Protective glass and reinforced protective glass

Abstract

The invention provides a protective glass and a reinforced protective glass with excellent irradiation stability. The protective glass comprises the following components in percentage by weight: 50.0 to 70.0 percent of SiO2; 3.0% to 30.0% of B2O3; 3.0 to 20.0 percent of Al2O3 (aluminum oxide); na2O: 3.0 to 20.0% of Na2O: 3.0 to 20.0%; 1.0 to 15.0 percent of K2O; 1.0 to 7.0 percent of CeO2; 0.1 to 5.0 percent of TeO2 (TeO2); and 0.5 to 10.0 percent of P2O5. Through reasonable component design, the obtained protective glass has excellent irradiation stability and is suitable for chemical strengthening, the strengthened protective glass prepared through chemical strengthening has excellent irradiation stability and high bending strength, space rays can be effectively protected, the thickness of the protective glass for space equipment can be reduced, and the service life of the protective glass is prolonged. And miniaturization and light weight of space equipment are realized.

Description

Technical Field

[0001] This invention relates to a protective glass, and more particularly to a protective glass with excellent radiation stability and a reinforced protective glass. Background Technology

[0002] Solar protective glass effectively blocks high-energy particles and rays from space from affecting spacecraft and solar cells, protecting solar cells from space ion radiation. Therefore, solar protective glass is a crucial guarantee for the energy supply of space equipment. Current solar protective glass technologies suffer from poor radiation stability and low bending strength. To prevent breakage during processing and use, the glass used in space equipment is relatively thick and cannot be processed into curved surfaces, resulting in larger equipment sizes and increased launch and maintenance costs. Therefore, improving the bending strength and radiation stability of protective glass can reduce its thickness, which is of great significance for the miniaturization and weight reduction of space equipment. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a protective glass with excellent radiation stability and a reinforced protective glass.

[0004] The technical solution adopted by this invention to solve the technical problem is:

[0005] The protective glass, with its components expressed as a weight percentage, contains: SiO2: 50.0–70.0%; B2O3: 3.0–30.0%; Al2O3: 3.0–20.0%; Na2O: 3.0–20.0%; K2O: 1.0–15.0%; CeO2: 1.0–7.0%; TeO2: 0.1–5.0%; P2O5: 0.5–10.0%.

[0006] Furthermore, the protective glass, in terms of its composition by weight percentage, also contains: Li₂O: 0–10.0%; and / or MO: 0–10.0%; and / or ZrO₂: 0–10.0%; and / or Sb₂O₃: 0–2.0%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

[0007] The protective glass, whose composition is expressed as a weight percentage, consists of SiO2: 50.0–70.0%; B2O3: 3.0–30.0%; Al2O3: 3.0–20.0%; Na2O: 3.0–20.0%; K2O: 1.0–15.0%; CeO2: 1.0–7.0%; TeO2: 0.1–5.0%; P2O5: 0.5–10.0%; Li2O: 0–10.0%; MO: 0–10.0%; ZrO2: 0–10.0%; and Sb2O3: 0–2.0%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

[0008] Furthermore, the protective glass, whose components are expressed as weight percentages, satisfies one or more of the following three conditions:

[0009] 1) The ratio of (B2O3+SiO2) / Al2O3 is 3.0 to 12.0, preferably 3.0 to 10.0, more preferably 3.0 to 9.0, and even more preferably 4.0 to 9.0;

[0010] 2) The ratio of (Li2O+Na2O) / K2O is 1.0 to 6.0, preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.5 to 4.0;

[0011] 3) The CeO2 / TeO2 ratio is 5.0 to 20.0, preferably 5.0 to 18.0, more preferably 5.0 to 15.0, and even more preferably 8.0 to 15.0.

[0012] Furthermore, the protective glass comprises, by weight percentage: SiO2: 55.0–70.0%, preferably SiO2: 55.0–67.0%, more preferably SiO2: 55.0–65.0%; and / or B2O3: 3.0–25.0%, preferably B2O3: 3.0–20.0%, more preferably B2O3: 4.0–13.0%; and / or Al2O3: 3.0–18.0%, preferably Al2O3: 5.0–18.0%, more preferably Al2O3: 7.0–16.0%; and / or Na2O: 3.0–18.0%, preferably Na2O: 3.0–16.0%, more preferably Na2O: 7.0–16.0%; and / or K2O: 3.0–15.0%, preferably K2O: 3.0–12.0%, more preferably K2O: 3.0–10.0%; and / or CeO2: 1.0–6.0%, preferably CeO2: 3.0–6.0%. 0%, more preferably CeO2: 4.0-5.0%; and / or TeO2: 0.1-4.0%, preferably TeO2: 0.1-2.0%, more preferably TeO2: 0.2-1.0%; and / or P2O5: 1.0-8.0%, preferably P2O5: 1.0-5.0%, more preferably P2O5: 1.0-3.0%; and / or Li2O: 0-8.0%, preferably Li2O: 0-3.0%; and / or MO: 0-8.0%. The preferred content of MO is 0-7.0%, more preferably 1.0-5.0%; and / or ZrO2 is 0-7.0%, preferably 1.0-7.0%, more preferably 3.0-7.0%; and / or Sb2O3 is 0.05-1.5%, preferably 0.1-1.0%, more preferably 0.2-0.5%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

[0013] Furthermore, the light transmittance τ of the protective glass in the range of 500–2000 nm is... 500～2000nm The content is 88% or more, preferably 90% or more, more preferably 92-92.5%; and / or the average irradiation stability Δτ at 500-2000 nm is 0.5% or less, preferably 0.3% or less, more preferably 0.2% or less; and / or the elastic modulus is 65 GPa or more, preferably 68 GPa or more, more preferably 70 GPa or more; and / or the density ρ is 2.70 g / cm³. 3 The preferred value is 2.60 g / cm³. 3 The following is more preferably 2.55 g / cm³. 3 the following.

