CN107098579B

CN107098579B - Environment-friendly lanthanum crown optical glass and preparation method thereof

Info

Publication number: CN107098579B
Application number: CN201710340121.4A
Authority: CN
Inventors: 王鹏飞
Original assignee: HUBEI GEBIJIA PHOTOELECTRIC TECHNOLOGY CO LTD
Current assignee: HUBEI GEBIJIA PHOTOELECTRIC TECHNOLOGY CO LTD
Priority date: 2017-05-15
Filing date: 2017-05-15
Publication date: 2020-07-17
Anticipated expiration: 2037-05-15
Also published as: CN107098579A

Abstract

The invention discloses environment-friendly lanthanum crown optical glass which comprises the following chemical components in parts by weight: b is₂O₃3 to 53 parts by weight of L a₂O₃: 3-45 parts of CaO: 0 to 30 parts of SiO₂: 4 to 30 parts of Al₂O₃: 0-5 parts of ZnO: 0 to 18 parts of ZrO₂0 to 8 parts by weight of L i₂O: 0-3 parts of BaO: 0 to 55 parts of TiO₂: 0 to 10 parts of Sb₂O₃: 0.001 to 1 part of Y₂O₃: 0 to 18 parts of Na₂O: 0 to 6 parts of WO₂: 0-3 parts of SrO: 0 to 15 parts of Nb₂O₅: 0 to 15 parts. The environment-friendly lanthanum crown optical glass does not contain Pb and As which are harmful to the environment greatly, and the product has the refractive index (nd) of 1.65-1.76 and the Abbe number (Vd) of 50-60. The environment-friendly lanthanum crown optical glass has stable optical constant, good consistency, excellent bubble and stripe grade, simple production process and high yield.

Description

Environment-friendly lanthanum crown optical glass and preparation method thereof

Technical Field

The invention belongs to the field of glass preparation, and particularly relates to environment-friendly lanthanum crown optical glass and a preparation method thereof.

Background

The prior lanthanum crown optical glass causes environmental pollution due to the lead oxide and arsenic oxide, along with the development of society, the awareness of people on environmental protection is gradually strengthened, and the traditional optical glass containing harmful substances is gradually replaced by the environmental protection optical glass. Merely replacing lead oxide with one or more components does not generally achieve the function that lead oxide plays in a glass system to form a glass with desired optical properties.

The environment-friendly lanthanum crown optical glass is mainly used as a lens and a prism in an optical system, is used for image transmission, and is a core part of an optical instrument. In recent years, the glass is widely used in camera lenses and security systems, and with the increasing popularity of digital cameras, digital video cameras, camera phones and the like, the demand for optical glass is increasing, and higher requirements are made on the performance of the optical glass.

The optical glass needs to have high refractive index and low Abbe number, so that the purpose of compensating and correcting chromatic aberration can be realized in the design of a special optical system; in addition, the product needs to have higher strength and wear resistance to prolong the service life and ensure the product quality. Most products in the prior art usually only focus on pursuing high refractive index and ignore other properties required by optical glass.

Disclosure of Invention

In view of the above, it is necessary to provide an environment-friendly lanthanum crown optical glass with a refractive index (nd) of 1.65-1.76, an abbe number (Vd) of 50-60, no heavy metal elements such As Pb and As harmful to the environment, stable optical constants, good consistency, excellent bubble and streak grades, simple production process, and high yield.

The invention provides environment-friendly lanthanum crown optical glass which comprises the following chemical components in parts by weight: b is₂O₃3 to 53 parts by weight of L a₂O₃: 3-45 parts of CaO: 0 to 30 parts of SiO₂: 4 to 30 parts of Al₂O₃: 0-5 parts of ZnO: 0 to 18 parts of ZrO₂0 to 8 parts by weight of L i₂O: 0-3 parts of BaO: 0 to 55 parts of TiO₂: 0 to 10 parts of Sb₂O₃: 0.001 to 1 part of Y₂O₃: 0 to 18 parts of Na₂O: 0 to 6 parts of WO₂: 0-3 parts of SrO: 0 to 15 parts of Nb₂O₅: 0 to 15 parts.

