Anti-halation material, anti-halation microcrystalline glass, anti-halation reinforced microcrystalline glass, and preparation method and application of anti-halation material, anti-halation microcrystalline glass and anti-halation reinforced microcrystalline glass

Abstract

The invention discloses an anti-halation material, anti-halation microcrystalline glass, anti-halation reinforced microcrystalline glass and a preparation method and application thereof.The anti-halation microcrystalline glass comprises a glass body and a surface blackening layer, the thickness of the blackening layer is 0.15-0.35 mm, the average spectrum transmittance of the blackening layer within the wavelength range of 380-780 nm is smaller than or equal to 1%, and the average light transmittance of the glass body is gt; 92%, and the maximum light transmittance gt; the preparation method comprises the following steps: melting the glass substrate, performing hydrogen reduction to form the blackened layer, and performing crystallization heat treatment. By optimizing the components and the process, after the glass is chemically strengthened, the bending strength is larger than or equal to 700 MPa, the falling ball impact height is larger than or equal to 1.3 m, and the falling heights of 80-mesh abrasive paper and 180-mesh abrasive paper are larger than or equal to 1.3 m / 1.6 m respectively. The anti-halation glass solves the technical problem that the existing anti-halation glass is difficult to give consideration to high light transmittance and high strength, and is suitable for optical windows in the fields of optical devices, display equipment and photovoltaics.

Description

Technical Field

[0001] The present invention belongs to the field of glass-ceramics, and particularly relates to an anti-halation material, an anti-halation glass-ceramic, an anti-halation strengthened glass-ceramic, and their preparation methods and applications. Background Art

[0002] Anti-halation glass is a special type of glass, which is coated with a black glass layer of a certain thickness on its periphery, namely the blackening layer. This blackening layer is formed by high-temperature reduction treatment of the surface of the glass substrate, enabling the glass material to eliminate stray light and prevent halation. However, with the development of technology, higher requirements are put forward for the performance of anti-halation glass. It not only needs to have a good anti-halation effect, but also needs to take into account high light transmittance and high mechanical strength.

[0003] Existing technologies are difficult to meet the above multi-faceted requirements simultaneously. Therefore, it is necessary to explore a new type of high-strength anti-halation glass-ceramic material. Glass-ceramics have high light transmittance like glass and high strength like ceramics by precipitating crystalline phases inside the glass. Their mechanical properties, thermal properties, etc. are superior to those of ordinary glass. The crystalline phases in the above-mentioned glass-ceramics can hinder the propagation path of microcracks, thereby improving the scratch resistance, impact resistance, drop resistance, etc. of the glass. Summary of the Invention

[0004] In order to improve the above problems, the present invention has developed an anti-halation glass-ceramic with high light transmittance, high strength, excellent impact resistance and drop resistance, and further enhanced its mechanical properties through chemical strengthening, so as to meet the urgent needs of the future optical material field for high-performance anti-halation glass. The present invention provides an anti-halation material, an anti-halation glass-ceramic, an anti-halation strengthened glass-ceramic, and their preparation methods and applications. The specific technical solutions are as follows: The first technical solution provided by the present invention is: an anti-halation material, the components of which are expressed in weight percentages and contain: SiO2: 42 - 75%, Al2O3: 2 - 12%, P2O5: 0.5 - 5%, Na2O: 0 - 15%, Li2O: 0 - 20%, CaO: 0 - 6%, K2O: 0 - 5%, ZrO2: 0.1 - 10% and oxides that can generate color centers: 0.1 - 5%.

[0005] Furthermore, the oxides that can generate color centers are one or more of Bi2O3, PbO, Sb2O3, and As2O3.

[0006] The second technical solution provided by the present invention is as follows: an anti-halation microcrystalline glass, the components of which are expressed in weight percentages and contain: SiO2: 42-75%, Al2O3: 2-12%, P2O5: 0.5-5%, Na2O: 0-15%, Li2O: 0-20%, CaO: 0-6%, K2O: 0-5%, ZrO2: 0.1-10% and oxides capable of generating color centers: 0.1-5%. Its overall crystallinity is greater than or equal to 40wt%, and the main crystal phases are lithium disilicate and lithium metasilicate.

[0007] Further, the oxides capable of generating color centers are one or more of Bi2O3, PbO, Sb2O3, and As2O3.

[0008] The anti-halation microcrystalline glass includes a glass body and a blackening layer covering the surface of the glass body. The thickness of the blackening layer is 0.15-0.35 mm, and the average spectral transmittance of the blackening layer at 380 nm-780 nm is as low as 1%.

[0009] The average spectral transmittance of this glass in the wavelength range of 380 nm to 780 nm is greater than 92%, and the maximum average spectral transmittance is greater than 93.0%.