[0014] Furthermore, the thickness of the protective glass is 0.05-0.5 mm, preferably 0.1-0.4 mm, and more preferably 0.1 mm, 0.2 mm, or 0.3 mm.

[0015] The reinforced protective glass contains, by weight percentage: SiO2: 50.0–70.0%; B2O3: 3.0–30.0%; Al2O3: 3.0–20.0%; Na2O: 3.0–20.0%; K2O: 1.0–15.0%; CeO2: 1.0–7.0%; TeO2: 0.1–5.0%; P2O5: 0.5–10.0%.

[0016] Furthermore, the reinforced protective glass, in terms of its components expressed as a weight percentage, also contains: Li₂O: 0–10.0%; and / or MO: 0–10.0%; and / or ZrO₂: 0–10.0%; and / or Sb₂O₃: 0–2.0%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

[0017] The reinforced protective glass comprises, by weight percentage, SiO2: 50.0–70.0%; B2O3: 3.0–30.0%; Al2O3: 3.0–20.0%; Na2O: 3.0–20.0%; K2O: 1.0–15.0%; CeO2: 1.0–7.0%; TeO2: 0.1–5.0%; P2O5: 0.5–10.0%; Li2O: 0–10.0%; MO: 0–10.0%; ZrO2: 0–10.0%; and Sb2O3: 0–2.0%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

[0018] Furthermore, the reinforced protective glass, whose components are expressed as weight percentages, satisfies one or more of the following three conditions:

[0019] 1) The ratio of (B2O3+SiO2) / Al2O3 is 3.0 to 12.0, preferably 3.0 to 10.0, more preferably 3.0 to 9.0, and even more preferably 4.0 to 9.0;

[0020] 2) The ratio of (Li2O+Na2O) / K2O is 1.0 to 6.0, preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.5 to 4.0;

[0021] 3) The CeO2 / TeO2 ratio is 5.0 to 20.0, preferably 5.0 to 18.0, more preferably 5.0 to 15.0, and even more preferably 8.0 to 15.0.

[0022] Furthermore, the reinforced protective glass comprises, by weight percentage: SiO2: 55.0–70.0%, preferably SiO2: 55.0–67.0%, more preferably SiO2: 55.0–65.0%; and / or B2O3: 3.0–25.0%, preferably B2O3: 3.0–20.0%, more preferably B2O3: 4.0–13.0%; and / or Al2O3: 3.0–18.0%, preferably Al2O3. Al₂O₃: 5.0–18.0%, more preferably Al₂O₃: 7.0–16.0%; and / or Na₂O: 3.0–18.0%, preferably Na₂O: 3.0–16.0%, more preferably Na₂O: 7.0–16.0%; and / or K₂O: 3.0–15.0%, preferably K₂O: 3.0–12.0%, more preferably K₂O: 3.0–10.0%; and / or CeO₂: 1.0–6.0%, preferably CeO₂: 3.0–6.0%. 0.0%, more preferably CeO2: 4.0-5.0%; and / or TeO2: 0.1-4.0%, preferably TeO2: 0.1-2.0%, more preferably TeO2: 0.2-1.0%; and / or P2O5: 1.0-8.0%, preferably P2O5: 1.0-5.0%, more preferably P2O5: 1.0-3.0%; and / or Li2O: 0-8.0%, preferably Li2O: 0-3.0%; and / or MO: 0-8.0%. The preferred content of MO is 0-7.0%, more preferably 1.0-5.0%; and / or ZrO2 is 0-7.0%, preferably 1.0-7.0%, more preferably 3.0-7.0%; and / or Sb2O3 is 0.05-1.5%, preferably 0.1-1.0%, more preferably 0.2-0.5%, wherein MO is one or more of MgO, CaO, SrO, BaO, and ZnO.

[0023] Furthermore, the light transmittance τ of the reinforced protective glass in the 500-2000 nm range... 500～2000nm The content is 88% or more, preferably 90% or more, more preferably 92-92.5%; and / or the average irradiation stability Δτ at 500-2000 nm is 0.5% or less, preferably 0.3% or less, more preferably 0.2% or less; and / or the elastic modulus is 65 GPa or more, preferably 68 GPa or more, more preferably 70 GPa or more; and / or the density ρ is 2.70 g / cm³. 3 The preferred value is 2.60 g / cm³.3 The following is more preferably 2.55 g / cm³. 3 The following are also true; and / or the flexural strength σ is 700 MPa or more, preferably 800 MPa or more, and more preferably 850 to 950 MPa.

[0024] Furthermore, the thickness of the reinforced protective glass is 0.05-0.5 mm, preferably 0.1-0.4 mm, and more preferably 0.1 mm, 0.2 mm, or 0.3 mm.

[0025] The glass component is made of the protective glass described above, or of the reinforced protective glass described above.

[0026] An apparatus comprising the aforementioned protective glass, or the aforementioned reinforced protective glass, or the aforementioned glass element.

