Environment-friendly high-refractive-index glass and application thereof

Abstract

The invention discloses environment-friendly glass with a high refractive index and an application of the environment-friendly glass. The environment-friendly glass with the high refractive index is prepared from the following oxides in percentage by mass: 27.0 to 35.0 wt.% of B2O3, 42.0 to 48.0 wt.% of La2O3, 4.0 to 10.0 wt.% of Nb2O5, 6.0 to 12.0 wt.% of Gd2O3, 0.5 to 4.0 wt.% of Y2O3, 0.1 to 4.0 wt.% of SiO2, 0.5 to 5.0 wt.% of ZnO, 0 to 5.0 wt.% of TiO2 and 0 to 5.0 wt.% of Ta2O5. The environment-friendly high-refractive-index glass has the following advantages that the environment-friendly high-refractive-index glass does not contain any one of heavy metal oxides such as As2O3, Sb2O3, BaO, PbO, Tl2O, CdO, BeO and V2O5 harmful to the environment, the refractive index is larger than or equal to 1.76, the devitrification resistance, the chemical stability and the mechanical strength are excellent, and the invention further provides application of the environment-friendly high-refractive-index glass to wearable AR equipment.

Description

Technical Field

[0001] The invention relates to an environmentally friendly high-refractive index glass material and application thereof, belonging to the technical field of optical glass materials and electronic equipment. Background Art

[0002] Augmented Reality (AR) is a technology that cleverly integrates virtual information with the real world. It widely uses multimedia, three-dimensional modeling, real-time tracking, intelligent interaction, sensing and other technical means to simulate computer-generated text, images, three-dimensional models, music, video and other virtual information, and apply them to the real world. The two types of information complement each other, thereby achieving "enhancement" of the real world. "Augmented reality looks like a real scene." AR technology is a relatively new technical content that promotes the integration of real-world information and virtual-world information content. It simulates and processes physical information that is difficult to experience in the spatial scope of the real world based on computers and other scientific and technological means, and effectively applies virtual information content in the real world. In this process, it can be perceived by human senses, thereby achieving a sensory experience beyond reality. It is precisely because of the disruptive and revolutionary nature of AR technology that AR technology has broad application prospects and optimistic industry development prospects. It can be applied to 3D games, urban planning, virtual simulation teaching, cultural heritage protection, transportation, financial services, security monitoring, education and training, clinical surgery, industrial design, information retrieval, advertising shopping, commercial applications, personal consumption, cultural relics display, children's AR books, 3D virtual maps and other aspects.

[0003] As new AR applications continue to emerge, users' demand for AR will inevitably grow. People will become more and more accustomed to using AR technology in life and work. With the development of AR technology, many AR display devices such as AR glasses and helmet displays have also appeared. In particular, AR glasses used in conjunction with mobile phones are popular among consumers due to their simple structure, high resolution, and no visual deviation. As the fastest growing AR market in the world, my country has a strong smartphone manufacturing supply chain. However, the AR glasses used in conjunction with mobile phones on the market either use a mobile phone head-up solution, which makes the mobile phone stand upright on the glasses, which is too large to affect the appearance and user experience, or the mobile phone is placed behind the lens, which cannot fully utilize the mobile phone camera for AR interaction and related functions, making the experience of AR glasses greatly reduced. At present, the AR devices on the market are not ideal in terms of field of view and volume. For AR display, field of view is very important, because to achieve a certain sense of immersion, the AR world must be seamlessly integrated with the real world. If the AR world in front of you cannot be seen in real time, users will unnaturally move their heads to "scan" the surrounding environment, just like looking at the world through a telescope. In this way, the brain cannot see the AR world as part of the real world through intuitive mapping, and the so-called immersion will also disappear. The result is that the immersion is not strong enough and cannot become people's natural consciousness, which also means that it cannot become a natural human-computer interaction for the consumer and entertainment markets. The current AR technology has a field of view of only 30 to 90 degrees; and the AR devices on the market with a wide field of view are very bulky. If you want to reduce the size of the AR device, you have to reduce the screen and goggles at the same time, so that the field of view angle will also be reduced. However, if you don't sacrifice a certain field of view, you can't reduce the size of the optical system. Therefore, the optical components of the AR device are very important. It needs to have an optical system that is as thin as possible to achieve a large angle of view, so it is necessary to increase the refractive index of the optical system as much as possible in order to project the picture displayed on the screen into the user's eyes.