[0010] The preparation method of the aforementioned anti-halation microcrystalline glass includes the following steps: Step 1: Prepare glass raw materials according to the mass ratio of SiO2: 42-75%, Al2O3: 2-12%, P2O5: 0.5-5%, Na2O: 0-15%, Li2O: 0-20%, CaO: 0-6%, K2O: 0-5%, ZrO2: 0.1-10% and oxides capable of generating color centers: 0.1-5%. Melt the glass, then cool it and form it in a graphite mold, and perform annealing treatment to obtain an anti-halation glass substrate. Step 2: Perform a reduction treatment on the glass substrate in an H2 atmosphere. The reduction temperature is 550-680 °C, the reduction pressure is 0.01-0.5 MPa, and the reduction time is 4-30 h to form a blackening layer. Step 3: Heat-treat the glass material obtained in Step 2. The heat treatment process is to heat it to a temperature of 500-680 °C at a heating rate of 1-3 °C / min, hold it for 2-5 hours for nucleation; heat the nucleated glass to a temperature of 680-780 °C, hold it for 1-4 hours for crystallization to obtain the anti-halation microcrystalline glass.

[0011] The third technical solution provided by the present invention is: an anti-halation strengthened glass-ceramics, the components of which are expressed in weight percentages and contain: SiO2: 42-75%, Al2O3: 2-12%, P2O5: 0.5-5%, Na2O: 0-15%, Li2O: 0-20%, CaO: 0-6%, K2O: 0-5%, ZrO2: 0.1-10% and oxides capable of generating color centers: 0.1-5%. Its crystallinity is greater than or equal to 40wt%, the main crystal phases are lithium disilicate and lithium metasilicate, its flexural strength is 740-860 Mpa, the drop ball height is 1.3-1.5 meters, the drop height on 80-mesh sandpaper is ≥1.3 m, and the drop height on 180-mesh sandpaper is ≥1.6 m.

[0012] The anti-halation strengthened glass-ceramics includes a glass body and a blackening layer covering the surface of the glass body. The thickness of the blackening layer is 0.15-0.35 mm, and the average spectral transmittance of the blackening layer at 380 nm-780 nm is as low as 1%.

[0013] The average spectral transmittance of the anti-halation strengthened glass-ceramics in the wavelength range of 380 nm to 780 nm is greater than 92%, and the maximum average spectral transmittance is greater than 93.0%.

[0014] The oxides capable of generating color centers are one or more of Bi2O3, PbO, Sb2O3, and As2O3.

[0015] The preparation method of the aforementioned anti-halation strengthened glass-ceramics includes the following steps: Step 1: Prepare glass raw materials according to the mass ratio of SiO2: 42-75%, Al2O3: 2-12%, P2O5: 0.5-5%, Na2O: 0-15%, Li2O: 0-20%, CaO: 0-6%, K2O: 0-5%, ZrO2: 0.1-10% and oxides capable of generating color centers: 0.1-5%. Melt the glass, then cool and form it in a graphite mold, and perform annealing treatment to obtain an anti-halation glass substrate. Step 2: Perform a reduction treatment on the glass substrate in an H2 atmosphere by heating it to 550-680 °C and holding it for 4-30 h to form a blackening layer. Step 3: Heat-treat the glass material obtained in Step 2. The heat-treatment process is to heat it to a temperature of 500-680 °C at a heating rate of 1-3 °C / min and hold it for 2-5 hours for nucleation; heat the nucleated glass to a temperature of 680-780 °C and hold it for 1-4 hours for crystallization to obtain anti-halation glass-ceramics. Step 4: Chemically strengthen the glass material prepared in Step 3. The strengthening treatment is carried out by ion exchange strengthening with molten sodium nitrate / potassium nitrate mixed salt, and the strengthening treatment is carried out at 400-500 °C for 2-8 h to obtain anti-halation strengthened glass-ceramics.

[0016] The fourth technical solution provided by the present invention is: An anti-halation material product is prepared by processing the aforementioned anti-halation material, anti-halation glass-ceramics or anti-halation strengthened glass-ceramics, and is used for optical devices, display devices or optical input windows or industrial windows in the photovoltaic field.

[0017] Furthermore, the blackening layers on the upper and lower surfaces of the aforementioned anti-halation glass-ceramics or anti-halation strengthened glass-ceramics can be processed to remove the blackening layers on the upper and lower surfaces. At the same time, the blackening layers on the inclined surfaces, stepped surfaces and cylindrical surfaces are ground and polished to remove the reduction layer, exposing the transparent glass part, but the reduction layer on the remaining surfaces is retained to obtain the final product.

[0018] In the present invention, the formation mechanism of the blackening layer of the anti-halation glass-ceramics or anti-halation strengthened glass-ceramics is that oxides such as Bi2O3, PbO, Sb2O3, As2O3, etc. doped in the glass that can generate color centers undergo reduction reactions in hydrogen: taking Bi2O3 as an example, Bi2O3 + 3H2 → 2Bi 0 + 3H2O, and part of Bi 0 is further oxidized to BiO x , Bi 0 and BiO x nanoparticles are formed on the glass surface to form a dense blackening layer. The formation mechanism of the blackening layers of other oxides (PbO, Sb2O3, As2O3, etc.) is similar to the above.

