CN103435261B - Optical glass, and preparation method and application thereof - Google Patents

Abstract

The invention discloses a piece of optical glass which is prepared from the following components in parts by weight and by taking an oxide as a reference: 27-30 parts of SiO2, 5-6 parts of B2O3, 13-14 parts of ZnO, 5-6 parts of TiO2, 19-20.5 parts of BaO, 11-12 parts of La2O3, 4-4.5 parts of ZrO2, 5-5.5 parts of CaO, 4-4.5 parts of SrO, 1-2 part(s) of Li2O, 0.05-0.1 part of Sb2O3, wherein the B2O3 is introduced in a boric acid manner; the CaO is introduced in a carbonate manner; the SrO is introduced in a nitrate manner; the Li2O is introduced in a carbonate manner; the BaO is introduced in a carbonate and nitrate manner. The optical glass prepared according to the formula is stable in optical constant and good in consistency, has good profiling property and good processing property, and has little possibility of crystallization. The invention further relates to a preparation method of the optical glass and an optical element adopting the optical glass.

Description

A kind of opticglass and its production and use

Technical field

The present invention relates to a kind of opticglass and its production and use.

Background technology

Opticglass is mainly used as lens in optical system and prism, for the transmission of picture, is the core of opticinstrument.The glass of the high refraction of early stage making, high dispersion is with SiO ₂generate body as glass, introduce relatively large TiO ₂and Nb ₂o ₅as host glass composition, along with the increase of specific refractory power and dispersion, more TiO will be introduced ₂and Nb ₂o ₅, this will make the bad stability of glass, painted also more serious, and bring the devitrification problem of glass.

In recent years in Optical System Design, people usually with glass of high refractive index promote digital camera, pick up camera, mobile phone camera to miniaturization, ultrathin development and the realization of wide angle.And when designing special optical system, more wish aberration to be reduced to minimum.

Summary of the invention

Technical problem to be solved by this invention is to provide a kind of opticglass, and optical constant is stablized, and consistence is good, and has good die mould performance and good processing characteristics, not easily crystallization.

For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of opticglass, by by oxide compound being making with the following component of parts by weight of benchmark:

Preferably, this opticglass is by by oxide compound being making with the following component of parts by weight of benchmark:

Described B ₂o ₃with boric acid (H ₃bO ₃) form introducing; CaO is with carbonate (CaCO ₃) form introducing; SrO is with nitrate (Sr (NO ₃) ₂) form introducing; Li ₂o is with carbonate Li ₂cO ₃form is introduced, and BaO introduces with the form of carbonate and nitrate.

BaO in described formula introduces, wherein with barium carbonate (BaCO with the form of carbonate and nitrate ₃) form introducing 14-15 part BaO, with nitrate of baryta (Ba (NO3) ₂) form introducing 5-5.5 part BaO.

The present invention, based on early stage glass formula, introduces a large amount of network intermediate and network outer body, increases stability, glass, adjusts the crystallization property of glass simultaneously.

In above-mentioned formula, SiO ₂be network former, form irregular contiguous network with the tetrahedral structural component of silicon-oxygen, become the skeleton of glass.SiO in glass ₂the thermal expansivity of glass can be reduced, improve thermostability, chemical stability, thermotolerance, hardness, the physical strength of glass.

B ₂o ₃also be the formation oxide compound of glass, with boron-oxygen tetrahedron for structural component, jointly form structural network with silicon-oxygen tetrahedron.B is introduced in glass ₂o ₃the thermal expansivity of glass can be reduced, improve thermostability, the chemical stability of glass, improve the mechanical property of glass.

ZnO is intermediate oxide, in the ordinary course of things using zinc oxygen octahedra as network modifying oxide, when the free oxygen in glass is enough, can forms zinc oxygen tetrahedron and enter the structural network of glass, making the structure of glass more stable.ZnO can reduce the thermal expansivity of glass, improves chemical stability and the thermostability of glass.

TiO ₂be intermediate oxide, in silicate glass, a part of titanium oxide enters in structural network with titanyl tetrahedron, and a part is in outside structural network with titanyl octahedral body.It can improve specific refractory power and the chemical stability of glass.

BaO is also also be network outer body, and it can increase the specific refractory power of glass, density and chemical stability.Part BaO introduces with nitrate salts, coordinates Sb ₂o ₃play clarification.It is stablizer that CaO will act on as network outer body group in glass, namely increases chemical stability and the physical strength of glass.

La ₂o ₃increase the water resisting property of glass, the specific refractory power of glass can be improved, reduce glass dispersion.