[0004] Therefore, in terms of miniaturization of AR technology display devices and improvement of field of view, the lens part of AR glasses can be further improved by adjusting the refractive index, density and processing convenience of the glass. dHigher than 1.5 or even 1.6 is very common in the field of optical glass. By adding PbO, it is easy to increase the refractive index of glass to above 1.7. Using As2O3 as a clarifier can obtain optical glass with good melting quality. However, PbO and As2O3 have serious environmental and ecological hazards, and they can cause harm to the human body during processing. In addition, glass with a refractive index higher than 1.6 has a high tendency to crystallize during the hot forming process due to the strong change of viscosity with temperature, which reduces its anti-crystallization performance. Therefore, manufacturers of optical instruments and products using high-refractive-index glass are very eager to use ecologically friendly and environmentally friendly glass. For this reason, environmentally friendly high-refractive-index glass is of great significance. Summary of the invention

[0005] The purpose of the present invention is to provide a low-cost, environmentally friendly, high-refractive index glass with excellent anti-crystallization performance, excellent chemical stability and mechanical strength and its application in view of the deficiencies of the prior art.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] An environmentally friendly high refractive index glass is prepared by including the following oxides in weight percentage (wt.%):

[0008]

[0009] The environmentally friendly high refractive index glass is characterized in that it is preferably prepared by including the following oxides in accordance with mass percentage (wt.%):

[0010]

[0011] The environmentally friendly high refractive index glass of the present invention belongs to borate glass, wherein 1.35≤La2O3 / B2O3≤1.56 can obtain high refractive index glass;

[0012] In the present invention, rare earth oxide ∑(La2O3+Nb2O5+Ta2O5+Gd2O3+Y2O3)≥60%;

[0013] The environmentally friendly high refractive index glass of the present invention is characterized in that it substantially does not contain any of alkali metal and alkaline earth metal oxides;

[0014] Furthermore, the alkali metal oxide herein refers to any one of Li2O, Na2O, K2O, Rb2O, Cs2O, Fr2O, etc.;

[0015] Furthermore, the alkaline earth metal oxide herein refers to any one of MgO, CaO, SrO, BaO, etc.;

[0016] The environmentally friendly high-refractive index glass of the present invention is characterized in that the high-refractive index glass of the present invention does not contain any of the metal oxides harmful to the environment, such as As2O3, Sb2O5, BaO, PbO, Tl2O, CdO, BeO, V2O5, etc.;

[0017] The environmentally friendly high-refractive index glass of the present invention is characterized in that the refractive index of the glass is greater than 1.76;

[0018] The environmentally friendly high-refractive index glass described in the present invention is characterized in that the environmentally friendly high-refractive index glass provided by the present invention has good chemical stability and mechanical strength in the use environment.

[0019] Compared with the prior art, the environmentally friendly high refractive index glass provided by the present invention has the following significant advantages:

[0020] (1) The present invention does not contain any metal oxide or heavy metal oxide harmful to the environment, such as As2O3, Sb2O5, BaO, PbO, Tl2O, CdO, BeO, V2O5, etc., and is green and environmentally friendly;

[0021] (2) The refractive index of the environmentally friendly high-refractive-index glass of the present invention is n d The refractive index of glass is higher than 1.76. According to the optical principle, the internal total reflection angle of the lens of the AR device plays the role of projecting the image. The environmentally friendly high-refractive index glass of the present invention increases the internal total reflection angle by nearly one-fold, expands the field of view of the AR device by nearly two-fold and greatly improves the imaging quality, presenting a high-definition picture comparable to the real world, bringing unlimited possibilities for AR application innovation and realizing a more realistic augmented reality (AR) experience. AR device manufacturers can use this breakthrough technology of the present invention to expand the user's field of view to the limit of human vision;

[0022] (3) The environmentally friendly high-refractive index glass provided by the present invention has good chemical stability and mechanical strength in the use environment, can achieve high-resolution imaging, can generate clear and high-contrast natural color images, and seamlessly integrate with the natural environment;

[0023] (4) The raw materials selected by the present invention are cheap and have diverse sources. The raw materials are easy to obtain, the process is simple and stable, the production cost is low, and large-scale production can be achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The above and / or additional aspects and advantages of the present invention will become apparent and easily understood from the following description of the embodiments in conjunction with the accompanying drawings, in which:

[0025] Figure 1 The environmentally friendly high refractive index glass of the present invention is applied to AR glasses;

[0026] In the picture, 1-AR glasses; 2-environmentally friendly high-refractive index glass lenses. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical solution and advantages of the present invention clearer, the embodiments of the present invention are further described in detail below. The present invention is further described in detail below in conjunction with specific embodiments, but it is not intended to limit the present invention.

