WO2008028341A1

WO2008028341A1 - Environmental protection type dense flint glass with high refractive index and high dispersion, and method and device for preparing the same

Info

Publication number: WO2008028341A1
Application number: PCT/CN2006/002483
Authority: WO
Inventors: Wei Sun; Mingxin Lu; Congxun Yan; Jiayou Liu
Original assignee: Cdgm Glass Co., Ltd
Priority date: 2006-08-31
Filing date: 2006-09-21
Publication date: 2008-03-13
Also published as: CN1915875B; JP2009527442A; JP5044573B2; CN1915875A

Abstract

An environmental protection type dense flint glass with high refractive index and high dispersion is provided, the glass comprises, in wt%, SiO2 20-44, TiO2 22-34, Nb2O5 5-22, Na2O 7-18, BaO 9-17, K2O 0-9, CaO 0-3, ZrO2 0-3, SrO 0-0.5 and Sb2O3 0-0.5. A method for preparing the above glass is also provided, the method comprises the following the steps: 1) mixing raw materials sufficiently to allow them to be uniformly distributed; 2) melting the raw materials to an glass melt in a tank furnace at 1150-1300 ºC to ensure uniform refractive index; 3) molding the glass melt into glass strips after refining and homogenizing the glass melt having qualified refractive index; and 4) annealing the glass strips in the annealing oven. The device for producing the above glass comprises a tank furnace and an annealing oven, wherein the molten pool of the tank furnace is connected with automatically combustion-controlling system. The glass is free of PbO, As2O3 and GdO which pollute environment, and is produced in a mode of melting the raw material at a time, thereby decreasing the number of melting raw materials at high temperature and enhancing the optical transmittance.

Description

High refractive index high dispersion environmentally friendly heavy flint optical glass and production method and equipment thereof

The invention relates to an optical glass and a production method and equipment thereof, in particular to a high refractive index (Nd) high dispersion environmental protection heavy flint optical glass and a production method and equipment thereof.

Background technique

With the improvement of people's living standards, in order to meet the requirements of high image quality, small size and light weight of high-end digital products, the demand for heavy flint optical glass with high refractive index, high dispersion (low Abbe number) and low density is increasing. large, but contained Pb0 optical glass, As ₂ 0 ₃ and GdO serious pollution of the environment by the optical equipment manufacturer the glass having the same optical properties does not contain Pb0, As ₂ 0 ₃ and GdO ingredients.

In order to make the optical glass have a high refractive index, the content of components such as Ti0 ₂ and Nb ₂ 0 ₅ in the glass component is correspondingly large, and these components cause the viscosity of the molten glass during the production process to be dilute, the crystallization is severe, and the constant fluctuation is large. Difficult to form, the quality of the glass stripe is not high, and the production is very difficult.

At present, optical glass manufacturers generally use a pool furnace to produce secondary materials. The production process is: After the prepared raw materials are thoroughly mixed, they are melted into glass slag of suitable particle size at a high temperature by a single crucible, and the glass slag is tested. The refractive index of the glass slag with acceptable refractive index is re-introduced into a high-temperature smelting furnace to form a molten glass, which is clarified and sufficiently homogenized to form a glass strip. Since the production method undergoes two high temperatures, the optical transmission performance of the glass is affected, and the number of steps is large, the production cycle is long, and the production cost is high.

Summary of the invention

The technical problem to be solved by the present invention is to provide a high refractive index and high dispersion environmentally friendly heavy flint optical glass, which does not contain Pb0, As ₂ 0 ₃ and Gd0.

The present invention also provides a method for producing the above optical glass. The method has a high optical temperature, a glass having good optical transmission performance, a small number of steps, and a short cycle.

The present invention also provides a production apparatus for the above optical glass.

The technical solution adopted by the invention to solve the technical problem is: high refractive index and high dispersion environment-friendly heavy flint optical glass, the weight percentage composition thereof is: Si0 _{2 :} 20-44%, Ti0 ₂ : 22-34%, Nb ₂ 0 ₅ : 5 - 22%, Ν3⁄40: 7-18°/. , BaO: 9-17°/. , K ₂ 0: 0 - 9%, CaO: 0-3%, Zr0 ₂ : 0-3%, SrO: 0-0. 5%, Sb ₂ 0 ₃ : 0-0. 5%.

