CN103833219B

CN103833219B - Opticglass

Info

Publication number: CN103833219B
Application number: CN201410101679.3A
Authority: CN
Inventors: 戎俊华; 张卫; 王拓
Original assignee: Hubei New Huaguang Information Materials Co Ltd
Current assignee: Hubei New Huaguang Information Materials Co Ltd
Priority date: 2011-06-17
Filing date: 2011-06-17
Publication date: 2016-04-27
Anticipated expiration: 2031-06-17
Also published as: CN102303952B; CN103833219A; CN102303952A

Abstract

The invention provides a kind of opticglass, the specific refractory power of described opticglass is the refractive index n d of described opticglass is 1.8160, and Abbe number υ d is 46.7, described opticglass by weight percent oxide containing following component: SiO ₂, 6.8%; B ₂o ₃, 18.3%; La ₂o ₃, 34.1%; Gd ₂o ₃, 24.9%; Y ₂o ₃, 2.0%; Ta ₂o ₅, 6.2%; ZrO ₂, 5.8%; SnO ₂, 0.5%; ZnO, 1.4%; Described opticglass is not containing objectionable constituent and expensive GeO such as thorium, lead, cadmium, mercury, arsenic ₂.According to opticglass provided by the invention, there is low tendency towards devitrification and high permeability and cost is comparatively cheap.

Description

Opticglass

The divisional application that the application is the applying date is on June 17th, 2011, application number is 201110168344.X, denomination of invention is the Chinese patent application of " opticglass ".

Technical field

The present invention relates to a kind of opticglass, especially relate to a kind of opticglass of high refractive index.

Background technology

In Optical System Design, this kind of glass of high refractive index of usual employing or utilize the optical elements such as non-spherical lens sheet to accomplish miniaturization, ultrathin and wide angle, and this kind of glass more can realize this object, mate with high refractive index, low Abbe number glassy phase simultaneously, carrying out in special optical system design, can realize making up the object with correcting chromatic aberration.

This kind of glass of early stage making all contains a large amount of Ta ₂o ₅.In recent years, along with the rise in price of rare earth element, Ta ₂o ₅price sharply rise, to production cost and unfavorable, and in recent years, along with the raising of opticglass manufacture craft, state of the art, realize the low Ta of this kind of glass ₂o ₅change and stable processing performance become possibility.

As the close specific refractory power of the object of the invention, Abbe number opticglass is existing is disclosed in a large number.Particular case is as follows:

CN101857358A disclose a kind of specific refractory power 1.69 ~ 1.82, Abbe number 33 ~ 46 glass, wherein containing 4 ~ 12% TiO ₂, easily cause photochromic effect, be unfavorable for the raising of the light transmission performance of glass;

CN1510002A disclose a kind of specific refractory power 1.75 ~ 1.85, the optical glass for mold press molding of Abbe number more than 35, wherein containing 15.5 ~ 25% expensive Ta ₂o ₅;

CN101003417A disclose a kind of specific refractory power 1.74 ~ 1.83, Abbe number 32 ~ 47 environment friendly heavy-lanthanide flint glass, wherein containing 5 ~ 20% TiO ₂, easily cause photochromic effect, and be unfavorable for the light transmission performance improving glass;

CN1152836C disclose a kind of specific refractory power 1.64 ~ 1.83, Abbe number 36 ~ 46 opticglass, wherein with 10 ~ 25%SiO ₂for glass production body, the smelting temperature of glass is high;

CN1729147A discloses a kind of opticglass.With specific refractory power, Abbe number for the elements of a fix, in (1.835,46.5), (1.835,38), (1.90,40) and (1.90,35) region, wherein containing 10 ~ 25% expensive Ta ₂o ₅;

CN101117268A disclose a kind of specific refractory power more than 1.83, the high refractive index of Abbe number more than 35, wherein containing 15 ~ 25% expensive Ta ₂o ₅;

CN1182058C disclose a kind of specific refractory power 1.825 ~ 1.845, Abbe number 41 ~ 47 opticglass, wherein containing 10 ~ 15% expensive Ta ₂o ₅;

CN1876589A disclose a kind of specific refractory power 1.75 ~ 1.85, Abbe number 34 ~ 44 opticglass, wherein containing be greater than 15 and be less than 35% expensive Ta ₂o ₅.