[0028] The present invention provides an environmentally friendly high refractive index glass, which is prepared by including the following oxides in accordance with mass percentage (wt.%):

[0029] B2O3 27.0-35.0

[0030] La2O3 42.0-48.0

[0031] Nb2O5 4.0-10.0

[0032] Gd2O3 6.0-12.0

[0033] Y2O3 0.5-4.0

[0034] SiO2 0.1-4.0

[0035] ZnO 0.5-5.0

[0036] TiO2 0-5.0

[0037] Ta2O5 0-5.0

[0038] Preferably, the environmentally friendly high refractive index glass is characterized by comprising the following oxides in accordance with mass percentage (wt.%):

[0039]

[0040] The environmentally friendly high-refractive index glass of the present invention belongs to borate glass, wherein 1.35≤La2O3 / B2O3≤1.56 can obtain high-refractive index glass.

[0041] In the present invention, rare earth oxide ∑(La2O3+Nb2O5+Ta2O5+Gd2O3+Y2O3)≥60%,

[0042] In the present invention, B2O3 is a glass-forming oxide and a component of the glass skeleton. It is also a solvent for reducing the viscosity of the glass melt and a main component for increasing the refractive index of the glass. Boron oxide triangles [BO3] and boron oxide tetrahedrons [BO4] are structural components. Boron may exist in the form of triangles [BO3] or boron oxide tetrahedrons [BO4] under different conditions. Under high temperature melting conditions, it is generally difficult to form boron oxide tetrahedrons and can only exist in the form of trihedrons. However, at low temperatures, under certain conditions, B 3+ It has a tendency to capture free oxygen to form tetrahedrons, making the structure compact and increasing the low-temperature viscosity of the glass. However, due to its characteristics of reducing the viscosity of the glass at high temperatures and increasing the viscosity of the glass at low temperatures, its content range is also relatively small. The mass percentage (wt.%) of B2O3 is 27-35. When the content of B2O3 is lower than 27wt.%, it cannot play a role in increasing the refractive index of the glass, and at the same time it will reduce the chemical stability of the glass; when the content of B2O3 is greater than 35wt.%, it will reduce the expansion coefficient and mechanical strength of the glass, and at the same time increase the phase separation tendency of the glass.

[0043] La2O3 is a lanthanide rare earth oxide. 3+ The large ion radius and strong electric field produce a strong aggregation effect in the glass, which can significantly increase the refractive index of the glass. The mass percentage (wt.%) of La2O3 is 42-48, but when the La2O3 content is greater than 48wt%, the thermal expansion coefficient of the glass will increase, and at the same time, the crystallization tendency of the glass will increase.

[0044] Nb2O5 is also a rare earth oxide, which can increase the refractive index of glass and improve the chemical resistance of glass. The mass percentage (wt.%) of Nb2O5 is 4.0-10.0. However, when the Nb2O5 content is greater than 10.0wt.%, the density and thermal expansion coefficient of the glass will increase, and the crystallization tendency of the glass will also increase.

[0045] Gd2O3 is also a rare earth oxide that can increase the mass of cations, increase the refractive index of glass, and improve the chemical stability of glass. The mass percentage of Gd2O3 is 6.0-12.0%, but when the Gd2O3 content is greater than 12.0wt.%, the density and thermal expansion coefficient of the glass will increase, and the crystallization tendency of the glass will also increase.

[0046] Y2O3 is a rare earth oxide that can reduce the thermal expansion coefficient and softening point of glass, improve the chemical resistance of glass, and effectively reduce the crystallization of glass and reduce the melting temperature. The mass percentage (wt.%) of Y2O3 is 0.5-4.0. If the content of Y2O3 is less than 0.5wt.%, it will not improve the chemical resistance of glass; if the content of Y2O3 is greater than 4.0wt.%, it will increase the tendency of glass to crystallize.

[0047] SiO2 is a glass-forming oxide. The mass percentage (wt.%) of SiO2 is 0.1-4.0. SiO2 can reduce the thermal expansion coefficient of glass, improve the thermal stability, chemical stability, mechanical strength, etc. of the glass. However, a content higher than 4.0wt.% will increase the melting temperature of the glass. A small amount can effectively improve the chemical resistance and mechanical strength of the glass.