High refractive index high dispersion environmentally friendly heavy flint optical glass production method, the method comprises the following steps: 1) thoroughly mixing the prepared raw materials to ensure uniformity thereof; 2) melting in a pool furnace at a high temperature of 1150-1300 ° C The glass liquid is made to make the refractive index consistency of the glass liquid good; 3) After the clarified and fully homogenized glass liquid is clarified and sufficiently homogenized, it is formed into a glass strip; 4) The glass strip is annealed in an annealing furnace.

The production equipment of high refractive index and high dispersion environmentally-friendly heavy flint optical glass comprises a pool furnace and an annealing furnace, and the melting furnace of the pool furnace is connected with an automatic combustion control system.

7-1. 85, Vd (Abbe number) is 23. The optical glass of the present invention does not contain Pb0, As ₂ 0 ^ n GdO environmentally polluting components, the Nd is 1. 7-1. 85, Vd (Abbe number) is 23. 5-28. 5, is a high refractive index and high dispersion environmentally friendly heavy flint optical glass. The invention adopts a pool furnace to produce optical glass in a single material manner, the production process is coherent and simple, the number of high-temperature melting times is reduced, the optical transmission performance can be improved under the condition of the same raw material quality, and the process is small and the production cycle is short. , reducing production costs.

DRAWINGS

Figure 1 is a flow chart of a conventional secondary chemical production method.

Fig. 2 is a flow chart showing the production mode of the primary chemical material of the present invention.

Figure 3 is a schematic view of a frame stirrer.

Figure 4 is a schematic view of a disc agitator. (Where: Fig. 4a is a front view of the disc agitator; Fig. 4b is a side view of the disc agitator; and Fig. 4c is a partial cross-sectional view of the disc agitator.)

Figure 5 is a schematic view showing the configuration of a production apparatus of the present invention.

detailed description

The optical glass of the present invention contains 20-44% of the glass forming body Si0 ₂ . If the Si0 content is too high, the glass transmittance and the dispersion index cannot meet the requirements, and the melting temperature becomes high and is not easily melted; if Si0 ₂ If the content ratio is too low, the crystallization property and chemical stability are lowered, and the preferable SiO ₂ content is 23-44%, and the particularly preferable SiO ₂ content is 25 - 37%.

In addition to the glass former, a certain proportion of flux is required to reduce the high refractive index component with a higher melting temperature. If the flux content is too high, the polishing property and chemical stability of the glass are affected; the flux content is excessive. Low, the high refractive index component is refractory. Therefore, the flux in the glass N3⁄40 + K ₂ 0 A total content of 7-27%, wherein the content of N is 7-18% 0, ₂ 0 content of 0-9%; preferred content of Na ₂ 0 10-16%, the content of K ₂ 0 is from 0 8%; particularly preferred Ν 0 content is 12-15%, Κ ₂₀ content is 0-8%

In order to achieve the optical index of the glass, it is necessary to contain a relatively high proportion of the high refractive index component, so the ratio of the glass former Si0 ₂ and the fluxes Na ₂ 0 and Κ ₂₀ is limited, and the preferred Si0 ₂ + Na The total content of ₂ 0+ ₂ 0 is 50%, and the total content of Si0 ₂ + Na ₂ 0+K ₂ 0 is particularly preferably 45%.

The alkaline earth metal oxides Ba0, CaO and SrO can adjust the microstructure of the glass and improve the chemical stability of the glass. The preferred content of BaO+CaO+SrO is 10-20%, wherein the BaO content is 9-17%. The content of CaO is 0-3%, and the content of SrO is 0-0. 5%; the total content of Ba0+Ca0+Sr0 is particularly preferably 12-18°/. 5%。 The content of BaO is 12-16%, the content of CaO is 0-3%, and the content of SrO is 0-0. 5%.

Ti0 ₂ can make the glass have a high refractive index, but if the content is too high, the dispersion coefficient will be greatly reduced and the crystallization tendency will be greatly increased; if the content is too small to achieve the required high refractive index, the Ti0 ₂ content is 22-34%, preferably 27-34%, particularly preferably 28-32%.

Nb ₂ 0 ₅ can make the glass have a high refractive index, and replacing the Ti0 ₂ with an appropriate amount of Nb ₂ 0 ₅ can ensure that the glass has a high refractive index and at the same time reduce the tendency of crystallization, but an excessive Nb ₂ 0 ₅ content causes a refractive index, The dispersion coefficient cannot simultaneously meet the requirements, so the Nb ₂ 0 ₅ content is 5-22%, preferably 10-22%, particularly preferably 12-20%.