[0027] The beneficial effects of this invention are: through reasonable component design, the protective glass obtained by this invention has excellent radiation stability; the protective glass of this invention is suitable for chemical strengthening, and the strengthened protective glass made by chemical strengthening has excellent radiation stability and high bending strength, which can effectively protect against space rays, and is conducive to reducing the thickness of protective glass for space equipment, realizing the miniaturization and weight reduction of space equipment. Detailed Implementation

[0028] The embodiments of the protective glass and strengthened protective glass of the present invention will now be described in detail. However, the present invention is not limited to the embodiments described below, and appropriate modifications can be made to implement it within the scope of the purpose of the present invention. Furthermore, while there are appropriate omissions in the repeated descriptions, this does not limit the spirit of the invention. In the present invention, unstrengthened glass is called protective glass (in this specification, protective glass can be simply referred to as glass); protective glass that has been chemically strengthened is called strengthened protective glass.

[0029] [Protective glass and tempered protective glass]

[0030] The component (composition) ranges of the protective glass and reinforced protective glass of the present invention are described below. In this invention, unless otherwise specified, the content, total content, and total amount of each component are expressed as a weight percentage (wt%), that is, the weight percentage of the content, total content, and total amount of each component relative to the total amount of glass material converted into oxide composition. Here, "converted into oxide composition" means that when the oxides, composite salts, and hydroxides used as raw materials for the protective glass or reinforced protective glass of the present invention decompose and transform into oxides upon melting, the total amount of such oxides is taken as 100%.

[0031] Unless otherwise specified in the specific context, the numerical ranges listed in this invention include upper and lower limits, and "above" and "below" include endpoint values ​​and all integers and fractions included in the range, but are not limited to the specific values ​​listed when the range is defined. The term "and / or" as used herein is inclusive; for example, "A and / or B" means only A, or only B, or both A and B.

[0032] <Essential and Optional Components>

[0033] SiO2, as a glass-forming component, forms the framework of glass and can improve its thermal stability, chemical stability, light transmittance, and elastic modulus, while reducing its refractive index. However, excessive SiO2 content increases the difficulty of glass melting and refining, resulting in a thinner ion exchange layer in the chemically strengthened protective glass. Therefore, the SiO2 content is 50.0%–70.0%, preferably 55.0%–70.0%, more preferably 55.0%–67.0%, and even more preferably 55.0%–65.0%.

[0034] B2O3, as a glass-forming agent, can improve the glass-forming properties of glass, reduce its coefficient of thermal expansion and density, and increase its elastic modulus, radiation protection capability, and flexural strength. However, if the B2O3 content is too high, the ultraviolet transmittance of the glass increases. Under prolonged ultraviolet radiation, the surface film of the solar panel reacts, resulting in reduced conversion efficiency and lifespan. It also deteriorates the chemical strengthening properties of the glass, leading to only a slight increase in the flexural strength of the strengthened protective glass. Furthermore, it reduces the visible light transmittance and worsens the thermal and chemical stability of the glass. Therefore, the B2O3 content is 3.0–30.0%, preferably 3.0–25.0%, more preferably 3.0–20.0%, and even more preferably 4.0–13.0%.

[0035] Al2O3, as an intermediate component in the glass network, can increase the stability of the glass network, improve the elastic modulus, enhance glass-forming properties, and also broaden the network spatial channels, increasing the Kc during glass chemical strengthening. + -Na + The ion exchange threshold increases the depth of the ion exchange layer, thereby significantly improving the bending strength of the strengthened protective glass. However, if the Al2O3 content is too high, it will increase the difficulty of melting the glass and reduce its light transmittance. Therefore, the Al2O3 content is 3.0–20.0%, preferably 3.0–18.0%, more preferably 5.0–18.0%, and even more preferably 7.0–16.0%.

[0036] Through extensive experimental research, the inventors discovered that in some embodiments, controlling the (B2O3+SiO2) / Al2O3 ratio within the range of 3.0 to 12.0 can improve the light transmittance and elastic modulus of protective and tempered protective glass, and is also beneficial for improving the bending strength of tempered protective glass. Therefore, it is preferable that the (B2O3+SiO2) / Al2O3 ratio is 3.0 to 12.0, more preferably 3.0 to 10.0, even more preferably 3.0 to 9.0, and still more preferably 4.0 to 9.0.

[0037] Na₂O is an essential component for ion exchange during the chemical strengthening of glass in this invention, through K... + -Na + Ion exchange creates compressive stress on the glass surface, forming reinforced protective glass with high bending strength. Na₂O also reduces the viscosity and density of the glass, making it easier to melt and clarify. However, excessive Na₂O content significantly reduces the glass's radiation stability, chemical stability, and elastic modulus. Therefore, the Na₂O content is 3.0–20.0%, preferably 3.0–18.0%, more preferably 3.0–16.0%, and even more preferably 7.0–16.0%.

[0038] K₂O can reduce the viscosity and density of glass, making it easier to melt and clarify. However, excessive K₂O content can adversely affect the chemical strengthening properties of glass, significantly reducing its radiation stability, chemical stability, and elastic modulus. Therefore, the K₂O content is 1.0–15.0%, preferably 3.0–15.0%, more preferably 3.0–12.0%, and even more preferably 3.0–10.0%.

[0039] Li2O can be converted by K + -Li + and / or Na + -Li + Ion exchange creates compressive stress on the glass surface, forming reinforced protective glass with higher bending strength. Li₂O also reduces the viscosity of the glass, making it easier to melt and clarify, and increasing its elastic modulus. However, excessive Li₂O content increases the ultraviolet transmittance of the glass. Under prolonged ultraviolet radiation, the surface film of the solar panel reacts, reducing conversion efficiency and lifespan. It also decreases the radiation stability and chemical stability of the glass. Therefore, the Li₂O content is 0–10.0%, preferably 0–8.0%, and more preferably 0–3.0%.