[0048] ZnO is a glass intermediate oxide. It usually exists as a network exosome in the form of [ZnO6] octahedron. When there is enough free oxygen in the glass, it can also enter the glass network structure in the form of [ZnO4] tetrahedron. The mass percentage (wt.%) of ZnO is 0.5-5.0. When the content of ZnO is lower than 0.5wt.%, it cannot play a solubilizing role and will reduce the chemical stability of the glass. When the content of ZnO is higher than 5.0wt.%, the expansion coefficient of the glass will be increased and the phase separation tendency of the glass will be increased.

[0049] TiO2 mainly acts as a stabilizer, which can improve the refractive index, mechanical strength and chemical stability of glass and reduce the melting temperature of glass. The mass percentage (wt.%) of TiO2 is 0-5.0. When the TiO2 content is higher than 5.0wt.%, it will increase the crystallization tendency of glass.

[0050] Ta2O5 is also a component that improves the chemical resistance and refractive index of glass. The mass percentage (wt.%) of Ta2O5 is 0-5.0. If its content exceeds 5.0wt.%, the crystallization tendency of glass will increase.

[0051] The environmentally friendly high refractive index glass described in the present invention is characterized in that it does not substantially contain any of alkali metal and alkaline earth metal oxides, where the alkali metal oxide refers to any of Li2O, Na2O, K2O, Rb2O, Cs2O, Fr2O, etc.; the alkaline earth metal oxide refers to any of MgO, CaO, SrO, BaO, etc.

[0052] According to the requirements of environmentally friendly materials, especially the requirements for the properties of high-refractive-index glass used in wearable devices, communications, microelectronics, etc., one type of environmentally friendly high-refractive-index glass of the present invention is a borate glass that does not contain alkali metal oxides and alkaline earth metal oxides. The glass has the characteristics of high refractive index and does not contain any heavy metal oxides harmful to the environment, such as As2O3, Sb2O5, BaO, PbO, Tl2O, CdO, BeO, V2O5, etc. Even if it contains a very small amount, it is due to other glass raw materials.

[0053] Furthermore, the environmentally friendly high-refractive index glass is characterized in that the refractive index of the glass is greater than 1.76.

[0054] Furthermore, the environmentally friendly high-refractive index glass provided by the present invention has good chemical stability and mechanical strength in the use environment.

[0055] The parameters, measuring methods and instruments for the environmentally friendly high refractive index glass of the present invention are as follows. Table 1 lists in detail the glass chemical composition (wt.%) and glass properties of the embodiment.

[0056] (1) Refractive index n D [Refractive index of glass at λ = 589.3 nm];

[0057] (3) Thermal expansion coefficient α 30 / 300 The average thermal expansion coefficient α is 30-300℃ 30 / 300 [10 -7 / ℃].

[0058] Among them, the samples were subjected to various physical and chemical performance tests after surface grinding and polishing according to the test requirements; the refractive index of the glass n D The linear expansion coefficient at 30-300°C is measured by a horizontal expansion meter and is expressed as the average linear expansion coefficient using the method specified in ISO 7991.

[0059] Table 1 Chemical composition (wt.%) and glass properties of the examples

[0060]

[0061]

[0062] The following are the raw materials used in the examples and their requirements:

[0063] Boric acid or boric anhydride (400μm sieve material is less than 10%, 63μm sieve material is less than 10%), lanthanum oxide (analytical grade), niobium oxide (analytical grade), gadolinium oxide (analytical grade), yttrium oxide (analytical grade), quartz sand (high purity, 150μm sieve material is less than 1%, 45μm sieve material is less than 30%, Fe2O3 content is less than 0.01wt.%), zinc oxide (analytical grade), titanium oxide (analytical grade), tantalum oxide (analytical grade).

[0064] Example 1

[0065] First, the raw materials are selected according to the glass composition of Example 1 in Table 1, and the content of alkali metal and alkaline earth metal in the glass raw materials is strictly controlled so that the ingredients meet the glass chemical composition of Table 1. Then, after the glass batch materials are melted into a homogeneous glass melt, the glass melt is poured into a preheated heat-resistant steel mold with a size of 70 mm×70 mm×10 mm for casting and then annealing. Its test properties are shown in Table 1. (1) The average linear expansion coefficient at 30-300°C is 65×10 -7 / ℃; (2) The refractive index of glass is 1.79.

