阅读说明：本技术 一种全息成像玻璃组合物、玻璃基片及制备方法 (holographic imaging glass composition, glass substrate and preparation method ) 是由 陈立新 希日莫 杜川 刘钦 赵德伟 王巍 吴生鸿 陈民生 周昌文 于 2019-08-22 设计创作，主要内容包括：本发明公开了一种全息成像玻璃组合物、玻璃基片及制备方法,玻璃组合物包含按质量百分比计的下述组分：SiO<Sub>2</Sub>:50～60％；Al<Sub>2</Sub>O<Sub>3</Sub>:3～8％；CaO:5～8％；MgO:1～5％；Na<Sub>2</Sub>O:10～15％；K<Sub>2</Sub>O:1～3％；B<Sub>2</Sub>O<Sub>3</Sub>:0～5％；稀土金属氧化物:1～10％；所述稀土金属氧化物选自La<Sub>2</Sub>O<Sub>3</Sub>、Y<Sub>2</Sub>O<Sub>3</Sub>或Gd<Sub>2</Sub>O<Sub>3</Sub>中的至少一种,将原料混合、熔化得到玻璃熔液,并对玻璃熔液进行澄清、均化、成型、退火,得到全息成像玻璃基片。本发明生产出的成像玻璃基片具有粘度适中,析晶现象明显减少,热成型难度低等特性。(the invention discloses a holographic imaging glass composition, a glass substrate and a preparation method thereof, wherein the glass composition comprises the following components in percentage by mass: 50-60% of SiO 2; 3-8% of Al2O 3; 5-8% of CaO; 1-5% of MgO; 10-15% of Na 2O; 1-3% of K2O; 0-5% of B2O 3; 1-10% of rare earth metal oxide; the rare earth metal oxide is at least one of La2O3, Y2O3 or Gd2O3, the raw materials are mixed and melted to obtain molten glass, and the molten glass is clarified, homogenized, molded and annealed to obtain the holographic imaging glass substrate. The imaging glass substrate produced by the invention has the characteristics of moderate viscosity, obviously reduced crystallization phenomenon, low thermoforming difficulty and the like.)

1. A holographic imaging glass composition is characterized by comprising the following components in percentage by mass: 50-60% of SiO 2; 3-8% of Al2O 3; 5-8% of CaO; 1-5% of MgO; 10-15% of Na 2O; 1-3% of K2O; 0-5% of B2O 3; 1-10% of rare earth metal oxide; the rare earth metal oxide is selected from at least one of La2O3, Y2O3 or Gd2O 3.

2. The holographic imaging glass composition of claim 1, wherein the contents of SiO2, B2O3, and rare earth oxide satisfy: 8.5> SiO 2/(rare earth metal oxide + B2O3) > 3.3.

3. holographic imaging glass composition according to claim 1 or 2, wherein the SiO2 content is 55-60%.

4. Holographic imaging glass composition according to claim 1 or 2, wherein the rare earth metal oxide content is 4-6%.

5. Holographic imaging glass composition according to claim 1 or 2, wherein the B2O3 content is 2 to 5%.

6. A holographic imaging glass substrate prepared from the holographic imaging glass composition of any of claims 1 to 5.

7. A preparation method of a holographic imaging glass substrate is characterized in that raw materials are mixed and melted according to the mass percentage of each component of the holographic imaging glass composition of any claim 1 to 5 to obtain molten glass, and the molten glass is clarified, homogenized, formed and annealed to obtain the holographic imaging glass substrate.

8. the method of claim 7, wherein the melting temperature is 1450-1580 ℃ and the fining temperature is 1400-1450 ℃.

9. the method for preparing the holographic imaging glass substrate as claimed in claim 7, wherein the forming is performed by a float method, the tin liquor temperature is 590-790 ℃, and the tin bath space temperature is 570-950 ℃.

10. The method for preparing a glass substrate for holographic imaging according to claim 7, wherein the annealing is performed at 500 to 550 ℃, 420 to 490 ℃ and 270 to 320 ℃ in sequence.

Technical Field

The invention belongs to the field of holographic imaging, and particularly relates to a holographic imaging glass composition, a glass substrate and a preparation method.

Background

The holography technology is a technology for recording and reproducing a real three-dimensional image of an object using interference and diffraction principles. The holographic camera uses laser as lighting source, and divides the light from the light source into two beams, one beam is directly emitted to the sensitive film, and the other beam is reflected by the shot object and then emitted to the sensitive film. Two beams of light are superposed on the photosensitive sheet to generate interference, and finally, the hologram reproduced by the digital image basic principle is utilized for further processing to remove digital interference and obtain a clear holographic image.