Chemical stability and physical strength that network outer body CaO, BaO increase glass is introduced in formula.

ZrO ₂be intermidate oxide, the viscosity of glass, hardness, elasticity, specific refractory power, chemical stability can be improved, reduce the thermal expansivity of glass.But content can not exceed 5% of effective oxide component, otherwise crystallization can be caused.

Lithium Oxide 98min Li is introduced with the form of carbonate in formula ₂o, because Lithium Oxide 98min fusing point is much higher than the fusing point of Quilonum Retard, can reduce the glass melting temperature of glass by adding Quilonum Retard, improve the seed output and quality of glass, can reduce the coefficient of expansion of glass simultaneously, and the crystallization tendency of glass is reduced.

In the formula of described opticglass, the add-on of SrO is Sb ₂o ₃40 ~ 80 times, the form with nitrate in formula adds SrO, because strontium nitrate pyrolytic decomposition discharges oxygen, nitrogen protoxide and nitrogen peroxide, compares in traditional technology and directly adds SrO, plays high temperature clarification; Chemical stability and the physical strength of glass can be increased simultaneously.

The preparation method of above-mentioned opticglass, concrete steps are:

Proportionally take the material of each component, then with V-arrangement mixer, each component raw material is mixed, then add the fusing of electric mixture manufacturing line, clarification, homogenizing, adopt stream material mode shaping, after annealing, namely obtain described opticglass.

Test according to the method for GB/T7962.1-2010, the specific refractory power of this opticglass is 1.71980 ~ 1.72020, and dispersion is 0.01646 ~ 0.01650, and Abbe number is 43.57 ~ 43.83.

Test according to the method for GB/T7962.16-2010, the transition temperature Tg of described opticglass is 584-602 DEG C; The vertical temperature Ts that speeds is 637-655 DEG C; Annealing temperature T ₁₀ ¹³576-591 DEG C; Coefficient of expansion α _{20 DEG C/300 DEG C}(10 ^-7/ K) be 84-105.

Carry out crystallization experiment to this opticglass to detect, its recrystallization temperature is 760 DEG C-1140 DEG C, higher than Annealing Temperature of Glass and vertical temperature of speeding, crystallization can not occur, affect quality product in the process of compression moulding and annealing.

Adopt the glass that above-mentioned formula is made, detect according to the method for GB/T7962.8-2010, its bubble rank reaches the A00 that GB/T903-87 standard specifies; Test according to the method for GB/T7962.9-2010, its photoabsorption coefficient reaches 0 grade of GB/T903-87 standard regulation; Test according to the method for GB/T7962.2-2010, its optical homogeneity reaches 1 grade of GB/T903-87 standard regulation; Test according to the method for GB/T7962.19-2010, its relative abrasion hardness FA is 0.62.

Optical element prepared by the opticglass described in employing is also related in the present invention, as lens, plane mirror etc.

Opticglass provided by the invention, its optical constant all can meet the requirement of GB/903-87, and consistence is good, by its relative abrasion hardness F _athis opticglass known has good processing characteristics, and by speeding, vertical temperature and the coefficient of expansion can find out that this opticglass has good die mould performance.And this kind of height reflects, the glass of low Abbe number can make up and correcting chromatic aberration, makes aberration be decreased in lower scope.

Embodiment

Further illustrate the present invention below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope of embodiment statement.

Take each material according to ratio cited in table 1, then with V-arrangement mixer, each component raw material is mixed, then add the fusing of electric mixture manufacturing line, clarification, homogenizing, adopt stream material mode shaping, after annealing, namely obtain described opticglass.Each optical constant of obtained opticglass is same in table 1, and the unit of each material weighing is g.

	Embodiment 1	Embodiment 2	Embodiment 3
				SiO 2	27.62	29.5	29.07
B 2O 3	5.5	6	5.8
				ZnO	14.2	12.32	13.3
TiO 2	5.8	6.1	5.95
				BaO	20.2	19.5	19.6
La 2O 3	11.5	12	11.8
				ZrO 2	4.2	4	4.1
CaO	5.3	5	5
				SrO	4.1	4	4
Li 2O	1.5	1.5	1.5
				Sb 2O 3	0.08	0.08	0.08
Refractive index n d	1.71843	1.72011	1.72
				Dispersion nf-nc	0.01642	0.01653	0.01648
Abbe number υ d	43.75	43.56	43.7
				Transition temperature Tg	602	593	584
Speed vertical temperature Ts	655	648	637
				Annealing temperature Tt	591	584	576
Coefficient of expansion α 20℃/300℃(10 -7/K)	105	102	84
				Relative grinding hardness Fa	0.68	0.65	0.62
Crystallization upper limit LT (DEG C)	1130	1132	1140
				Crystallization lower limit X T (DEG C)	750	755	760

Table 1

B wherein in formula ₂o ₃with boric acid H ₃bO ₃form is introduced; CaO is with carbonate CaCO ₃form is introduced; SrO is with nitrate Sr (NO ₃) ₂form is introduced; Li ₂o is with carbonate Li ₂cO ₃form is introduced.