[0019] In the present invention, the selection and function of the glass composition have an important influence on the performance of the high-strength anti-halation glass-ceramics material. A suitable composition ratio can enable the glass material described in the present invention to meet higher usage requirements on the premise of ensuring mechanical properties and chemical stability.

[0020] SiO2 (silicon dioxide) is one of the main components of glass and plays a role in forming the glass network structure. It can significantly improve the mechanical strength and chemical stability of glass. When combined with other metal oxides, it forms a dense glass film, thereby reducing light reflection and scattering and effectively reducing the halation phenomenon. SiO2 can endow glass with good corrosion resistance and high-temperature stability, and can extend the service life of blackened layer glass. In the embodiments of the present invention, the content of SiO2 is 42 - 75% by mass. In some embodiments of the present invention, the content of SiO2 by mass can also be selected from the following ranges or ranges composed of any values between the following ranges or be any value in the following ranges: 45 - 65%, 50 - 65%, 45 - 60%, 55 - 75%, 58 - 72%, etc. In some preferred embodiments of the present invention, the content of SiO2 is 55 - 75% by mass, preferably 58 - 73%.

[0021] Al2O3 (aluminum oxide) is an intermediate oxide of glass and can significantly improve the mechanical properties and thermal stability of glass. An appropriate amount of Al2O3 can enhance the wear resistance and scratch resistance of glass and at the same time help reduce light reflection. In the embodiments of the present invention, the content of Al2O3 is 2 - 12% by mass. The content of Al2O3 by mass can also be selected from the following ranges or ranges composed of any values between the following ranges or be any value in the following ranges: 8 - 12%, 3 - 10%, 2 - 10%, 5 - 10%, 4 - 12%, etc. In some preferred embodiments of the present invention, the content of Al2O3 is 3 - 10% by mass, preferably 4 - 9%.

[0022] Color center oxides such as Bi2O3 (bismuth oxide), PbO (lead oxide), Sb2O3 (antimony oxide), As2O3 (arsenic oxide), etc. have relatively high refractive indices and low dispersions and are an ideal optical material. They can be reduced to metal nanoparticles at high temperatures to form a dense blackened layer with a thickness of greater than or equal to 0.2 mm. Bi2O3, PbO, Sb2O3, As2O3, etc. are used in combination with other oxides to optimize the transparency and optical properties of glass. In the embodiments of the present invention, the content of Bi2O3, PbO, Sb2O3, As2O3, etc. is 0.1 - 5% by mass. By mass, it can also be selected from the following ranges or ranges composed of any values between the following ranges or be any value in the following ranges: 0.1 - 4.5%, 0.1 - 4%, 0.15 - 4%, 0.2 - 3.5%, 0.1 - 3%, etc. In some preferred embodiments of the present invention, the content is 0.2 - 4% by mass, preferably 0.2 - 3%.

[0023] P2O5 (phosphorus pentoxide) not only plays an important role as a network former but also plays an important role in the nucleation process. The presence of P2O5 can refine the crystal grain size and improve the uniformity of crystal distribution. The synergistic effect of P2O5 and Li2O further reduces the melting temperature of the glass and promotes the nucleation process. In the embodiments of the present invention, the content of P2O5 is 0.5 - 5% by mass. The content of P2O5 by mass can also be selected from the following ranges or ranges composed of any values between the following ranges or be any value in the following ranges: 0.5 - 4.5%, 0.5 - 4%, 1 - 4%, 0.8 - 3.5%, 1 - 3%, and so on. In some preferred embodiments of the present invention, the content of P2O5 is 1 - 4.5% by mass, preferably 2 - 4%.

[0024] CaO (calcium oxide) is a network modifier oxide. While assisting in optical design, it can increase the refractive index and mechanical strength of the glass and reduce the thermal expansion coefficient of the glass. During the chemical strengthening process (ion exchange), the presence of CaO can provide more channels for ion diffusion, thus accelerating the ion exchange reaction. This reaction usually forms a compressive stress layer on the glass surface, further enhancing its mechanical properties. In the embodiments of the present invention, the content of CaO is 0 - 6% by mass. The content of CaO by mass can also be selected from the following ranges or ranges composed of any values between the following ranges or be any value in the following ranges: 0.2 - 5%, 0.5 - 5.5%, 0.5 - 4.5%, 0.5 - 4%, 0.5 - 3.2%, and so on. In some preferred embodiments of the present invention, the content of CaO is 0.5 - 4% by mass, preferably 0.5 - 3.2%.