Summary of the invention

Object of the present invention be exactly to provide a kind of specific refractory power (nd) 1.81 ~ 1.84 for above-mentioned weak point, Abbe number (υ d) in 42 ~ 47 scopes, not objectionable constituent and the expensive GeO such as thoriated, lead, cadmium, mercury, arsenic ₂composition and expensive Ta ₂o ₅content is low, has low tendency towards devitrification and the optical glass having high refractive index of high permeability.

For solving above-mentioned problem, the present invention is through repeatedly studying and finding, at low Ta in the result of test ₂o ₅content and not containing objectionable constituent and the expensive GeO such as thorium, cadmium, mercury, lead, arsenic ₂on the basis of composition, can realize having good devitrification resistance performance and required specific refractory power and Abbe.

Moreover, further to improve for the purpose of transmitance and chemical stability in research, so that complete the present invention.

The invention provides a kind of opticglass, the specific refractory power of described opticglass is 1.81≤nd≤1.84, and Abbe number is 42≤υ d≤47, described opticglass by weight percent oxide containing following component: SiO ₂, 0.2 ~ 7.5%; B ₂o ₃, 18 ~ 30%; La ₂o ₃, 33 ~ 45%; Gd ₂o ₃, 9 ~ 30%; Y ₂o ₃, 1.5 ~ 7.5%; Ta ₂o ₅, 2.0 ~ 9.5%; Nb ₂o ₅, 0 ~ 8%; ZrO ₂, 5 ~ 7%; SnO ₂, 0 ~ 1%; WO ₃, 0 ~ 1%; ZnO, 0 ~ 2%.Described opticglass is not containing objectionable constituent and expensive GeO such as thorium, cadmium, lead, mercury, arsenic ₂.

According to opticglass provided by the invention, its specific refractory power (nd) 1.81 ~ 1.84, Abbe number (υ d) in 42 ~ 47 scopes, not containing harmful composition and the expensive GeO such as thorium, cadmium, lead, mercury, arsenic ₂composition and expensive Ta ₂o ₅content is low, has low tendency towards devitrification and high permeability and cost is comparatively cheap.

Embodiment

According to opticglass provided by the invention, the specific refractory power of described opticglass is 1.81≤nd≤1.84, and Abbe number is 42≤υ d≤47, described opticglass by weight percent oxide containing following component: SiO ₂, 0.2 ~ 7.5%; B ₂o ₃, 18 ~ 30%; La ₂o ₃, 33 ~ 45%; Gd ₂o ₃, 9 ~ 30%; Y ₂o ₃, 1.5 ~ 7.5%; Ta ₂o ₅, 2.0 ~ 9.5%; Nb ₂o ₅, 0 ~ 8%; ZrO ₂, 5 ~ 7%; SnO ₂, 0 ~ 1%; WO ₃, 0 ~ 1%; ZnO, 0 ~ 2%.Described opticglass is not containing objectionable constituent and expensive GeO such as thorium, cadmium, lead, mercury, arsenic ₂.

In the preferred case, the content of said components is as follows: SiO ₂, 0.2 ~ 7.5%; B ₂o ₃, 18 ~ 26.5%; La ₂o ₃, 33 ~ 40%; Gd ₂o ₃, 9.5 ~ 26%; Y ₂o ₃, 1.5 ~ 7.5%; Ta ₂o ₅, 2.0 ~ 7.0%; Nb ₂o ₅, 0 ~ 8%; ZrO ₂, 5 ~ 7%; SnO ₂, 0 ~ 1%; WO ₃, 0 ~ 1%; ZnO, 0 ~ 2%.

In the preferred case, SiO ₂with B ₂o ₃the weight ratio of content is SiO ₂/ B ₂o ₃≤ 0.4, this can improve the crystallization property of glass, reduces the liquidus temperature of glass, can improve the shaping viscosity of glass simultaneously.