Zr0 ₂ can make the glass have a high refractive index, and at the same time improve the chemical stability and swelling properties of the glass. The Zr0 ₂ part can be used instead of Ti0 ₂ to make the optical index meet the requirements, but the ∑]:0 ₂ content will increase the crystallization. 5%。 The tendency to lower the refractive index, so Zr0 ₂ content is 0-3%, preferably 0-2%, particularly preferably 0-1. 5%.

Sb ₂ 0 ₃ is a clarifying agent, which can reversibly absorb and release gas with other gases in different temperature zones of the glass melting stage, and accumulates a small gas into a larger gas, which is floated to the surface by buoyancy in the glass liquid to eliminate but excess Sb ₂ 0 ₃ content will affect the glass color and reduce the life of the platinum container, so Sb ₂ 0 ₃ content of 0-0. 5%, preferably 0-0. 3%, particularly preferably 0-0. 15%.

Table 1 shows nine examples of the optical glass of the present invention.

Table 1

It can be seen from Table 1 that the optical glass of the present invention does not contain PbO, As ₂ ₃ and GdO which are polluting to the environment, and the optical properties are: Nd is 1. 7-1. 85, Vd is 23. 5-28. 5.

1 is a flow chart of a conventional secondary chemical production mode, which comprises the following steps: batching; melting glass slag in a single crucible; testing constant and batching; qualified glass slag melting glass in pool furnace Liquid; clarification; homogenization; molding; annealing furnace annealing.

2 is a flow chart of the production method of the primary chemical material of the present invention, and the specific steps of the production method are as follows: 1. The prepared raw materials are thoroughly mixed to ensure uniformity thereof.

1) Using a rapid moisture tester to enhance the moisture monitoring of raw materials, especially moisture-absorbing materials, in accordance with the standards of optical glass raw materials, disqualified; 2) a small number of multiple weighing methods, each weighing less than 30 Weighing equipment of kilograms of glass; Weighing equipment using high-precision weighing equipment (such as electronic scales), the accuracy is 0. 01kg; 3) Mixing evenly with a stirrer; 4) In order to prevent serious delamination of raw materials, use a small amount of packing, each The sub-packed glass powder does not exceed 30 kg; 5) Due to the manual feeding, in order to reduce the stratification of the transportation and storage process, manual mixing is used before each feeding.

Two: The glass furnace of the present invention is melted into a molten glass at a high temperature of 1,150 to 1,300 Torr to make the refractive index of the molten glass uniform.

1) Increase the bubbler of the melting tank from 1 to 2-4 bubblers; 2) Use auto-ignition The burning control system maintains the oxidizing atmosphere of the combustion flame and automatically adjusts the temperature to ensure the stability of the melting temperature and atmosphere in accordance with the process requirements. 3) Increase the number of refractive indexes of the test molten glass, once every 4 hours, and if necessary, correct in time. Calibration with the same series of glass grades or raw materials with different refractive indices to ensure that the calibration material does not introduce components that are not in the corrected glass; 4) Replace the frame stirrer with a disc-shaped stirrer. Fig. 3 is a schematic view of the frame stirrer. The stirring principle of the frame stirrer is to agitate and cut by the frame 1, and the width of the frame 1 is small. Fig. 4 is a schematic view of a disc agitator, the discs 2 being joined together by a shaft, and the bezel 3 is disposed on both sides of the outer edge of the disc 2 and is raised in a stair shape. The principle of the agitating of the disc-shaped agitator is to change the flow direction of the glass liquid through the disc 2, and the frame 3 is cut, and the width of the frame 3 is large. Because the viscosity of the glass is very small, the resistance to the rotating agitator is small, and the disc-shaped agitator having a relatively large frame width is relatively more resistant and has a high stirring ability, and can better stir the glass of the dilute viscosity.

Three: The glass liquid with acceptable refractive index is clarified and fully homogenized, and then formed into a glass strip. Four: The glass strip is annealed in an annealing furnace.