[0025] Li2O (lithium oxide) and Na2O (sodium oxide) are basic oxides. They can significantly reduce the melting temperature and slightly adjust the overall refractive index, but introducing an excessive amount will reduce the chemical stability. Li + / Na + is also an important condition for chemical strengthening and can improve the surface hardness. In the embodiments of the present invention, the content of Li2O is 0 - 20% by mass. The content of Li2O by mass can also be selected from the following ranges or ranges composed of any values between the following ranges or be any value in the following ranges: 2 - 20%, 1 - 15%, 4 - 15%, 2 - 18%, 3 - 17%, and so on. In some preferred embodiments of the present invention, the content of Li2O is 4 - 18% by mass, preferably 6 - 15%.

[0026] In an embodiment of the present invention, the content of Na2O is 0-15% by mass percentage. The content of Na2O by mass percentage can also be selected from the following ranges or ranges composed of any values between the following ranges or any value in the following ranges: 10-15%, 1-10%, 5-14%, 2-12%, 0-8%, etc. In some preferred embodiments of the present invention, the content of Na2O is 0-10% by mass percentage, preferably 0-8%.

[0027] K2O (potassium oxide) is an alkali metal oxide with a large ionic radius. It has special function regulation, can reduce the thermal expansion coefficient, and at the same time can reduce the refractive index fluctuation in the micro-region caused by the migration of alkali metals. In an embodiment of the present invention, the content of K2O is 0-5% by mass percentage. The content of K2O by mass percentage can also be selected from the following ranges or ranges composed of any values between the following ranges or any value in the following ranges: 0-4%, 0.5-3%, 2-4%, 2-5%, 1.5-4.5%, etc. In some preferred embodiments of the present invention, the content of K2O is 0-4% by mass percentage, preferably 0-3%.

[0028] ZrO2 (zirconia), as a nucleating agent, can promote the uniform precipitation of crystals. At the same time, as a high-refractive-index oxide, it can assist the reduced oxide to optimize the optical properties. It has a low thermal expansion coefficient, good high-temperature resistance, and can improve the thermal stability and chemical stability of the glass. In an embodiment of the present invention, the content of ZrO2 is 0.1-10% by mass percentage. The content of ZrO2 by mass percentage can also be selected from the following ranges or ranges composed of any values between the following ranges or any value in the following ranges: 0.5-5%, 0.5-8%, 1-6%, 1.6-9%, 2-9%, etc. In some preferred embodiments of the present invention, the content of ZrO2 is 2-9% by mass percentage, preferably 4-9%.

[0029] In some embodiments of the present invention, by mass percentage, the anti-halation glass material / anti-halation glass-ceramics / anti-halation toughened glass comprises the following components: 50-75% of SiO2, 2-10% of Al2O3, 1-4% of P2O5, 0-10% of Na2O, 5-18% of Li2O, 0.5-5% of CaO, 0-3% of K2O, 2-9% of ZrO2, and 0.5-4% of oxides that can generate color centers (one or more of Bi2O3, PbO, Sb2O3, As2O3, etc.).

[0030] In some embodiments of the present invention, by mass percentage, the anti-halation glass material / anti-halation glass-ceramics / anti-halation toughened glass comprises the following components: 45-74% of SiO2, 2-10% of Al2O3, 0.5-4% of P2O5, 0-12% of Na2O, 2-16% of Li2O, 1-5% of CaO, 0-3% of K2O, 3-10% of ZrO2, and 0.1-3% of oxides that can generate color centers (one or more of Bi2O3, PbO, Sb2O3, As2O3, etc.).

[0031] In some embodiments of the present invention, by mass percentage, the anti-halation glass material / anti-halation glass-ceramics / anti-halation toughened glass comprises the following components: 48-75% of SiO2, 3-11% of Al2O3, 0.5-4% of P2O5, 1-10% of Na2O, 2-16% of Li2O, 0-4% of CaO, 0-3% of K2O, 4-10% of ZrO2, and 0.1-4.5% of oxides that can generate color centers (one or more of Bi2O3, PbO, Sb2O3, As2O3, etc.).

[0032] In some embodiments of the present invention, by mass percentage, the anti-halation glass material / anti-halation glass-ceramics / anti-halation toughened glass comprises the following components: 50-75% of SiO2, 2-10% of Al2O3, 1-4.5% of P2O5, 0-8% of Na2O, 4-18% of Li2O, 0-4% of CaO, 0-3.5% of K2O, 3-9% of ZrO2, and 0.5-4.5% of oxides that can generate color centers (one or more of Bi2O3, PbO, Sb2O3, As2O3, etc.).

[0033] In some embodiments of the present invention, by mass percentage, the anti-halation glass material / anti-halation glass-ceramics / anti-halation toughened glass comprises the following components: 42-75% of SiO2, 2-12% of Al2O3, 0.5-5% of P2O5, 0-15% of Na2O, 0-20% of Li2O, 0-6% of CaO, 0-5% of K2O, 0.1-10% of ZrO2, and 0.1-5% of oxides that can generate color centers (one or more of Bi2O3, PbO, Sb2O3, As2O3, etc.).