In the preferred case, by weight percentage, La ₂o ₃with Gd ₂o ₃total content be more than 48% to less than 60%, this can improve the crystallization property of glass, reduces the liquidus temperature of glass.

In the preferred case, by weight percentage, Ta ₂o ₅with Nb ₂o ₅total content be more than 6% to less than 10.5%, the optical property of glass can be ensured, the crystallization property of glass can be improved simultaneously, reduce the liquidus temperature of glass.

With opticglass of the present invention stem from boron group of the lanthanides unite and add to the present invention be very important and from but required Ta ₂o ₅, Gd ₂o ₃composition and/or Y ₂o ₃the borate salt system of content.

In the component of above-mentioned opticglass, SiO ₂composition is network former, is the composition improving devitrification resistance and chemical stability simultaneously.In order to reach above-mentioned effect, its content need more than 0.2 % by weight, but add-on more than 7.5 % by weight time, specific refractory power is difficult to reach more than 1.82, can reduce La simultaneously ₂o ₃meltbility in glass.

B ₂o ₃composition is the required composition as network former in the opticglass of the present invention containing rare earth oxide in a large number.Its content is difficult to when being less than 18 % by weight form stabilized glass, and when more than 30 % by weight, chemical stability will be deteriorated.Content lower limit is preferably 18 % by weight, and upper content limit is preferably 26.5 % by weight.

La ₂o ₃composition is the effective constituent improving glass refraction and increase Abbe number.When its content is less than 33 % by weight, the specific refractory power of glass, Abbe number are difficult to reach specified range of the present invention, but during more than 45 % by weight, tendency towards devitrification increases, and liquidus temperature raises.Therefore, for keeping satisfactory stability further, upper content limit is preferably 40 % by weight.

Gd ₂o ₃composition and La ₂o ₃the effect of composition is identical, is the effective constituent improving glass refraction and increase Abbe number equally.Its containing quantity not sufficient 9 % by weight time glass devitrification tendency will increase, in addition, during more than 30 % by weight glass devitrification be inclined to will increase.Therefore, for keeping satisfactory stability further, content lower limit is preferably 9.5 % by weight, and upper content limit is preferably 26 % by weight.

Y ₂o ₃composition and La ₂o ₃the effect of composition is identical, is equally also the effective constituent improving glass refraction, increase Abbe number.When add 1.5 % by weight and above time can improve the crystallization property of glass.But when its content is more than 7.5 % by weight, devitrification resistance property worsens.

Ta ₂o ₅composition has high effect to raising devitrification resistance and specific refractory power.But its content is less than 2% and is difficult to reach above-mentioned effect, as during more than 9.5 % by weight, devitrification resistance is easily deteriorated on the contrary, specific refractory power, Abbe number are also difficult to reach above-mentioned requirements.For above-mentioned requirements can be reached smoothly further, upper content limit preferably 7 % by weight.

Nb ₂o ₅composition has fabulous effect to raising specific refractory power, but in order to the specific refractory power that ensures glass and Abbe number, by Nb ₂o ₅as selectable composition.But Nb ₂o ₅when amount is greater than 8 % by weight, Abbe number will be caused to diminish, do not reach the lower limit 42 of Abbe number.

ZrO ₂the effect that composition has adjustment specific refractory power, reduces liquidus temperature, improves chemical stability.Its content not easily reaches above-mentioned requirements when being less than 5.0%, and during more than 7.0%, stability will be deteriorated.

WO ₃composition optionally adds as raising chemical stability, and when its content is more than 1.0%, stability, glass will be deteriorated.

SnO ₂composition optionally adds as raising chemical stability, and when its content is more than 1.0%, stability, glass will be deteriorated.

ZnO component optionally adds as raising chemical stability, and when its content is more than 2.0%, stability, glass will be deteriorated.

