnO content is 1～8%, is preferably 2～5%.
Na 2o not only can regulate the optical constant of glass, can also reduce solvent temperature and the high temperature viscosity of glass, is conducive to save energy and reduce the cost, and also helps the eliminating of Bubbles in Glass simultaneously.In order to reach effect of the present invention, Na 2the content of O is 1～8%, is preferably 1～5%.
K 2o is one of the component that must add of the present invention, for the solvent temperature that regulates optical constant and reduce glass.When its content is lower than 2% time, cannot reach above-mentioned effect; If content surpasses 12%, can cause the deterioration of chemical durability of glass.Therefore, K 2o content is 2～12%, is preferably 6～10%.
In addition, work as NaO 2with K 2the total amount of O reaches 10% when above, could significantly reduce solvent temperature and the high temperature viscosity of glass.But work as NaO 2with K 2when the total amount of O surpasses 20%, the chemical stability of glass can worsen.Therefore, NaO 2with K 2the total amount of O is 10～20%.
CaO can improve stability, glass, can also when melting is produced, help raw material fusing, but its content is higher than 8% time, and the tendency towards devitrification of glass increases, so the content of CaO is defined as 0～8%, is preferably 0～5%.
ZrO 2viscosity, hardness, elasticity, specific refractory power and the chemical stability of opticglass can be improved, and the thermal expansivity of glass can be reduced.Work as ZrO 2content while surpassing 5%, will there is crystallization, and reduce the devitrification resistance of glass.Therefore, ZrO 2content be 0～5%, preferred content is 0～3%.
Sb 2o 3as finings, use in the present invention, its content range is 0～0.1%, is preferably and does not add.
To the performance of opticglass of the present invention be described below.
Specific refractory power and Abbe number are according to < < GB/T7962.1-1987 colouless optical glass testing method specific refractory power and abbe number > > test.
Transition temperature (Tg) is according to < < GB/T7962.16-1987 colouless optical glass testing method linear expansivity, transition temperature and sag temperature > > test, that is: sample is in certain temperature range, 1 ℃ of the every rising of temperature, on the expansion curve of sample, low-temperature region and the extension of high-temperature area straight line portion are intersected to the corresponding temperature of its intersection point.
Density is tested according to < < GB/T7962.20-1987 colouless optical glass testing method density measurement method > >.
Water-fast effect stability D w(powder method), by the test of GB/T17129 testing method, according to following formula, calculate:
D W＝(B-C)/(B-A)*100
In formula: D w-glass leaches percentage ratio (%)
The quality of B-strainer and sample (g)
The quality (g) of sample after C-strainer and erosion
A-filter quality (g)
By the leaching percentage ratio calculating, the water-fast effect of opticglass is stablized to D wbeing divided into 6 classes sees the following form.
Classification 1 2 3 4 5 6
Leach percentage ratio (D W) ＜0.04 0.04-0.10 0.10-0.25 0.25-0.60 0.60-1.10 ＞1.10
Acidproof effect stability D a(powder method), tests by GB/T17129 testing method.
Opticglass shortwave transmitted spectrum degree of staining (λ for characteristic 80/ λ 5) represent.Be that thickness of sample is 10mm ± 0.1mm, λ 80refer to wavelength corresponding when glass transmittance reaches 80%, λ 5refer to wavelength corresponding when glass transmittance reaches 5%.
Through test, opticglass of the present invention has following performance: density (ρ) is 3.3g/cm 3below; Specific refractory power (nd) 1.58～1.65; Abbe number (vd) is 40～50; Transition temperature (Tg) is below 600 ℃; Corresponding wavelength X when transmittance reaches 80% 80be less than 390nm, corresponding wavelength X when transmittance reaches 5% 5be less than 350nm; D wit is 1 grade; D ait is 1 grade.
The present invention also provides a kind of optical element, formed, and described optical element can be applied to the equipment such as digital camera, digital camera, camera cell phone by above-mentioned opticglass according to method well known to those skilled in the art.
Embodiment
In order further to understand technical scheme of the present invention, by describing the embodiment of opticglass of the present invention, should be noted that below, these embodiment do not limit the scope of the invention.
The embodiment 1～30th showing in table 1～table 3, by weighing according to the ratio of each embodiment shown in table 1～3 and hybrid optical common raw material (as oxide compound, oxyhydroxide, carbonate, nitrate and fluorochemical) for glass, mixing raw material is placed in platinum crucible, melting in certain temperature, and after fusing, clarification, stirring and homogenizing, obtain not having bubble and do not contain the not homogeneous melten glass of dissolved substance, this melten glass casting mold in mould is also annealed and formed.
The composition of the embodiment of the present invention 1～30 and specific refractory power (nd), Abbe number (vd), density (ρ), glass transformation temperature (Tg), water-fast effect stability (D w), acidproof effect stability (D a), degree of staining (λ 80/ λ 5) result in table 1～3, represent together.In these tables, the composition of each component represents by % by weight.
Table 1
Table 2
Table 3
By the embodiment in above-mentioned table 1～table 3, can find out, glass of the present invention does not add expensive Nb 2o 5and Li 2o, has reduced production cost, has saved resource; By reasonable adjustment SiO 2, TiO 2etc. component, make the light transmission rate of glass excellent, not containing PbO, As 2o 3with the pollution components such as fluorochemical, make glass density (ρ) for 3.3g/cm 3below, specific refractory power (nd) is 1.58～1.65, and Abbe number (vd) is 40～50, and transition temperature (Tg) is below 600 ℃, corresponding wavelength X when transmittance reaches 80% 80be less than 390nm, corresponding wavelength X when transmittance reaches 5% 5be less than 350nm; Water-fastly act as 1 grade, acidproofly act as 1 grade.