[0034] In some embodiments of the present invention, the anti-halation glass product prepared from the anti-halation glass material / anti-halation glass-ceramics / anti-halation toughened glass according to the present invention has good transmittance, and its average spectral transmittance in the wavelength range of 380 nm - 780 nm is greater than 92%, and the maximum average spectral transmittance is greater than 93.0%.

[0035] In some embodiments of the present invention, for the anti-halation glass material / anti-halation glass-ceramics / anti-halation toughened glass according to the present invention, the thickness range of the blackening layer is 0.15 - 0.35 mm, and the average spectral transmittance of the blackening layer in the range of 380 nm - 780 nm can be as low as 0.18%. Specifically, in some embodiments, the average spectral transmittance of the blackening layer in the range of 380 nm - 780 nm is in the range of 0.01 - 1%.

[0036] In some embodiments of the present invention, the anti-halation toughened glass of the present invention has a flexural strength ≥ 700 MPa. In some embodiments of the present invention, the flexural strength of the glass material after chemical strengthening is 700 - 780 MPa.

[0037] In some embodiments of the present invention, for the anti-halation toughened glass of the present invention, the test height of a 1 mm glass and a falling ball (150 g steel ball) is ≥ 1.3 m, and preferably the falling ball test height is 1.5 m. In some specific embodiments, after the glass material is impacted by a falling ball at 1.5 m, the glass sheet does not break or crack.

[0038] In some embodiments of the present invention, the falling test height of 80-mesh sandpaper is ≥ 1.3 m, and preferably the falling ball test height is 1.8 m; the falling test height of 180-mesh sandpaper is ≥ 1.6 m, and preferably the falling ball test height is 1.8 m. In some specific embodiments, after the glass material is dropped from a height of 1.8 m (80 mesh / 180 mesh), it does not break.

[0039] In some embodiments of the present invention, the anti-halation glass material / anti-halation glass-ceramics / anti-halation toughened glass and products thereof can be applied to optical input windows in optical devices, electronic devices and industrial windows, which can significantly improve the imaging quality and optical performance of the devices and meet the requirements of modern society for high-precision and high-reliability optical systems.

[0040] For all the specific technical features described in all embodiments in the above aspects of the present invention, without contradiction, they can be combined in any suitable way. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0041] Unless otherwise specified, the numerical ranges described in the present invention include all the numerical values within this range, and include the range values composed of any two numerical values within this range. For example, for 1 - 3.2%, this numerical range includes all the numerical values between 1 and 3.2%, and includes any several numerical values within this range (for example: 1%, 1.6%, 2.8%) and the range values that may be composed of them (such as 1 - 1.3%, 1 - 2.5%, 2 - 3.2%); different numerical values of the same index that appear in all embodiments of the present invention can be arbitrarily combined to form range values.

[0042] Compared with the prior art, the present invention provides an anti-halation material, an anti-halation glass-ceramics, an anti-halation strengthened glass-ceramics, and their preparation methods and applications, having the following beneficial effects: The glass material has good transmittance, and its average spectral transmittance in the wavelength range of 380nm - 780nm is greater than 92%, and the maximum average spectral transmittance is greater than 93.0%. The average spectral transmittance of the blackening layer in the range of 380nm - 780nm can be as low as 1%. Moreover, the flexural strength of the glass material provided by the present invention is ≥700MPa, the impact height of the falling ball (150g steel ball) is ≥1.3m, the falling test height of 80-mesh sandpaper is ≥1.3m, and the falling test height of 180-mesh sandpaper is ≥1.6m. The glass material has excellent mechanical strength and optical properties, and can be applied to high-precision optical imaging, display devices and the photovoltaic field, and can meet the requirements of high-quality optical input devices. Description of the Drawings

[0043] Figure 1 It is the XRD pattern of the crystals of the anti-halation strengthened glass-ceramics prepared in Example 2 of the present invention; Figure 2 It is the crystal morphology diagram of the anti-halation strengthened glass-ceramics prepared in Example 2 of the present invention; Figure 3 It is the test result diagram of the transmittance of the glass materials of Examples 1 - 5 and Comparative Examples 1 - 4; Figure 4 It is the physical photo of the anti-halation strengthened glass-ceramics prepared in Example 2 of the present invention. Detailed Embodiments

[0044] In order to better understand the technical solution of the present invention, the above content of the present invention will be further described in detail through specific embodiments in the form of examples. However, it should not be understood that the scope of the above-mentioned subject matter of the present invention is limited to the following examples. All technologies implemented based on the above content of the present invention belong to the scope of the present invention. Example 1