A preparation method of environment-friendly lanthanum crown optical glass comprises the following steps: weighing the raw materials according to the proportion, uniformly mixing the raw materials of the components by using a V-shaped mixer, melting glass slag by using powder, adding into an electric mixing production line for melting, clarifying and homogenizing, forming in a flow mode, and annealing to obtain the optical glass.

The invention has the following advantages:

firstly, the environment-friendly lanthanum crown optical glass does not contain Pb and As which are harmful to the environment, the refractive index (nd) of the product is 1.65-1.76, and the Abbe number (Vd) is 50-60;

secondly, the environment-friendly lanthanum crown optical glass has stable optical constant, good consistency, simple production process, batch production, good quality and high yield;

thirdly, the environment-friendly lanthanum crown optical glass does not contain heavy metal elements such As Pb, As and the like which are harmful to the environment, has higher strength and wear resistance, has long service life, and can better meet the market demand of the optical glass.

Detailed Description

The present invention is described in detail below with reference to specific embodiments, and the description in this section is only exemplary and explanatory and should not be construed as limiting the scope of the present invention in any way.

The embodiment provides environment-friendly lanthanum crown optical glass which comprises the following chemical components in parts by weight: b is₂O₃3 to 53 parts by weight of L a₂O₃: 3-45 parts of CaO: 0 to 30 parts of SiO₂: 4 to 30 parts of Al₂O₃: 0-5 parts of ZnO: 0 to 18 parts of ZrO₂0 to 8 parts by weight of L i₂O: 0-3 parts of BaO: 0 to 55 parts of TiO₂: 0 to 10 parts of Sb₂O₃: 0.001 to 1 part of Y₂O₃: 0 to 18 parts of Na₂O: 0 to 6 parts of WO₂: 0-3 parts of SrO: 0 to 15 parts of Nb₂O₅: 0 to 15 parts.

As a preferred scheme, the environment-friendly lanthanum crown optical glass comprises the following chemical components in parts by weight: b is₂O₃13 to 37.75 parts by weight of L a₂O₃: 3.82-41.55 parts of CaO: 0 to 10 parts of SiO₂: 5-24.32 parts of Al₂O₃: 0-2.5 parts of ZnO: 0 to 13.27 parts of ZrO₂0 to 6.06 parts by weight of L i₂O: 0-1.8 parts of BaO: 15.5 to 48 parts of TiO₂: 0 to 8.64 parts of Sb₂O₃: 0 to 0.25 part of Y₂O₃: 0 to 9.65 parts of Na₂O: 0 to 5 parts of WO₂: 0-2.62 parts of SrO: 0 to 10.5 parts of Nb₂O₅: 0 to 9.15 portions.

As a preferred scheme, the environment-friendly lanthanum crown optical glass comprises the following chemical components in parts by weight: b is₂O₃6 to 50 parts by weight of L a₂O₃: 3-43 parts of CaO: 2 to 26 parts of SiO₂: 3 to 28 parts of Al₂O₃: 0.5-2.5 parts of ZnO: 1 to 15 parts of ZrO₂1 to 6.5 parts by weight of L i₂O: 0.5-1.8 parts of BaO: 3 to 52 parts of TiO₂: 8 to 9 parts of Sb₂O₃: 0.005 to 0.3 part of Y₂O₃: 3 to 14 parts of Na₂O: 3.5 to 4.5 parts of WO₂: 0.1-2 parts of SrO: 0.3 to 11 parts of Nb₂O₅: 0.05 to 1 portion.

L a in the invention₂O₃The glass has high refractive index and low dispersion, and is an ideal composition of optical glass with high refractive index and low dispersion.

In the invention, because ZrO₂Is an intermediate oxide and can improve the glassThe crystallization performance and chemical stability of the glass are improved, and the thermal expansion coefficient of the glass is reduced. Further, the ZrO₂The content in the optical glass raw material formula is less than 7 percent.

L i in the invention₂O plays a role in breaking bonds, has strong dissolving-assisting effect, reduces the expansion coefficient of glass, reduces the crystallization tendency, but has opposite effects when the introduced amount is too large L i in the formula₂O is introduced in the form of lithium carbonate.

Na in the invention₂O is both a glass component and an important fluxing agent, and only one preferred option is used in the present formulation.

In the invention, a small amount of substituted Ba is introduced into the crown glass by ZnO, so that the erosion of the glass to the brick can be reduced, and the viscosity and the expansion coefficient of the glass are reduced.