The preparation method of opticglass of the present invention can adopt the method for well known to a person skilled in the art, such as following methods can be adopted: mixed by all components of frit by weight percentage and be heated as molten mass at 1270 DEG C ~ 1300 DEG C, by fully clarifying at 1350 DEG C ~ 1380 DEG C, the molten glass of homogenizing flows out from fistulae, flow into and close in isolated forming mould and expand molten glass in the form of flat sheets, thus formation sheet glass, finally by traction stress relieving by annealing.

The mode of embodiment is below adopted to be explained in further detail the present invention.

embodiment 1-5 and comparative example 1-2

The content of each composition listed according to the form below 2 respectively, respectively take quartz sand, boric acid and other oxide compound (table 1 is consumption and the content of each composition in the frit of 100kg calculated amount in embodiment 2 and glass melt) that purity is more than 99%, melt at 1270 DEG C ~ 1300 DEG C in single crucible melting equipment after they are fully mixed, clarification and homogenizing at 1350 DEG C ~ 1380 DEG C afterwards, under the mold temperature of 1170 DEG C ~ 1200 DEG C, carry out drawing by required specification shaping, and after annealing, cut into required specification.

Table 1

Oxide compound	% by weight	Raw material	Weigh (KG)
				SiO ₂	2.5	SiO ₂	2.53
B ₂O ₃	27	H ₃BO ₃	48.45
				La ₂O ₃	37.8	La ₂O ₃	38.19
Gd ₂O ₃	13.0	Gd ₂O ₃	13.13
				Y ₂O ₃	4.0	Y ₂O ₃	4.04
Ta ₂O ₅	5.5	Ta ₂O ₅	5.51
				Nb ₂O ₅	2.2	Nb ₂O ₅	2.20
ZrO ₂	6.0	ZrO ₂	6.00
				WO ₃	0.5	WO ₃	0.50
SnO ₂	0.5	SnO ₂	0.50
				ZnO	1.0	ZnO	1.00

performance test

1, the measurement of refractive index n d and Abbe number υ d

Measure according to the testing method of GB/T7962.1 standard.

2、λ ₈₀：

Making thickness is 10 ± 0.1mm, has the flat glass sample be parallel to each other through optical grinding, and injecting intensity from the direction with above-mentioned plane orthogonal to this glass specimen is I _inlight, measure the intensity I of emergent ray _out, by strength ratio I _out/ I _inbe called the outside transmitance of glass.In the scope of wavelength 200 ~ 700nm, be that the wavelength of 80% is denoted as λ by outside transmitance ₈₀.

3, liquidus temperature L _t

The GM-N16P type gradient furnace of day book mountain company is used to carry out liquidus temperature L _tmensuration.

Tested according to the method described above respectively by the glass that embodiment 1-5 and comparative example 1-2 obtains, acquired results is listed in table 2.

Table 2 (wherein each component concentration represents with % by weight)

Illustrate: 1, λ ₈₀represent within the scope of wavelength 200 ~ 700nm, thickness is the outside transmitance that the described opticglass sample of 10mm does not comprise surface reflection loss, wavelength corresponding when reaching 80%; 2, L _trepresent liquidus temperature; 3, the prices of raw and semifnished materials that adopt for per kilogram theoretical glass of material cost, unit is unit/Kg glass.

The opticglass of the present invention of the embodiment 1 to 5 in table reaches required specific refractory power and Abbe number, has high light transmission rate and low liquidus temperature, is suitable for quantizing to produce.Also there is cost low, be conducive to reducing production cost.

Ta in comparative example 1 and 2 ₂o ₅composition is higher than 10%, and the material cost of glass is higher more than 100 yuan than the material cost per kilogram glass of embodiment 1 ~ 5.Glass long wave direction light transmission rate declines, and the crystallization ceiling temperature of glass is higher than the crystallization ceiling temperature of embodiment 1 ~ 5 more than 100 DEG C, is unsuitable for batch production.

Claims

1. an opticglass, is characterized in that, the refractive index n d of described opticglass is 1.8160, and Abbe number υ d is 46.7, and described opticglass is composed of the following components by weight percent oxide:

Described opticglass is not containing thorium, cadmium, mercury, lead, arsenic and GeO ₂.