[0045] To prepare an anti-halation strengthened glass-ceramics, raw materials are weighed by mass percentage: SiO2 65.0%, Al2O3 6.5%, P2O5 3.2%, CaO 2.5%, Li2O 10.0%, Na2O 1.5%, K2O 0.2%, ZrO2 7.0%, Bi2O3 1.5%, PbO 1.2%, Sb2O3 0.8%, As2O3 0.6%. First, the raw materials are mixed and melted at 1500 °C for 6 hours, then injected into a graphite mold preheated to 480 °C for shaping, and annealed at 500 °C for 4 hours. Next, hydrogen reduction treatment is carried out on the glass substrate: heated to 570 °C in an H2 atmosphere, the reduction pressure is 0.2 MPa, and kept warm for 18 hours to form a blackened layer. Subsequently, it is heated to 580 °C at a rate of 2 °C / min for nucleation for 3 hours, and then heated to 690 °C for crystallization for 2 hours. Then, a mixed molten salt of sodium nitrate / potassium nitrate is used for ion exchange at 480 °C for 5 hours for chemical strengthening. Finally, the blackened layers on the upper and lower surfaces of the glass formed body are processed to remove the blackened layers on the upper and lower surfaces, and at the same time, the blackened layers on the inclined surfaces, stepped surfaces and cylindrical surfaces are ground and polished to remove the reduction layer, exposing the transparent glass part, but retaining the reduction layer on the remaining surfaces, thus obtaining the anti-halation strengthened glass-ceramics. Example 2

[0046] To prepare an anti-halation strengthened glass-ceramics, by mass percentage, the glass raw material composition is: SiO2 67.8%, Al2O3 5.8%, P2O5 4.1%, CaO 1.6%, Li2O 12.0%, Na2O 0.5%, K2O 0.0%, ZrO2 7.8%, Bi2O3 0.2%, PbO 0.0%, Sb2O3 0.2%, As2O3 0.0%. The melting process is the same as that in Example 1; in the hydrogen reduction process, the hydrogen reduction temperature is 590 °C, the reduction pressure is 0.2 MPa, and the reduction time is 6 hours; in the heat treatment stage, the nucleation temperature is 550 °C and kept warm for 2 hours; the crystallization temperature is 710 °C and kept warm for 2 hours; the chemical strengthening condition is treatment in a mixed molten salt of sodium nitrate / potassium nitrate at 480 °C for 6 hours. The XRD, crystal phase diagram and physical photos of the final product obtained are respectively as Figure 1 、 Figure 2 and Figure 4 shown. Example 3

[0047] Prepare an anti-halation strengthened glass-ceramics. In terms of mass percentage, the glass raw material composition is as follows: SiO2 60.0%, Al2O3 8.0%, P2O5 2.5%, CaO 3.4%, Li2O 4.5%, Na2O 5.8%, K2O 3.1%, ZrO2 10%, Bi2O3 1.1%, PbO 1.2%, Sb2O3 0.0%, As2O3 0.4%. The melting process is the same as that in Example 1; in the hydrogen reduction process, the hydrogen reduction temperature is 620 °C, the reduction pressure is 0.2 MPa, and the reduction time is 12 hours; in the heat treatment stage, the nucleation temperature is 610 °C and the heat preservation time is 4 hours; the crystallization temperature is 710 °C and the heat preservation time is 3 hours; the chemical strengthening condition is to treat in a sodium nitrate / potassium nitrate mixed molten salt at 460 °C for 8 hours. Example 4

[0048] In terms of mass percentage, the glass raw material composition is as follows: SiO2 52.0%, Al2O3 8.4%, P2O5 5.0%, CaO 5.4%, Li2O 5.8%, Na2O 12.0%, K2O 2.7%, ZrO2 7.2%, Bi2O3 0.5%, PbO 0.7%, Sb2O3 0.2%, As2O3 0.1%. The melting process is the same as that in Example 1; in the hydrogen reduction process, the hydrogen reduction temperature is 600 °C, the reduction pressure is 0.2 MPa, and the reduction time is 15 hours; in the heat treatment stage, the nucleation temperature is 600 °C and the heat preservation time is 2.5 hours; the crystallization temperature is 740 °C and the heat preservation time is 1.5 hours; the chemical strengthening condition is to treat in a sodium nitrate / potassium nitrate mixed molten salt at 460 °C for 8 hours. Example 5

[0049] The glass raw material composition and melting process of Example 5 are the same as those of Example 2. Subsequently, heat treatment is first carried out: heat up to 550 °C at a rate of 2 °C / min for nucleation for 2 hours, and then heat up to 710 °C for crystallization for 2 hours. Subsequently, reduction treatment is carried out at 590 °C in a hydrogen atmosphere for 6 hours (the reduction pressure is 0.2 MPa). The chemical strengthening process is the same as that of Example 2.