SiO in the invention₂The glass forms oxide, and the structural components of silicon-oxygen tetrahedron form irregular continuous network to form the framework of the glass. SiO in glass₂The thermal expansion coefficient of the glass can be reduced, and the thermal stability, chemical stability, heat resistance, hardness and mechanical strength of the glass are improved;

in the invention B₂O₃Also a glass forming oxide, which takes boron-oxygen tetrahedron as a structural component and forms a structural network together with silicon-oxygen tetrahedron. Introduction of B into glass₂O₃The devitrification tendency of the glass can be reduced, and the chemical stability of the glass can be improved, but the glass can have obvious change of certain properties along with the increase of the introduced amount. In the present formulation B₂O₃Introduced in the form of boric acid.

The BaO serving as an external body of the optical glass network can improve the refractive index, specific gravity and glossiness of the glass, so that the chemical stability and thermal stability of the glass can be reduced, and meanwhile, the corrosion to refractory materials can be aggravated. In the formula, the barium carbonate and the barium nitrate are introduced.

The essential role of CaO as a network entity in the glass in the present invention is as a stabilizer, i.e. to increase the chemical stability and mechanical strength of the glass. In the present formulation CaO is incorporated in the form of calcium carbonate

Al in the invention₂O₃The thermal stability and chemical stability of the glass can be improved, but the smelting is difficult and the bubbles are difficult to eliminate due to the excessive introduction amount.

TiO in the invention₂The introduction of the compound enables the content of the network oxide of the optical glass to be increased, thereby increasing the refractive index of the glass, reducing the high-temperature viscosity of the glass and being beneficial to the clarification and the elimination of the stripes of the optical glass. There is only one preferred option for use in the present formulation.

Sb in the invention₂O₃As is replaced by As and is introduced As a new fining agent, and the nitrate is introduced simultaneously, so that the bubble in the glass is eliminated.

SrO、Nb₂O₅、Y₂O₃The dispersion is low, and the optical glass is an important composition of optical glass with an Abbe number of more than 45. The lanthanide series glass is introduced to improve the crystallization performance of the glass.

WO in the invention₂The dispersion is greatly influenced in the optical glass, and the dispersion of the optical glass can be obviously adjusted by introducing a small amount.

Table 1 details of the raw materials for 7 examples of the present invention and the parameters of the optical glass produced (data obtained after-4 ℃/h annealing) are shown.

Table 1:

the embodiment also provides a preparation method of the environment-friendly lanthanum crown optical glass, which comprises the following steps: weighing the raw materials according to the proportion, uniformly mixing the raw materials of the components by using a V-shaped mixer, melting glass slag by using powder, adding into an electric mixing production line for melting, clarifying and homogenizing, forming in a flow mode, and annealing to obtain the optical glass.

The environment-friendly lanthanum crown optical glass provided by the invention does not contain heavy metal elements harmful to the environment, such As Pb, As and the like, and has excellent environment-friendly performance, the refractive index (nd) is 1.65-1.76, and the Abbe number (Vd) is 50-60. In actual production, the optical constant is stable, the consistency is good, and the bubble and stripe grades are excellent; the production process is simple and the yield is high.

The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. The environment-friendly lanthanum crown optical glass is characterized by comprising the following chemical components, by weight, 31.87 parts of B2O3, 41.55 parts of L a2O3, 2.66 parts of CaO, 4.96 parts of SiO2, 5.41 parts of ZnO, 6.06 parts of ZrO2, 0.008 parts of Sb2O3, 7.17 parts of Y2O3, 1.36 parts of WO2 and 10 parts of SrO, the environment-friendly lanthanum crown optical glass is prepared by weighing the raw materials according to a ratio, uniformly mixing the raw materials by using a V-shaped mixer, melting glass slag by using powder, adding an electric mixing production line for melting, clarifying, homogenizing, forming by using a flow method, annealing to obtain the optical glass, the prepared optical glass has a refractive index of 1.746 and an Abbe number of 50.96, and SiO2 forms a continuous network by using a silicon-oxygen tetrahedron structure component to form an irregular glass skeleton and becomes a glass skeleton and an irregular B-glass skeleton₂O₃The boron-oxygen tetrahedron is used as a structural component and forms a structural network together with the silicon-oxygen tetrahedron.