[0040] Through extensive experimental research, the inventors discovered that in some embodiments, controlling the (Li₂O+Na₂O) / K₂O ratio within the range of 1.0 to 6.0 can improve the light transmittance and elastic modulus of protective and tempered protective glass, and is also beneficial for improving the bending strength of tempered protective glass. Therefore, it is preferable that the (Li₂O+Na₂O) / K₂O ratio is 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and even more preferably 1.5 to 4.0.

[0041] MO (Mo is one or more of MgO, CaO, SrO, BaO, and ZnO) can improve the light transmittance, chemical stability, elastic modulus, and radiation protection capability of glass. However, if the MO content is too high, it will lead to an increase in the density of the glass and a decrease in its thermal stability. Therefore, the MO content is 0–10.0%, preferably 0–8.0%, more preferably 0–7.0%, and even more preferably 1.0–5.0%.

[0042] CeO2 possesses excellent radiation resistance, preventing a decrease in light transmittance of glass under cosmic ray irradiation, which could affect the performance of solar cells or imaging devices. It also shields against ultraviolet rays, reducing ultraviolet transmittance and preventing UV damage to the lifespan of solar cells or imaging devices. Furthermore, CeO2 is a good clarifying agent, helping to eliminate bubbles. However, excessive CeO2 content can significantly reduce the light transmittance of the glass. Therefore, the CeO2 content is 1.0–7.0%, preferably 1.0–6.0%, more preferably 3.0–6.0%, and even more preferably 4.0–5.0%.

[0043] TeO2 can improve the radiation protection capability and devitrification resistance of glass, increase the elastic modulus of glass, and is beneficial to improving the bending strength of reinforced protective glass. The combination of TeO2 and Sb2O3 in a certain proportion can effectively improve the light transmittance of CeO2-containing glass. However, if the TeO2 content is too high, the glass's resistance to electron radiation stability will significantly decrease. Therefore, the TeO2 content is 0.1–5.0%, preferably 0.1–4.0%, more preferably 0.1–2.0%, and even more preferably 0.2–1.0%.

[0044] In some embodiments, controlling the CeO2 / TeO2 ratio within the range of 5.0 to 20.0 can improve the visible light transmittance of protective and tempered protective glass and prevent its radiation stability from deteriorating. Therefore, a CeO2 / TeO2 ratio of 5.0 to 20.0 is preferred, more preferably 5.0 to 18.0, even more preferably 5.0 to 15.0, and still more preferably 8.0 to 15.0.

[0045] P2O5, as a network generator, can improve glass structure, increase light transmittance, and reduce glass density and refractive index. However, excessive P2O5 content reduces the depth of the ion exchange layer during glass chemical strengthening, resulting in decreased flexural strength of the strengthened protective glass. It also reduces the glass's radiation stability and elastic modulus. Therefore, the P2O5 content is 0.5–10.0%, preferably 1.0–8.0%, more preferably 1.0–5.0%, and even more preferably 1.0–3.0%.

[0046] ZrO2 can improve the chemical stability, elastic modulus, and radiation protection of glass, and reduce its coefficient of thermal expansion. However, if its content is too high, the glass will be difficult to melt, and its density and refractive index will increase. Therefore, the ZrO2 content is 0–10.0%, preferably 0–7.0%, more preferably 1.0–7.0%, and even more preferably 3.0–7.0%.

[0047] Sb₂O₃ is a good clarifying agent, facilitating the escape of gases from glass. When used in combination with TeO₂ in a certain proportion, it can effectively improve the light transmittance of CeO₂-containing glass. However, if the Sb₂O₃ content is too high, the radiation stability of the glass decreases. Therefore, the Sb₂O₃ content is 0–2.0%, preferably 0.05–1.5%, more preferably 0.1–1.0%, and even more preferably 0.2–0.5%.

[0048] The term "0%" as used herein means that the compound, molecule, or element was not intentionally added as a raw material to the protective glass and reinforced protective glass of this invention. However, as raw materials and / or equipment used in the production of protective glass and reinforced protective glass, there may be certain impurities or components that are not intentionally added, which may be present in small or trace amounts in the final protective glass and reinforced protective glass. Such cases are also within the scope of protection of this patent.

[0049] The performance of the protective glass and the reinforced protective glass of the present invention will now be described.

[0050] <Light transmittance>

[0051] Light transmittance (τ) of protective glass and reinforced protective glass500～2000nm The test shall be conducted in accordance with the method specified in the standard GB / T7962.12-2010.

[0052] <Radiation stability>

[0053] The radiation stability of protective glass and reinforced protective glass was tested according to the method specified in the standard "GJB 1976A-2021 Specification for Radiation-resistant Glass Covers for Space".

[0054] <Elastic Modulus>

[0055] The modulus of elasticity of protective glass and reinforced protective glass shall be tested according to the method specified in standard GB / T 7962.6-2010.

[0056] <Density>

[0057] The density (ρ) of protective glass and reinforced protective glass shall be tested in accordance with the method specified in standard GB / T7962.20-2010.

[0058] <Flexural Strength>

[0059] The bending strength (σ) of reinforced protective glass is tested according to the method specified in standard GJB 1976A-2021.