[0050] Comparative Example 1 In terms of mass percentage, the glass raw material composition is as follows: SiO2 62.8%, Al2O3 4.8%, P2O5 5.1%, CaO 1.3%, Li2O 11.3%, Na2O 0.2%, K2O 0.4%, ZrO2 8.2%, Bi2O3 2.2%, PbO 1.5%, Sb2O3 1.6%, As2O3 0.6%. The melting process is the same as that of Example 1; in the hydrogen reduction process, the hydrogen reduction temperature is 580 °C, the reduction pressure is 0.2 MPa, and the reduction time is 12 hours; in the heat treatment stage, the nucleation temperature is 550 °C (holding for 3 hours), and the crystallization temperature is 740 °C (holding for 2.5 hours); the chemical strengthening condition is treatment in a mixed molten salt of sodium nitrate / potassium nitrate at 470 °C for 7 hours.

[0051] Comparative Example 2 In terms of mass percentage, the glass raw material composition is as follows: SiO2 67.0%, Al2O3 4.2%, P2O5 1.3%, CaO 10.0%, Li2O 0.0%, Na2O 14.0%, K2O 0.8%, ZrO2 2.1%, Bi2O3 0.3%, PbO 0.1%, Sb2O3 0.2%, As2O3 0.0%. The melting process is the same as that of Example 1; in the hydrogen reduction process, the hydrogen reduction temperature is 600 °C, the reduction pressure is 0.2 MPa, and the reduction time is 12 hours; in the heat treatment stage, the nucleation temperature is 570 °C (holding for 3 hours), and the crystallization temperature is 700 °C (holding for 2 hours); the chemical strengthening condition is treatment in a mixed molten salt of sodium nitrate / potassium nitrate at 480 °C for 4 hours.

[0052] Comparative Example 3 The glass raw material composition, melting process, hydrogen reduction process, and heat treatment process of Comparative Example 3 are the same as those of Example 2, and no chemical strengthening treatment is carried out.

[0053] Comparative Example 4 The glass raw material composition, melting process, hydrogen reduction process, and chemical strengthening process of Comparative Example 3 are the same as those of Example 2, and no crystallization treatment is carried out.

[0054] The following performance tests are carried out on Examples 1-5 and Comparative Examples 1-4: Use a high-precision spectral haze meter HAM-300 to measure the average transmittance of the obtained products at a wavelength of 380-780 nm.

[0055] After the tested glass samples are processed and polished, use a four-point bending testing machine to measure the bending strength of the products. The processing size of the test samples is 150 mm × 70 mm × 1 mm.

[0056] The impact resistance of the product is tested using a falling ball testing machine; specifically, the product is placed on a mold, and a 150 g steel ball is dropped from a specified height, and the maximum falling ball height that the product can withstand without breaking is measured; more specifically, the test is carried out starting from a height of 30 cm, dropping from the center point, increasing by 10 cm each time until the product breaks.

[0057] 4. 80 - mesh sandpaper drop test: The drop resistance of the product is characterized by the sandpaper drop value. The product is subjected to a surface drop test of 80 - mesh silicon carbide sandpaper using a drop testing machine to evaluate its drop resistance. The test conditions are as follows: 80 - mesh sandpaper, a total weight of 210 g (referring to the total mass of the chemically strengthened glass and the mobile phone model), a base height of 50 cm, increasing by 10 cm each time, dropping once at each height until the product breaks, and recording the breaking height.

[0058] Table 1 Composition, content and physical properties of the products of Examples 1 - 5 and Comparative Examples 1 - 4 of the present invention

[0059] As can be seen from Table 1, in Examples 1 - 4 of the present invention, through the processes of hydrogen reduction first and then heat treatment, combined with chemical strengthening, the thickness of the blackening layer of the anti - halation microcrystalline glass is controlled within 0.15 - 0.35 mm, the average transmittance of the transparent area is higher than 92%, the transmittance of the blackening area is lower than 1%, the bending strength exceeds 700 MPa, the falling ball impact height ≥ 1.3 m, the 80 - mesh sandpaper drop test height ≥ 1.3 m, and the 180 - mesh sandpaper drop test height ≥ 1.6 m. Comparing Example 5 with Example 2, adopting the process of heat treatment first and then hydrogen reduction, the test performance results are similar to those of Example 2. For the anti - halation microcrystalline glass of Comparative Examples 1 - 2, the transmittance of the transparent area is lower than 91%, and the transmittance of the blackening area is as high as more than 5.62%, and the mechanical properties are significantly deteriorated. In Comparative Example 3, the strengthening process is reduced based on Example 2, and there are obvious disadvantages in bending strength, falling ball and dropping. In Comparative Example 4, the crystallization process is reduced based on Example 2, and the impact resistance and drop resistance are also significantly reduced. The examples of the present invention are significantly superior to the comparative examples in terms of optical uniformity and mechanical strength. The transmittance test results of the glasses prepared in Examples 1 - 5 and Comparative Examples 1 - 4 Figure 3 are shown.

Claims

1. An anti-halation material, characterized in that, Its components are expressed in weight percentages and contain: SiO2: 42 - 75%, Al2O3: 2 - 12%, P2O5: 0.5 - 5%, Na2O: 0 - 15%, Li2O: 0 - 20%, CaO: 0 - 6%, K2O: 0 - 5%, ZrO2: 0.1 - 10% and oxides capable of generating color centers: 0.1 - 5%.