BaO introduces, with barium carbonate BaCO in embodiment 1 with the form of carbonate and nitrate ₃form introduces 15gBaO, with nitrate of baryta Ba (NO3) ₂form introduces 5.2gBaO; With barium carbonate BaCO in embodiment 2 ₃form introduces 14gBaO, with nitrate of baryta Ba (NO3) ₂form introduces 5.5gBaO; With barium carbonate BaCO in embodiment 3 ₃form introduces 14.6gBaO, with nitrate of baryta Ba (NO3) ₂form introduces 5gBaO;

Can be found out by above-described embodiment, every optical constant of opticglass provided by the invention all can meet the requirements, and consistence is good, has good chemical stability and physical strength, has good die mould performance and processing characteristics, not easily the advantage such as crystallization.The formula of embodiment 3 is the optimization formulas determined by test of many times in addition, and the parameter of its each side is all very stable, meets related request.

Claims (10)

1. an opticglass, is characterized in that: by by oxide compound being making with the following component of parts by weight of benchmark:

SiO ₂27-30 part;

B ₂o ₃5-6 part;

ZnO 13-14 part;

TiO ₂5-6 part;

BaO 19-20.5 part;

La ₂o ₃11-12 part;

ZrO ₂4-4.5 part;

CaO 5-5.5 part;

SrO 4-4.5 part;

Li ₂o 1-2 part;

Sb ₂o ₃0.05-0.1 part.

2. opticglass according to claim 1, is characterized in that: by by oxide compound being making with the following component of parts by weight of benchmark:

SiO ₂29.07 parts;

B ₂o ₃5.8 part;

ZnO 13.3 parts;

TiO ₂5.75 part;

BaO 19.6 parts;

La ₂o ₃11.8 parts;

ZrO ₂4.1 part;

CaO 5 parts;

SrO 4 parts;

Li ₂o 1.5 parts;

Sb ₂o ₃0.08 part.

3. opticglass according to claim 1, is characterized in that: B ₂o ₃with boric acid (H ₃bO ₃) form introducing; CaO is with carbonate (CaCO ₃) form introducing; SrO is with nitrate (Sr (NO ₃) ₂) form introducing; Li ₂o is with carbonate (Li ₂cO ₃) form introducing, BaO introduces with the form of carbonate and nitrate.

4. opticglass according to claim 3, is characterized in that: BaO introduces, wherein with barium carbonate (BaCO with the form of carbonate and nitrate ₃) form introducing 14-15 part BaO, with nitrate of baryta (Ba (NO3) ₂) form introducing 5-5.5 part BaO.

5. opticglass according to claim 1, is characterized in that: in the formula of opticglass, the add-on of SrO is Sb ₂o ₃40 ~ 80 times.

6., according to the arbitrary described opticglass of claim 1-5, it is characterized in that: the specific refractory power of described opticglass is 1.71980 ~ 1.72020, and dispersion is 0.01646 ~ 0.01650, and Abbe number is 43.57 ~ 43.83.

7., according to the arbitrary described opticglass of claim 1-5, it is characterized in that: the transition temperature Tg of described opticglass is 584-602 DEG C; The vertical temperature Ts that speeds is 637-655 DEG C; Annealing temperature T ₁₀ ¹³576-591 DEG C; Coefficient of expansion α _{20 DEG C/300 DEG C}(10 ^-7/ K) be 84-105.

8., according to the arbitrary described opticglass of claim 1-5, it is characterized in that: the recrystallization temperature of described opticglass is 760 DEG C-1140 DEG C.

9. prepare the method for the arbitrary described opticglass of claim 1-8, it is characterized in that: concrete steps are

Proportionally take the material of each component, then with V-arrangement mixer, each component raw material is mixed, then add the fusing of electric mixture manufacturing line, clarification, homogenizing, adopt stream material mode shaping, after annealing, namely obtain described opticglass.

10. adopt optical element prepared by the arbitrary described opticglass of claim 1-8.