The development of holographic imaging technology and its associated instrumentation is immaterial. The innovation of the holographic imaging technology often puts new requirements on the matched instrument, thereby promoting the development of the holographic imaging glass, and similarly, the successful trial production of new varieties of glass also often promotes the development of the holographic imaging technology. The development of an imaging glass substrate with remarkable reflection and refraction performances is applied to various holographic image technologies, and has remarkable benefits.

The existing holographic imaging glass substrate has the defects of high molding difficulty, serious crystallization, high production cost, complex production process and low efficiency due to low glass viscosity in the molding process.

Disclosure of Invention

The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and providing a holographic imaging glass composition with moderate glass viscosity and easy forming and processing, a glass substrate and a preparation method thereof.

In order to solve the technical problems, the technical scheme provided by the invention is as follows:

A holographic imaging glass composition comprises the following components in percentage by mass: 50-60% of SiO 2; 3-8% of Al2O 3; 5-8% of CaO; 1-5% of MgO; 10-15% of Na 2O; 1-3% of K2O; 0-5% of B2O 3; 1-10% of rare earth metal oxide; the rare earth metal oxide is selected from at least one of La2O3, Y2O3 or Gd2O 3.

preferably, the contents of SiO2, B2O3 and rare earth metal oxide satisfy the following formula: 8.5> SiO 2/(rare earth metal oxide + B2O3) > 3.3.

Preferably, the content of SiO2 is 55-60%.

Preferably, the content of the rare earth metal oxide is 4-6%.

preferably, the content of B2O3 is 2-5%.

The invention also provides a holographic imaging glass substrate which is prepared by adopting the holographic imaging glass composition.

The invention also provides a preparation method of the holographic imaging glass substrate, which comprises the following steps: mixing and melting the raw materials according to the mass percentage of each component of the holographic imaging glass composition to obtain molten glass, and clarifying, homogenizing, molding and annealing the molten glass to obtain the holographic imaging glass substrate.

Preferably, the melting temperature is 1450-1580 ℃, and the clarifying temperature is 1400-1450 ℃.

Preferably, the forming is performed by a float method, the tin liquor temperature is 590-790 ℃, and the tin bath space temperature is 570-950 ℃.

Preferably, the annealing is performed at 500-550 ℃, 420-490 ℃ and 270-320 ℃.

According to the invention, a proper amount of rare earth metal oxides such as La2O3, Y2O3 and Gd2O3 are added into the raw material of the original float glass, so that the influence of the oxides on the optical properties such as the transparency, the refractive index and the dispersion coefficient of the glass and the influence of the oxides on the properties such as the chemical stability, the thermal stability and the mechanical strength of the glass are researched, and a great deal of experimental research is carried out.

According to the invention, by introducing a proper amount of rare earth metal oxides such as La2O3, Y2O3, Gd2O3 and the like into the glass components, the glass has a certain refractive index, has optical performance and can be used for production and manufacturing of holographic imaging elements. However, La2O3, Y2O3, Gd2O3 and the like are network exo-oxides with large ionic radius, and the La3+, Y3+, Gd3+ and the like have strong accumulation effect to promote phase separation and crystallization of the glass, so when the content of La2O3, Y2O3 and Gd2O3 is too high, the viscosity of the glass is reduced, the crystallization of the glass product is serious, and the cost is correspondingly increased.

The content of SiO2 in general holographic imaging glass is low, the viscosity of the glass is low, and the devitrification of glass products is serious. According to the invention, by adjusting the proportion of La2O3, Y2O3, Gd2O3 and SiO2, the content of SiO2 is higher, and the contents of La2O3, Y2O3 and Gd2O3 are lower, so that the viscosity of the imaging glass substrate is moderate, the difficulty in glass thermoforming is reduced, the occurrence of glass devitrification phenomenon is reduced, and the production cost of the imaging glass substrate is reduced. On the basis, by introducing Al2O3 and B2O3 components, the imaging glass substrate has high thermal stability and high mechanical strength.

Aiming at the novel glass raw material formula, the novel melting, forming, annealing and other production processes of the specific glass are determined, the internal stress of the imaging glass substrate is reduced, and the high-quality imaging glass substrate with high stability is produced.

Detailed Description

In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.

Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.

unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.

The holographic imaging glass composition of one embodiment of the present invention has the following formulation (wt%): SiO2: 50-60%; 3-8% of Al2O 3; 5-8% of CaO; 1-5% of MgO; 10-15% of Na 2O; 1-3% of K2O; 0-5% of B2O 3; (La2O3+ Y2O3+ Gd2O3) in an amount of 1-10%.