2. The antihalation material according to claim 1, wherein The oxides capable of generating color centers are one or more of Bi2O3, PbO, Sb2O3, and As2O3.

3. A light-shielding glass-ceramics, characterized in that, Its components are expressed in weight percentages and contain: SiO2: 42 - 75%, Al2O3: 2 - 12%, P2O5: 0.5 - 5%, Na2O: 0 - 15%, Li2O: 0 - 20%, CaO: 0 - 6%, K2O: 0 - 5%, ZrO2: 0.1 - 10% and oxides capable of generating color centers: 0.1 - 5%, its crystallinity is ≥ 40 wt%, and the main crystal phases are lithium disilicate and lithium metasilicate.

4. The anti-halation glass-ceramics according to claim 3, characterized in that, The oxides capable of generating color centers are one or more of Bi2O3, PbO, Sb2O3, and As2O3.

5. A method for preparing the anti-halation glass-ceramics according to claim 3 or 4, characterized in that, It includes the following steps: Step 1: Prepare glass raw materials according to the mass ratio of SiO2: 42 - 75%, Al2O3: 2 - 12%, P2O5: 0.5 - 5%, Na2O: 0 - 15%, Li2O: 0 - 20%, CaO: 0 - 6%, K2O: 0 - 5%, ZrO2: 0.1 - 10% and oxides capable of generating color centers: 0.1 - 5%, melt the glass, then cool and form it in a graphite mold, and perform annealing treatment to obtain an anti-halation glass substrate; Step 2: Perform a reduction treatment on the glass substrate in an H2 atmosphere. The reduction temperature is 550 - 680 °C, the reduction pressure is 0.01 - 0.5 MPa, and the reduction time is 4 - 30 h to form a blackened layer; Step 3: Heat-treat the glass material obtained in Step 2. The heat-treatment process is to heat it to a temperature of 500 - 680 °C at a heating rate of 1 - 3 °C / min, hold for 2 - 5 hours for nucleation; heat the nucleated glass to a temperature of 680 - 780 °C, hold for 1 - 4 hours for crystallization to obtain an anti-halation glass-ceramic.

6. An anti-halation reinforced glass-ceramics, characterized in that, Its components are expressed in weight percentages and contain: SiO2: 42 - 75%, Al2O3: 2 - 12%, P2O5: 0.5 - 5%, Na2O: 0 - 15%, Li2O: 0 - 20%, CaO: 0 - 6%, K2O: 0 - 5%, ZrO2: 0.1 - 10% and oxides capable of generating color centers: 0.1 - 5%, its crystallinity is, the main crystal phases are lithium disilicate and lithium metasilicate, its flexural strength is 740 - 860 Mpa, the drop ball height is 1.3 - 1.5 m, the drop height on 80 - mesh sandpaper is ≥ 1.3 m, and the drop height on 180 - mesh sandpaper is ≥ 1.6 m.

7. The anti-halation enhanced glass-ceramics according to claim 6, wherein The oxides capable of generating color centers are one or more of Bi2O3, PbO, Sb2O3, and As2O3.

8. A method for preparing an anti-halation reinforced glass-ceramics as claimed in claim 6 or 7, characterized in that, It includes the following steps: Step 1: Prepare glass raw materials according to the mass ratio of SiO2: 42 - 75%, Al2O3: 2 - 12%, P2O5: 0.5 - 5%, Na2O: 0 - 15%, Li2O: 0 - 20%, CaO: 0 - 6%, K2O: 0 - 5%, ZrO2: 0.1 - 10% and oxides capable of generating color centers: 0.1 - 5%. Melt the glass, then cool and form it in a graphite mold, and perform annealing treatment to obtain an anti-halation glass substrate; Step 2: Perform a reduction treatment on the glass substrate in an H2 atmosphere by heating it to 550 - 680 °C and holding for 4 - 30 h to form a blackened layer; Step 3: Heat-treat the glass material obtained in Step 2. The heat-treatment process is to heat it to a temperature of 500 - 680 °C at a heating rate of 1 - 3 °C / min and hold for 2 - 5 hours for nucleation; heat the nucleated glass to a temperature of 680 - 780 °C and hold for 1 - 4 hours for crystallization to obtain an anti-halation microcrystalline glass; Step 4: Perform chemical strengthening treatment on the glass material obtained in Step 3. The strengthening treatment uses a molten sodium nitrate / potassium nitrate mixed salt for ion-exchange strengthening, and perform the strengthening treatment at 400 - 500 °C for 2 - 8 h to obtain an anti-halation strengthened microcrystalline glass.

9. An anti-halation material product, characterized in that, It is obtained by processing the product described in Claim 1 or Claim 3 or Claim 6 and is used for optical devices, display devices, or optical input windows or industrial windows in the photovoltaic field.

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