Claims (26)

1. environmental protection optical glass, is characterized in that, glass density is 3.3g/cm 3below, specific refractory power is 1.58～1.65, and Abbe number is 40～50, and transition temperature is below 600 ℃, corresponding wavelength X when transmittance reaches 80% 80be less than 390nm, corresponding wavelength X when transmittance reaches 5% 5be less than 350nm; Water-fastly act as 1 grade, acidproofly act as 1 grade, do not add Nb 2o 5, Li 2o, PbO, As 2o 3and fluorochemical.
2. environmental protection optical glass as claimed in claim 1, is characterized in that, consists of by weight percentage: SiO 2: 40～60%, B 2o 3: 1～10%, BaO:12～32%, ZnO:1～8%, tiO 2: 2～12%, K 2o:2～12%, Na 2o:1～8%, CaO:0～8%, ZrO 2: 0～5%, Sb 2o 3: 0～0.1%.
3. environmental protection optical glass as claimed in claim 2, is characterized in that, NaO 2with K 2the total amount of O is 10～20%.
4. environmental protection optical glass as claimed in claim 2, is characterized in that, SiO 2: 40～55%.
5. environmental protection optical glass as claimed in claim 2, is characterized in that, B 2o 3: 2～6%.
6. environmental protection optical glass as claimed in claim 2, is characterized in that, BaO:15～30%.
7. environmental protection optical glass as claimed in claim 2, is characterized in that, ZnO:2～5%.
8. environmental protection optical glass as claimed in claim 2, is characterized in that, TiO 2: 5～10%.
9. environmental protection optical glass as claimed in claim 2, is characterized in that, K 2o:6～10%.
10. environmental protection optical glass as claimed in claim 2, is characterized in that, Na 2o:1～5%.
11. environmental protection optical glass as claimed in claim 2, is characterized in that CaO:0～5%.
12. environmental protection optical glass as claimed in claim 2, is characterized in that ZrO 2: 0～3%.
13. environmental protection optical glass, is characterized in that, consist of by weight percentage: SiO 2: 40～60%, B 2o 3: 1～10%, BaO:12～32%, ZnO:1～8%, TiO 2: 2～12%, K 2o:2～12%, Na 2o:1～8%, CaO:0～8%, ZrO 2: 0～5%, Sb 2o 3: 0～0.1%.
14. environmental protection optical glass as claimed in claim 13, is characterized in that NaO 2with K 2the total amount of O is 10～20%.
15. environmental protection optical glass as claimed in claim 13, is characterized in that SiO 2: 40～55%.
16. environmental protection optical glass as claimed in claim 13, is characterized in that B 2o 3: 2～6%.
17. environmental protection optical glass as claimed in claim 13, is characterized in that BaO:15～30%.
18. environmental protection optical glass as claimed in claim 13, is characterized in that ZnO:2～5%.
19. environmental protection optical glass as claimed in claim 13, is characterized in that TiO 2: 5～10%.
20. environmental protection optical glass as claimed in claim 13, is characterized in that K 2o:6～10%.
21. environmental protection optical glass as claimed in claim 13, is characterized in that Na 2o:1～5%.
22. environmental protection optical glass as claimed in claim 13, is characterized in that CaO:0～5%.
23. environmental protection optical glass as claimed in claim 13, is characterized in that ZrO 2: 0～3%.
24. adopt the gas preform that in claim 1～23, the environmental protection optical glass described in arbitrary claim is made.
25. adopt the optical element that in claim 1～23, the environmental protection optical glass described in arbitrary claim is made.
26. adopt the opticinstrument that in claim 1～23, the environmental protection optical glass described in arbitrary claim is made.
CN201310058615.5A 2013-02-25 2013-02-25 Environmentally friendly optical glass, glass preform, optical element and optical instrument Pending CN104003615A (en)