[0060] The protective glass of this invention has the following properties:

[0061] 1) In some embodiments, the light transmittance (τ) of the protective glass of the present invention with a thickness of less than 0.5 mm at 500–2000 nm is... 500～2000nm The content is 88% or more, preferably 90% or more, and more preferably 92-92.5%.

[0062] The thickness of the aforementioned protective glass is preferably 0.05 to 0.5 mm, more preferably 0.1 to 0.4 mm, and even more preferably 0.1 mm, 0.2 mm, or 0.3 mm.

[0063] 2) In some embodiments, the average irradiance stability (Δτ) of the protective glass of the present invention with a thickness of less than 0.5 mm at 500-2000 nm is less than 0.5%, preferably less than 0.3%, and more preferably less than 0.2%.

[0064] The thickness of the aforementioned protective glass is preferably 0.05 to 0.5 mm, more preferably 0.1 to 0.4 mm, and even more preferably 0.1 mm, 0.2 mm, or 0.3 mm.

[0065] 3) In some embodiments, the elastic modulus of the protective glass of the present invention is 65 GPa or higher, preferably 68 GPa or higher, and more preferably 70 GPa or higher. A higher elastic modulus of the protective glass helps reduce the difficulty of processing the glass into curved or other shapes.

[0066] 4) In some embodiments, the density (ρ) of the protective glass of the present invention is 2.70 g / cm³. 3 The preferred value is 2.60 g / cm³. 3 The following is more preferably 2.55 g / cm³. 3 the following.

[0067] The reinforced protective glass of this invention has the following properties:

[0068] 1) In some embodiments, the light transmittance (τ) of the reinforced protective glass of the present invention with a thickness of less than 0.5 mm at 500–2000 nm is... 500～2000nm The content is 88% or more, preferably 90% or more, and more preferably 92-92.5%.

[0069] The thickness of the aforementioned reinforced protective glass is preferably 0.05 to 0.5 mm, more preferably 0.1 to 0.4 mm, and even more preferably 0.1 mm, 0.2 mm, or 0.3 mm.

[0070] 2) In some embodiments, the average irradiation stability (Δτ) of the reinforced protective glass of the present invention with a thickness of less than 0.5 mm at 500–2000 nm is less than 0.5%, preferably less than 0.3%, and more preferably less than 0.2%.

[0071] The thickness of the aforementioned reinforced protective glass is preferably 0.05 to 0.5 mm, more preferably 0.1 to 0.4 mm, and even more preferably 0.1 mm, 0.2 mm, or 0.3 mm.

[0072] 3) In some embodiments, the elastic modulus of the reinforced protective glass of the present invention is 65 GPa or more, preferably 68 GPa or more, and more preferably 70 GPa or more.

[0073] 4) In some embodiments, the density (ρ) of the reinforced protective glass of the present invention is 2.70 g / cm³. 3 The preferred value is 2.60 g / cm³. 3 The following is more preferably 2.55 g / cm³. 3 the following.

[0074] 5) In some embodiments, the bending strength (σ) of the reinforced protective glass of the present invention with a thickness of less than 0.5 mm is 700 MPa or more, preferably 800 MPa or more, and more preferably 850 to 950 MPa.

[0075] The thickness of the aforementioned reinforced protective glass is preferably 0.05 to 0.5 mm, more preferably 0.1 to 0.4 mm, and even more preferably 0.1 mm, 0.2 mm, or 0.3 mm.

[0076] The protective glass and reinforced protective glass of this invention, due to their superior properties, can be used to manufacture glass components (such as protective glass sheets, protective glass covers, etc.). The glass components of this invention can have any useful shape or thickness. The protective glass, reinforced protective glass, and glass components of this invention can be widely used in various types of equipment, including but not limited to spacecraft, solar cells, and aircraft.

[0077] [Manufacturing methods for protective glass and tempered protective glass]

[0078] The manufacturing method of the protective glass and the tempered protective glass of the present invention is as follows:

[0079] Forming the protective glass: The protective glass of this invention is produced using conventional raw materials and processes, including but not limited to oxides, hydroxides, complex salts (such as carbonates, nitrates, sulfates, phosphates, metaphosphates, etc.), boric acid, etc. After being prepared according to conventional methods, the prepared furnace charge is placed in a melting furnace (such as a platinum or platinum alloy crucible) at 1200–1500°C for melting. After clarification and homogenization, a homogeneous molten glass without bubbles or undissolved substances is obtained. This molten glass is then cast in a mold and annealed. Those skilled in the art can appropriately select raw materials, process methods, and process parameters according to actual needs.

[0080] The protective glass of the present invention can also be formed by well-known methods. In some embodiments, the protective glass described herein can be manufactured into glass preforms by various processes, including but not limited to sheets, lenses, prisms, etc. These processes include, but are not limited to, slot drawing, float glass, roll forming, and other processes known in the art for forming sheets, lenses, and prisms. Alternatively, the protective glass can be formed by float glass or roll forming methods known in the art. The protective glass and glass preforms of the present invention can have any reasonably useful thickness, shape, or structure, such as 2D, 2.5D, or 3D.

[0081] The protective glass of the present invention can be manufactured into sheet glass preforms by methods such as grinding or polishing, but the method of manufacturing glass preforms is not limited to these methods.

[0082] Glass preforms can be manufactured from the protective glass using methods such as grinding, hot pressing, or precision stamping. Specifically, glass preforms can be manufactured by machining the protective glass, such as grinding and polishing; or by hot pressing a preform made from the protective glass for molding and then grinding it; or by precision stamping a preform made from a ground preform. It should be noted that the methods for preparing glass preforms are not limited to the methods described above.