The advantage of the production method of the primary chemical material relative to the production method of the secondary chemical material is that the single-melting glass slag is eliminated, and the main purpose of this step is to ensure the refractive index consistency of the glass liquid. The key to the production method of using the primary furnace material is to take effective measures to ensure the uniformity of the raw materials from the preparation of raw materials to the melting process, and to increase the consistency of the refractive index of the molten glass by adding auxiliary devices in the molten glass.

The technical indexes of the high refractive index and high dispersion environmentally-friendly heavy flint optical glass produced by the production method of the invention all reach the product technical index, and the optical transmission performance is better. Using the same raw material, the production method of the second material produced H-ZF _52A color, the standard lens in 0HARA upper limit of the present invention using the production process of the color produced H- ZF _52A, in the lens Lower limit of the standard value (+10 dish); H-ZF _7LA strip color and internal _{transmittance} produced by the same raw material, using the secondary chemical production method, H-ZF ₇ LA produced by the production method of the present invention The chromaticity and internal permeability are about 10 nm, which is the lower limit of the standard value (-10 nm).

The production equipment of the present invention is shown in Fig. 5, including a pool furnace and an annealing furnace. The melting tank of the pool furnace is connected to an automatic combustion control system, wherein the connection relationship of the automatic combustion control system is accordingly: natural gas inlet, filter adjustment Pressure regulation automatic cut-off system, natural gas flow measurement control system, proportional adjustment system; combustion air inlet, pressure regulation automatic cut-off system, combustion air flow measurement control The system and the proportional adjustment system; wherein there is a temperature controller between the natural gas flow measurement control system and the melting pool of the pool furnace, the proportional adjustment system is connected to the burner of the melting pool.

The working principle of the production equipment of the invention is: setting the ratio of natural gas and air on the proportional adjustment system to ensure the full combustion of the natural gas, and measuring the actual temperature value of the melting pool of the furnace by the temperature controller and setting The constant temperature value is compared, a control command is issued to the natural gas flow measurement control system to adjust the flow of the natural gas, and the signal of the natural gas flow change is transmitted to the combustion air flow measurement control system through the proportional adjustment system, and the combustion air flow measurement control system will assist combustion The air flow is adjusted to match the natural gas flow, so that the flow rate of the two reaches the set value, and finally the temperature is maintained at the set temperature to maintain the stability of the process.

Claims

Claim

1. High refractive index and high dispersion environmentally friendly heavy flint optical glass, characterized in that: its weight percentage composition is: Si0 ₂ : 20-44%, Ti0 ₂ : 22-34%, Nb ₂ 0 ₅ : 5-22%, Na ₂ 0: 7-18%, BaO: 9-17%, K ₂ 0: 0-9%, CaO: 0-3%, Zr0 ₂ : 0-3%, SrO: 0-0. 5% and Sb ₂ 0 ₃ : 0-0. 5%.

The high refractive index high dispersion environmentally friendly heavy flint optical glass according to claim 1, wherein the sum of the weight percentages of Si0 ₂ , Na ₂ 0 and K ₂ 0 is 50%, and the weight percentage of Ba0, CaO and SrO The sum is 10-20%.

The high refractive index high dispersion environmentally friendly heavy flint optical glass according to claim 1, wherein the weight percentage composition is: Si0 ₂ : 23 - 44%, Ti0 _{2 :} 27-34%, Nb ₂ 0 ₅ : 10-22%, Na ₂ 0: 10-16%, BaO: 12-16%, K ₂ 0: 0-8%; CaO: 0-3%, Zr0 ₂ : 0-2%, SrO: 0- 0. 5% and Sb ₂ 0 ₃ : 0-0. 3%.

The high refractive index high dispersion environmentally-friendly heavy flint optical glass according to claim 1, wherein the weight percentage composition is: Si0 ₂ : 25-37%, Ti0 ₂ , 28-32%, Nb ₂ 0 ₅ : 12-20%, Na ₂ 0: 12-15%, BaO: 12-16%, K ₂ 0: 0-8%, CaO: 0-3%, Zr0 ₂ : 0-1. 5%, SrO: 0-0. 5% and Sb ₂ 0 ₃ : 0-0. 15%.

The high refractive index high dispersion environmentally friendly heavy flint optical glass according to claim 4, wherein: the sum of the weight percentages of the SiO ₂ , Na ₂ 0 and K ₂ 0 is 45%, the Ba0, CaO and The sum of the weight percentages of SrO is 12-18%.