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CN201310058615.5A CN104003615A (en) 2013-02-25 2013-02-25 Environmentally friendly optical glass, glass preform, optical element and optical instrument
CN201710874397.0A CN107473584A (en) 2013-02-25 2013-02-25 Environmental protection optical glass, gas preform, optical element and optical instrument

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105819683A (en) * 2016-03-04 2016-08-03 成都光明光电股份有限公司 Environmentally friendly optical glass and optical element
CN107098583A (en) * 2017-05-04 2017-08-29 湖北戈碧迦光电科技股份有限公司 A kind of optical glass
CN110550860A (en) * 2019-09-30 2019-12-10 成都光明光电股份有限公司 Optical glass

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109205616B (en) * 2018-11-21 2021-06-25 成都光明光电股份有限公司 Optical glass, glass preform, optical element and optical instrument
CN111217519A (en) * 2018-11-27 2020-06-02 宜城市泳瑞玻璃科技有限公司 Environment-friendly optical glass
CN109896740B (en) * 2019-04-24 2022-04-22 成都光明光电股份有限公司 Optical glass and optical element

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1214324A (en) * 1997-09-03 1999-04-21 肖特玻璃制造厂 Lead-free optical barium flint glass
DE19827568C1 (en) * 1998-06-20 2000-01-05 Schott Glas Lead-free optical barium flint glasses, light flint glasses and crown glasses
EP1275620B1 (en) * 2001-07-09 2007-10-24 Eurokera A lead-free enamel composition, the corresponding enamels and glassceramic articles, a new lead-free mineral glass

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1214324A (en) * 1997-09-03 1999-04-21 肖特玻璃制造厂 Lead-free optical barium flint glass
DE19827568C1 (en) * 1998-06-20 2000-01-05 Schott Glas Lead-free optical barium flint glasses, light flint glasses and crown glasses
EP1275620B1 (en) * 2001-07-09 2007-10-24 Eurokera A lead-free enamel composition, the corresponding enamels and glassceramic articles, a new lead-free mineral glass

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105819683A (en) * 2016-03-04 2016-08-03 成都光明光电股份有限公司 Environmentally friendly optical glass and optical element
CN107098583A (en) * 2017-05-04 2017-08-29 湖北戈碧迦光电科技股份有限公司 A kind of optical glass
CN107098583B (en) * 2017-05-04 2019-10-29 湖北戈碧迦光电科技股份有限公司 A kind of optical glass
CN110550860A (en) * 2019-09-30 2019-12-10 成都光明光电股份有限公司 Optical glass

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Application publication date: 20140827