[0083] The reinforced protective glass of this invention is obtained by chemically strengthening the protective glass or glass preform of this invention. The chemical strengthening process includes immersing the protective glass or glass preform in molten potassium salt, sodium salt, or a mixture of potassium and sodium salts at a specific temperature for a certain period of time. In some embodiments, the protective glass of this invention is processed into sheets of the required specifications, its surface is polished, and then it is immersed in a KNO3 and / or NaNO3 salt bath at 300–500°C for 2–5 hours to obtain the reinforced protective glass.

[0084] Example

[0085] To further illustrate and explain the technical solution of the present invention, the following non-limiting embodiments are provided.

[0086] <Example of Protective Glass>

[0087] In this embodiment, protective glass with the composition shown in Tables 1 to 3 was obtained using the above-described manufacturing method for protective glass. The characteristics of each glass were measured using the testing method described in this invention, and the measurement results are shown in Tables 1 to 3. In the following embodiments, the thickness of the test sample for the radiation stability and light transmittance of the protective glass was 0.2 mm.

[0088] Table 1.

[0089]

[0090]

[0091] Table 2.

[0092] Example (wt%) 6# 7# 8# 9# 10# <![CDATA[SiO2]]> 57.0 55.0 60.0 61.0 61.0 <![CDATA[B2O3]]> 5.0 11.0 4.5 4.0 4.0 CaO 0 1.0 0 0 0 BaO 0 0 0 0 0 MgO 1.0 0 0 0 0 SrO 0 0 0 0 0 ZnO 0 0 0 0 1.0 <![CDATA[Sb2O3]]> 0.4 0.2 0.3 0.2 0.4 <![CDATA[CeO2]]> 4.7 5.0 4.8 4.9 5.0 <![CDATA[Al2O3]]> 10.6 8.0 12.0 9.5 12.0 <![CDATA[ZrO2]]> 6.0 5.0 4.0 3.0 3.0 <![CDATA[TeO2]]> 0.3 0.6 0.4 0.4 0.6 <![CDATA[Li2O]]> 2.0 0 0 0 0 <![CDATA[Na2O]]> 8.0 9.0 9.5 11.5 8.0 <![CDATA[K2O]]> 4.0 4.2 3.5 4.5 3.0 <![CDATA[P2O5]]> 1.0 1.0 1.0 1.0 2.0 total 100.0 100.0 100.0 100.0 100.0 <![CDATA[(B2O3+SiO2) / Al2O3]]> 5.85 8.25 5.38 6.84 5.42 <![CDATA[CeO2 / TeO2]]> 15.67 8.33 12.00 12.25 8.33 <![CDATA[(Li2O+Na2O) / K2O]]> 2.50 2.14 2.71 2.56 2.67 <![CDATA[ρ(g / cm 3 )]]> 2.57 2.55 2.52 2.51 2.51 Elastic modulus (GPa) 74 75 73 69 73 <![CDATA[τ 500～2000nm (%)]]> 92.15 92.11 92.20 92.18 92.18 Δτ(%) 0.23 0.38 0.35 0.35 0.23

[0093] Table 3.

[0094] Example (wt%) 11# 12# 13# 14# 15# <![CDATA[SiO2]]> 62.0 63.0 57.2 55.0 55.4 <![CDATA[B2O3]]> 4.7 5.6 5.0 4.6 11.0 CaO 0 0 1.0 0 0 BaO 0 0 0 0 0 MgO 0 0 0 0 0 SrO 0 0 0 0 0 ZnO 0 0 0 2.0 0 <![CDATA[Sb2O3]]> 0.3 0.3 0.3 0.3 0.2 <![CDATA[CeO2]]> 4.7 4.6 4.9 4.7 4.9 <![CDATA[Al2O3]]> 8.0 8.0 13.0 14.0 8.0 <![CDATA[ZrO2]]> 5.0 5.0 3.0 7.0 4.0 <![CDATA[TeO2]]> 0.3 0.5 0.6 0.4 0.5 <![CDATA[Li2O]]> 0 0 0 0 0 <![CDATA[Na2O]]> 9.0 8.2 11.0 8.0 11.0 <![CDATA[K2O]]> 5.0 3.8 3.0 3.0 4.0 <![CDATA[P2O5]]> 1.0 1.0 1.0 1.0 1.0 total 100.0 100.0 100.0 100.0 100.0 <![CDATA[(B2O3+SiO2) / Al2O3]]> 8.34 8.58 4.78 4.26 8.30 <![CDATA[CeO2 / TeO2]]> 15.67 9.20 8.17 11.75 9.80 <![CDATA[(Li2O+Na2O) / K2O]]> 1.80 2.16 3.67 2.67 2.75 <![CDATA[ρ(g / cm 3 )]]> 2.52 2.53 2.52 2.57 2.52 Elastic modulus (GPa) 72 73 76 79 73 <![CDATA[τ 500～2000nm (%)]]> 92.20 92.21 92.15 92.17 92.10 Δτ(%) 0.25 0.28 0.37 0.11 0.35

[0095] <Example of reinforced protective glass>

[0096] In this embodiment, reinforced protective glass with the compositions shown in Tables 4 to 6 was obtained using the aforementioned manufacturing method. The characteristics of each reinforced protective glass were measured using the testing method described in this invention, and the results are presented in Tables 4 to 6. In the following embodiments, the thickness of the test samples for the radiation stability, light transmittance, and bending strength of the protective glass was 0.2 mm.