SiO2 is a component for forming a glass skeleton, and if the content is lower than 50%, the viscosity of the glass is low, so that the holographic imaging glass substrate product has serious crystallization and high forming difficulty. However, the content is too high, the viscosity of the glass is too high, the melting of the glass is not facilitated, and the existing kiln process is difficult to meet, so that the content of SiO2 is selected to be 50-60%, and is more preferably 55-60%.

the Al2O3 is used for improving the strength of the glass structure and improving the scratch resistance and the falling resistance of the glass. However, the content of Al2O3 is too high to be melted. On the contrary, the content of Al2O3 is too low, the glass is easy to crystallize, the mechanical strength is low, and the glass is not easy to form, so that the content of Al2O3 is selected from 3 to 8%, and more preferably from 4 to 6%.

CaO is a component that lowers high temperature viscosity and significantly improves meltability without lowering strain point. Moreover, CaO has an effect of suppressing precipitation of devitrified crystals containing Mg. The content of CaO is 5-8%. If the content of CaO is small, the above-described effects are hardly exhibited. On the other hand, if the content of CaO is large, devitrified crystals of anorthite are likely to precipitate and the density is likely to increase.

MgO can reduce the melting temperature of glass, is beneficial to melting the glass, improves the stability of the glass, inhibits the devitrification tendency of the glass, promotes ion exchange, and improves the stress strength and the depth of the glass after strengthening, but the MgO exceeds a certain amount to cause the glass to be devitrified, so the content of the MgO is selected to be 1-5%.

na2O and K2O are components that undergo ion exchange during the chemical strengthening treatment. When the content is higher, the expansion coefficient of the glass is increased, and the mechanical properties of the glass are reduced. As the amount of K2O increased, the compressive stress obtained by ion exchange decreased. Comprehensively considering 10-15% of Na2O and 1-3% of K2O.

the B2O3 can reduce the viscosity of the glass and improve the brittleness, toughness and light transmittance of the glass. B2O3 reduces the brittleness of the glass, making the glass less susceptible to devitrification and easier to vitrify. After debugging, the content of B2O3 is 0-5%, and more preferably 2-5%.

The rare earth metal oxides La2O3, Y2O3 and Gd2O3 can enable the glass to have a certain refractive index, so that the glass has optical performance, when the content of the components La2O3, Y2O3 and Gd2O3 is too high, the viscosity of the glass is reduced, the crystallization of the glass product is serious, the cost is correspondingly increased, and the content is 1-10 percent in total, and more preferably 4-6 percent.

fitting a large amount of experimental data, if the contents of SiO2, B2O3 and the rare earth metal oxide satisfy the following formula: 8.5> SiO 2/(rare earth metal oxide + B2O3) >3.3, the viscosity, the optical properties such as transparency, refractive index, dispersion coefficient and the like of the holographic imaging glass, and the properties such as chemical stability, thermal stability, mechanical strength and the like of the holographic imaging glass all reach the best, and the holographic imaging glass has the best effect when being used for holographic imaging.

The preparation method of the holographic imaging glass substrate comprises the steps of mixing and melting the raw materials according to the mass percentage of each component of the holographic imaging glass composition to obtain molten glass, and clarifying, homogenizing, forming and annealing the molten glass to obtain the holographic imaging glass substrate.

the preparation method of the holographic imaging glass substrate of one embodiment comprises the following steps: the raw material components are sent into a melting furnace to carry out melting reaction, the melting temperature is 1450-1580 ℃, the clarification temperature is 1400-1450 ℃, and the raw material components are cooled by a cooling part and then sent into a tin bath through a flow channel to be formed. The tin liquor temperature is 590-790 ℃, the tin bath space temperature is 570-950 ℃, the horizontal temperature difference of the glass is reduced through tin bath cooling devices, edge rollers and other equipment, the glass is processed into required thickness and width, and the glass drawing speed is 650-780 m/h.

And (3) feeding the semi-formed glass belt into an annealing kiln from a transition roller table, annealing the glass belt at the temperature of 500-550 ℃, 420-490 ℃ and 270-320 ℃, cutting out holographic imaging glass substrates with different specifications at a transverse cutting section after the annealing is finished, and further processing the holographic imaging glass substrates into various optical holographic glass elements. The annealing kiln is used for gradually controlling the temperature in the process of cooling the molten glass to room temperature so as to prevent thermal shock (glass breakage), 95% of permanent stress is released by the glass at the temperature of 500-550 ℃, 5% of permanent stress is released at the temperature of 420-490 ℃, and the permanent stress of the glass is fixed after the temperature is lower than the temperature. Therefore, the glass is soaked in water and cooled slowly in the two temperature ranges, the temperature difference in the glass is eliminated, and the internal stress is fully released. And after the internal stress is completely released and the permanent stress is fixed, rapidly cooling the glass again, and taking the intermediate temperature of 270-320 ℃ as a buffer transition stage to prevent the glass from being cracked due to overlarge temporary stress generated by excessively rapid cooling. Generally, the annealing temperature of glass is affected by the composition and needs to be adjusted according to the actual situation.