6. The method for producing high refractive index and high dispersion environmentally-friendly heavy flint optical glass according to claim 1, wherein the method comprises the following steps: 1) mixing the prepared raw materials to ensure uniformity thereof; 2) At a high temperature of 1150-1300 ° C, the glass furnace is melted into a glass liquid to make the refractive index of the glass liquid consistently good; 3) the glass liquid with the qualified refractive index is clarified and sufficiently homogenized, and then formed into a glass strip; The glass strip is annealed in an annealing furnace.

7. The method of producing high refractive index, high dispersion, environmentally-friendly heavy flint optical glass according to claim 6, wherein: said step 1 is sufficiently mixed: the compounding is carried out by a small amount of multiple weighing methods.

The method for producing high-refractive-index, high-dispersion environmentally-friendly heavy flint optical glass according to claim 7, wherein: the small amount of the plurality of weighing methods is: powder weighing no more than 30 kg of glass each time, The measuring device uses a high-precision weighing device.

The method for producing high refractive index and high dispersion environmentally-friendly heavy flint optical glass according to claim 6, wherein: the step 1 is sufficiently mixed to: uniformly mix using a stirrer.

10. The method of producing high refractive index high dispersion environmentally-friendly heavy flint optical glass according to claim 6, wherein: the step 1 is sufficiently mixed: using a small amount of packing.

A method of producing a high refractive index, high dispersion, environmentally-friendly heavy flint optical glass according to claim 10, wherein said small amount of packaging is: no more than 30 kg of glass powder per package.

12. The method of producing high refractive index, high dispersion, environmentally-friendly heavy flint optical glass according to claim 6, wherein: the thorough mixing in step 1 is: manual agitation before each feeding.

13. The method for producing high refractive index and high dispersion environmentally-friendly heavy flint optical glass according to claim 6, wherein: when the step 1 is performed, moisture monitoring is performed on the optical glass raw material by using a rapid moisture tester, which conforms to the optical glass. The raw material standard can be used, and it is disabled if it is not qualified.

14. The method for producing high refractive index and high dispersion environmentally-friendly heavy flint optical glass according to claim 6, wherein: the bubble burner of the pool furnace is 2-4.

15. The method for producing high refractive index and high dispersion environmentally-friendly heavy flint optical glass according to claim 6, wherein: the step furnace 2 adopts an automatic combustion control system to maintain an oxidizing atmosphere of the combustion flame and automatically adjust the temperature. Ensure that the melting temperature and atmosphere meet the stability requirements of the process.

16. The method for producing a high refractive index, high dispersion, environmentally-friendly heavy flint optical glass according to claim 6, wherein: the refractive index of the molten glass is consistent in step 2: the molten pool glass is tested every 4 hours. The refractive index of the liquid is corrected in time.

A method of producing a high refractive index, high dispersion, environmentally-friendly heavy flint optical glass according to claim 16, wherein: said correcting uses the same series of glass grades or raw material corrections having different refractive indices.

18. The method of producing high refractive index, high dispersion, environmentally-friendly heavy flint optical glass according to claim 6, wherein: the step of the pool is a disc-shaped agitator.

19. The production apparatus of high refractive index and high dispersion environmentally friendly heavy flint optical glass according to claim 1, comprising a pool furnace and an annealing furnace, wherein: the melting furnace of the pool furnace is connected to an automatic combustion control system.

20. The production of high-fractionation, high-dispersion environmentally-friendly heavy flint optical glass according to claim 19. The utility model is characterized in that: the connection relationship of the automatic combustion control system is accordingly: a natural gas inlet, a filter pressure regulation automatic cut-off system, a natural gas flow measurement control system, a proportional adjustment system; a combustion air inlet , pressure regulation, voltage regulation, automatic cut-off system, combustion air flow measurement control system, proportional adjustment system; wherein there is a temperature controller between the combustion air flow measurement control system and the melting pool of the pool furnace; the proportional adjustment system and the melting pool The burners are connected.

A production apparatus for high refractive index and high dispersion environmentally-friendly heavy flint optical glass according to claim 19, wherein: ???said pool furnace uses 2-4 bubblers.

The apparatus for producing high-refraction and high-dispersion environmentally-friendly heavy flint optical glass according to claim 19, wherein: the pool furnace adopts a disc-shaped agitator, and the discs (2) are connected by a shaft, a frame ( 3) Set on both sides of the outer edge of the disc (2).