[0097] Table 4.

[0098]

[0099]

[0100] Table 5.

[0101]

[0102]

[0103] Table 6.

[0104]

[0105]

Claims

1. Safety glass, characterized in that components in weight percent, comprising: SiO2: 50.0-70.0%; B2O3: 3.0-30.0%; Al2O3: 3.0-20.0%; Na2O: 3.0-20.0%; K2O: 1.0-15.0%; CeO2: 1.0-7.0%; TeO2: 0.1-5.0%; P2O5: 0.5-10.0%.

2. The protective glass according to claim 1, characterized in that, components in weight percent, further comprising: Li2O: 0-10.0%; and / or MO: 0-10.0%; and / or ZrO2: 0-10.0%; and / or Sb2O3: 0-2.0%, the MO being one or more of MgO, CaO, SrO, BaO, ZnO.

3. Safety glass, characterized in that components in weight percent, comprising: SiO2: 50.0-70.0%; B2O3: 3.0-30.0%; Al2O3: 3.0-20.0%; Na2O: 3.0-20.0%; K2O: 1.0-15.0%; CeO2: 1.0-7.0%; TeO2: 0.1-5.0%; P2O5: 0.5-10.0%; Li2O: 0-10.0%; MO: 0-10.0%; ZrO2: 0-10.0%; Sb2O3: 0-2.0%, the MO being one or more of MgO, CaO, SrO, BaO, ZnO.

4. The protective glass according to any one of claims 1 to 3, characterized in that components in weight percent, satisfying one or more of the following 3 cases: 1) (B2O3 + SiO2) / Al2O3 is 3.0-12.0, preferably (B2O3 + SiO2) / Al2O3 is 3.0-10.0, more preferably (B2O3 + SiO2) / Al2O3 is 3.0-9.0, further preferably (B2O3 + SiO2) / Al2O3 is 4.0-9.0; 2) (Li2O + Na2O) / K2O is 1.0-6.0, preferably (Li2O + Na2O) / K2O is 1.0-5.0, more preferably (Li2O + Na2O) / K2O is 1.0-4.0, further preferably (Li2O + Na2O) / K2O is 1.5-4.0; 3) CeO2 / TeO2 is 5.0-20.0, preferably CeO2 / TeO2 is 5.0-18.0, more preferably CeO2 / TeO2 is 5.0-15.0, further preferably CeO2 / TeO2 is 8.0-15.

0.

5. The protective glass according to any one of claims 1 to 3, characterized in that its components are expressed in weight percent, wherein: SiO2: 55.0-70.0%, preferably SiO2: 55.0-67.0%, more preferably SiO2: 55.0-65.0%; and / or B2O3: 3.0-25.0%, preferably B2O3: 3.0-20.0%, more preferably B2O3: 4.0-13.0%; and / or Al2O3: 3.0-18.0%, preferably Al2O3: 5.0-18.0%, more preferably Al2O3: 7.0-16.0%; and / or Na2O: 3.0-18.0%, preferably Na2O: 3.0-16.0%, more preferably Na2O: 7.0-16.0%; and / or K2O: 3.0-15.0%, preferably K2O: 3.0-12.0%, more preferably K2O: 3.0-10.0%; and / or CeO2: 1.0-6.0%, preferably CeO2: 3.0-6.0%, more preferably CeO2: 4.0-5.0%; and / or TeO2: 0.1-4.0%, preferably TeO2: 0.1-2.0%, more preferably TeO2: 0.2-1.0%; and / or P2O5: 1.0-8.0%, preferably P2O5: 1.0-5.0%, more preferably P2O5: 1.0-3.0%; and / or Li2O: 0-8.0%, preferably Li2O: 0-3.0%; and / or MO: 0-8.0%, preferably MO: 0-7.0%, more preferably MO: 1.0-5.0%; and / or ZrO2: 0-7.0%, preferably ZrO2: 1.0-7.0%, more preferably ZrO2: 3.0-7.0%; and / or Sb2O3: 0.05-1.5%, preferably Sb2O3: 0.1-1.0%, more preferably Sb2O3: 0.2-0.5%, said MO being one or more of MgO, CaO, SrO, BaO, ZnO.

6. The protective glass according to any one of claims 1 to 3, characterized in that The light transmittance τ of the protective glass in the 500-2000 nm range 500～2000nm The content is 88% or more, preferably 90% or more, more preferably 92-92.5%; and / or the average irradiation stability Δτ at 500-2000 nm is 0.5% or less, preferably 0.3% or less, more preferably 0.2% or less; and / or the elastic modulus is 65 GPa or more, preferably 68 GPa or more, more preferably 70 GPa or more; and / or the density ρ is 2.70 g / cm³. 3 The preferred value is 2.60 g / cm³. 3 The following is more preferably 2.55 g / cm³. 3 the following.

7. The cover glass of claim 6, wherein, The thickness of the protective glass is 0.05-0.5 mm, preferably 0.1-0.4 mm, more preferably 0.1 mm or 0.2 mm or 0.3 mm.

8. Safety glass, characterized in that its components are expressed in weight percent, and contain: SiO2: 50.0-70.0%; B2O3: 3.0-30.0%; Al2O3: 3.0-20.0%; Na2O: 3.0-20.0%; K2O: 1.0-15.0%; CeO2: 1.0-7.0%; TeO2: 0.1-5.0%; P2O5: 0.5-10.0%.