[0066] Example 2

[0067] The raw materials are selected according to the glass composition of Example 2 in Table 1, and the content of alkali metals and alkaline earth metals in the glass raw materials is strictly controlled so that the ingredients meet the glass chemical composition of Table 1. Then, after the glass batch materials are melted into a homogeneous glass melt, the glass melt is poured into a preheated heat-resistant steel mold with a size of 70mm×70mm×10mm for casting and then annealing. The basic properties of the samples are shown in Table 1. (1) The average linear expansion coefficient at 30-300℃ is 75×10 -7 / ℃; (2) The refractive index of glass is 1.78.

[0068] Example 3

[0069] The raw materials are selected according to the glass composition of Example 3 in Table 1, and the content of alkali metals and alkaline earth metals in the glass raw materials is strictly controlled so that the ingredients meet the glass chemical composition of Table 1. Then, after the glass batch materials are melted into a homogeneous glass melt, the glass melt is poured into a preheated heat-resistant steel mold with a size of 70mm×70mm×10mm for casting and then annealing. The basic properties of the samples are shown in Table 1. (1) The average linear expansion coefficient at 30-300℃ is 70×10 -7 / ℃; (2) The refractive index of glass is 1.96.

[0070] Example 4

[0071] The raw materials are selected according to the glass composition of Example 4 in Table 1, and the content of alkali metal and alkaline earth metal in the glass raw materials is strictly controlled so that the ingredients meet the glass chemical composition of Table 1. The same melting process system and test conditions as Example 1 are used. The basic properties of the samples are shown in Table 1. (1) Average linear expansion coefficient at 30-300°C 69×10 -7 / ℃; (2) The refractive index of glass is 1.89.

[0072] Example 5

[0073] The raw materials are selected according to the glass composition of Example 5 in Table 1, and the content of alkali metal and alkaline earth metal in the glass raw materials is strictly controlled so that the ingredients meet the glass chemical composition of Table 1. The same melting process system and test conditions as those of Example 1 are used. The basic properties of the samples are shown in Table 1. (1) Average linear expansion coefficient at 30-300°C 73×10 -7 / ℃; (2) The refractive index of glass is 1.82.

[0074] From the data obtained in the examples, it can be seen that the environmentally friendly high-refractive index glass of the present invention has the advantages of being free of harmful heavy metals, having a high refractive index, having good chemical stability and mechanical strength, and is suitable for use in the field of augmented reality (AR) equipment.

[0075] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. The protection scope of the present invention is defined by the claims. Those skilled in the art may make any modification or equivalent substitution, improvement, etc. to the present invention within the essence and protection scope of the present invention, and such modification or equivalent substitution is also deemed to fall within the protection scope of the present invention.

Claims

1. An environmentally friendly high refractive index glass, characterized in that: The invention comprises the following oxides prepared in accordance with mass percentage:

2. The environmentally friendly high refractive index glass according to claim 1, characterized in that: Preferably, the following oxides are prepared according to mass percentage:

3. The environmentally friendly high refractive index glass according to claim 1 or 2, characterized in that: The glass composition has a high refractive index when it satisfies 1.35≤La2O3 / B2O3≤1.

56.

4. The environmentally friendly high refractive index glass according to claim 1 or 2, characterized in that: The rare earth oxide ∑(La2O3+Nb2O5+Ta2O5+Gd2O3+Y2O3) in the glass composition is ≥60%.

5. The environmentally friendly high refractive index glass according to claim 1 or 2, characterized in that: The refractive index of the glass is greater than 1.76, and it has good chemical stability and mechanical strength in the use environment.

6. The environmentally friendly high refractive index glass according to claim 1 or 2, characterized in that: It does not contain substantially any metal oxides harmful to the environment, such as As2O3, Sb2O5, BaO, PbO, Tl2O, CdO, BeO, V2O5, etc.

7. The environmentally friendly high refractive index glass according to claim 1 or 2, characterized in that: It does not substantially contain any alkali metal or alkaline earth metal oxide, where the alkali metal oxide refers to any one of Li2O, Na2O, K2O, Rb2O, Cs2O, Fr2O, etc.; and the alkaline earth metal oxide refers to any one of MgO, CaO, SrO, BaO, etc.

8. An application of the environmentally friendly high refractive index glass according to claim 1 or 2, characterized in that: The environmentally friendly high-refractive index glass can be used in a wearable vision-based augmented reality device, and can also be used to manufacture lenses, prisms, optical fibers, optical windows, and optical components made of environmentally friendly high-refractive index glass. The optical components can be used in digital projection, photography, printing, wafers, and optical devices of computer integrated circuits, and can also be used in optical communications, information transmission, and optical lighting.

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