9. The strengthened glass of claim 8, wherein, its components are expressed in weight percent, and contain: SiO2: 50.0-70.0%; B2O3: 3.0-30.0%; Al2O3: 3.0-20.0%; Na2O: 3.0-20.0%; K2O: 1.0-15.0%; CeO2: 1.0-7.0%; TeO2: 0.1-5.0%; P2O5: 0.5-10.0%. its components are expressed in weight percent, and contain: SiO2: 50.0-70.0%; B2O3: 3.0-30.0%; Al2O3: 3.0-20.0%; Na2O: 3.0-20.0%; K2O: 1.0-15.0%; CeO2: 1.0-7.0%; TeO2: 0.1-5.0%; P2O5: 0.5-10.0%.

10. Safety glass, characterized in that The components thereof are represented by weight percentage, consisting of SiO2: 50.0-70.0%; B2O3: 3.0-30.0%; Al2O3: 3.0-20.0%; Na2O: 3.0-20.0%; K2O: 1.0-15.0%; CeO2: 1.0-7.0%; TeO2: 0.1-5.0%; P2O5: 0.5-10.0%; Li2O: 0-10.0%; MO: 0-10.0%; ZrO2: 0-10.0%; Sb2O3: 0-2.0%, wherein the MO is one or more of MgO, CaO, SrO, BaO, ZnO.

11. The strengthened glass of any of claims 8-10, wherein, The components thereof are represented by weight percentage, satisfying one or more of the following three situations: 1) (B2O3+SiO2) / Al2O3 is 3.0-12.0, preferably (B2O3+SiO2) / Al2O3 is 3.0-10.0, more preferably (B2O3+SiO2) / Al2O3 is 3.0-9.0, further preferably (B2O3+SiO2) / Al2O3 is 4.0-9.0; 2) (Li2O+Na2O) / K2O is 1.0-6.0, preferably (Li2O+Na2O) / K2O is 1.0-5.0, more preferably (Li2O+Na2O) / K2O is 1.0-4.0, further preferably (Li2O+Na2O) / K2O is 1.5-4.0; 3) CeO2 / TeO2 is 5.0-20.0, preferably CeO2 / TeO2 is 5.0-18.0, more preferably CeO2 / TeO2 is 5.0-15.0, further preferably CeO2 / TeO2 is 8.0-15.

0.

12. The strengthened glass of any of claims 8-10, wherein, its components are expressed in weight percent, wherein: SiO2: 55.0-70.0%, preferably SiO2: 55.0-67.0%, more preferably SiO2: 55.0-65.0%; and / or B2O3: 3.0-25.0%, preferably B2O3: 3.0-20.0%, more preferably B2O3: 4.0-13.0%; and / or Al2O3: 3.0-18.0%, preferably Al2O3: 5.0-18.0%, more preferably Al2O3: 7.0-16.0%; and / or Na2O: 3.0-18.0%, preferably Na2O: 3.0-16.0%, more preferably Na2O: 7.0-16.0%; and / or K2O: 3.0-15.0%, preferably K2O: 3.0-12.0%, more preferably K2O: 3.0-10.0%; and / or CeO2: 1.0-6.0%, preferably CeO2: 3.0-6.0%, more preferably CeO2: 4.0-5.0%; and / or TeO2: 0.1-4.0%, preferably TeO2: 0.1-2.0%, more preferably TeO2: 0.2-1.0%; and / or P2O5: 1.0-8.0%, preferably P2O5: 1.0-5.0%, more preferably P2O5: 1.0-3.0%; and / or Li2O: 0-8.0%, preferably Li2O: 0-3.0%; and / or MO: 0-8.0%, preferably MO: 0-7.0%, more preferably MO: 1.0-5.0%; and / or ZrO2: 0-7.0%, preferably ZrO2: 1.0-7.0%, more preferably ZrO2: 3.0-7.0%; and / or Sb2O3: 0.05-1.5%, preferably Sb2O3: 0.1-1.0%, more preferably Sb2O3: 0.2-0.5%, said MO being one or more of MgO, CaO, SrO, BaO, ZnO.

13. The strengthened glass of any of claims 8-10, wherein, The light transmittance τ of the strengthened glass in the range of 500 to 2,000 nm 500～2000nm is 88% or more, preferably 90% or more, and more preferably 92 to 92.5%; and / or the average irradiation stability Δτ in the range of 500 to 2,000 nm is 0.5% or less, preferably 0.3% or less, and more preferably 0.2% or less; and / or the elastic modulus is 65 GPa or more, preferably 68 GPa or more, and more preferably 70 GPa or more; and / or the density ρ is 2.70 g / cm 3 or more, preferably 2.65 g / cm 3 or more, and more preferably 2.60 g / cm 3 or more; and / or the bending strength σ is 700 MPa or more, preferably 800 MPa or more, and more preferably 850 to 950 MPa.

14. The strengthened glass of claim 13, wherein, The thickness of the strengthened protective glass is 0.05-0.5 mm, preferably 0.1-0.4 mm, more preferably 0.1 mm or 0.2 mm or 0.3 mm.

15. A glass element characterized by, made of the protective glass according to any one of claims 1-7, or made of the strengthened protective glass according to any one of claims 8-14.

16. An apparatus, comprising: containing the protective glass according to any one of claims 1-7, or containing the strengthened protective glass according to any one of claims 8-14, or containing the glass element according to claim 15.

Images